JP2021070766A - Adhesive composition, laminate and production method thereof, production method of electronic component, and polymer - Google Patents

Abstract

To provide: an adhesive composition for bonding a support and a substrate together, where the adhesive composition can form an adhesive layer with heat resistance and excellent adhesion to the substrate or support; a laminate based on the same and a production method thereof; a production method of an electronic component; and a polymer for use in the adhesive composition.SOLUTION: An adhesive composition for bonding a support and a substrate together contains a polymer (P1) having a constitutional unit (p1) represented by the general formula (p1-1) in the figure. In the formula, Ru11 to Ru14 each independently represent a C1-30 organic group or a hydrogen atom, provided that at least one of Ru11 to Ru14 is an organic group including an alkoxysilyl group; and n1 is an integer from 0 to 2.SELECTED DRAWING: None

Description

The present invention relates to an adhesive composition, a laminate and a method for producing the same, a method for producing an electronic component, and a polymer.

The semiconductor package (electronic component) including the semiconductor element has various forms depending on the corresponding size, and includes, for example, WLP (Wafer Level Package), PLP (Panel Level Package) and the like.
Examples of semiconductor package technology include fan-in type technology and fan-out type technology. As a semiconductor package based on the fan-in type technology, a fan-in type WLP (Fan-in Wafer Level Package) or the like in which the terminals at the end of the bare chip are rearranged in the chip area is known. As a semiconductor package based on the fan-out type technology, a fan-out type WLP (Fan-out Wafer Level Package) or the like in which the terminals are rearranged outside the chip area is known.

In recent years, in particular, fan-out type technology has been applied to fan-out type PLP (Fan-out Panel Level Package) in which semiconductor elements are arranged and packaged on a panel. It is attracting attention as a method that can realize thinning and miniaturization.

In order to reduce the size of the semiconductor package, it is important to reduce the thickness of the substrate in the element to be incorporated. However, if the thickness of the substrate is reduced, the strength of the substrate is reduced, and the substrate is liable to be damaged during the manufacture of the semiconductor package. On the other hand, a laminated body in which a support is attached to a substrate is adopted.

Here, when the substrate and the support are bonded to each other, an adhesive containing a polymer having a cycloolefin structure has been widely used because of its excellent light transmittance.
Patent Document 1 discloses an adhesive composition containing a polymer having a cycloolefin structure and a (meth) acrylate monomer compatible with the polymer.

Japanese Unexamined Patent Publication No. 2014-105316

By the way, in the manufacture of a semiconductor package, a substrate and a support are bonded together with an adhesive, and then high-temperature treatment such as sealing, thin film formation, and firing is performed. In the conventional adhesive composition, due to the influence of the high temperature treatment as described above, for example, the position of the substrate may shift before and after the sealing operation. Although it is conceivable to use a high temperature resistant adhesive composition, the high temperature resistant adhesive composition may not have sufficient adhesion to the substrate or the support.

The present invention has been made in view of the above circumstances, is an adhesive composition for adhering a support and a substrate, has heat resistance, and has excellent adhesion to the substrate or the support. It is an object of the present invention to provide an adhesive composition capable of forming an adhesive layer, a laminate using the same, a method for producing the same, a method for producing an electronic component, and a polymer used for the adhesive composition.

In order to solve the above problems, the present invention has adopted the following configuration.
That is, the first aspect of the present invention is an adhesive composition for bonding a support and a substrate, and a polymer having a structural unit (p1) represented by the following general formula (p1-1) (p1). An adhesive composition containing P1).

［式中、Ｒ^ｕ１１〜Ｒ^ｕ１４は、それぞれ独立に、炭素数１〜３０の有機基又は水素原子を表す。但し、Ｒ^ｕ１１〜Ｒ^ｕ１４の少なくとも１つは、アルコキシシリル基を含む有機基である。ｎ^１は、０〜２の整数である。］

[In the formula, R ^{u11 to} R ^u14 independently represent an organic group or a hydrogen atom having 1 to 30 carbon atoms. However, ^{at least one of Ru11 to Ru14} is an organic group containing an alkoxysilyl group. n ¹ is an integer from 0 to 2. ]

A second aspect of the present invention is a laminate in which a support and a substrate are bonded to each other via an adhesive layer, and the adhesive layer is formed by using the adhesive composition of the first aspect. It is a laminate containing the first adhesive composition layer.

A third aspect of the present invention is a method for producing a laminated body in which a support and a substrate are bonded to each other via an adhesive layer, and the first aspect is on at least one of the support and the substrate. Through the adhesive layer forming step of forming the adhesive layer including the first adhesive composition layer formed by using the adhesive composition of No. 1 and the adhesive layer formed in the adhesive layer forming step, the said It is a method for manufacturing a laminated body, which comprises a bonding step of bonding a support and the substrate.

A fourth aspect of the present invention is to obtain a laminate by the method for producing a laminate according to the third aspect, and then irradiate the separation layer with light via the support substrate to alter the separation layer. Thereby, a method for manufacturing an electronic component, which comprises a separation step of separating the support substrate from the substrate included in the laminate, and a removal step of removing the adhesive layer adhering to the substrate after the separation step. Is.

A fifth aspect of the present invention is a polymer used in an adhesive composition for bonding a support and a substrate, and has a structural unit (p1) represented by the following general formula (p1-1). It is a polymer.

［式中、Ｒ^ｕ１１〜Ｒ^ｕ１４は、それぞれ独立に、炭素数１〜３０の有機基又は水素原子を表す。ただし、Ｒ^ｕ１１〜Ｒ^ｕ１４の少なくとも１つは、アルコキシシリル基を含む有機基である。ｎは、０〜２の整数である。］

[In the formula, R ^{u11 to} R ^u14 independently represent an organic group or a hydrogen atom having 1 to 30 carbon atoms. However, ^{at least one of Ru11 to Ru14} is an organic group containing an alkoxysilyl group. n is an integer from 0 to 2. ]

According to the present invention, it is an adhesive composition for adhering a support and a substrate, and an adhesive composition capable of forming an adhesive layer having heat resistance and excellent adhesion to the substrate or the support. It is possible to provide a product, a laminate using the same, a method for producing the same, a method for producing an electronic component, and a polymer used for the adhesive composition.

It is a schematic diagram which shows one Embodiment of the laminated body to which this invention is applied. It is a schematic process diagram explaining one Embodiment of the manufacturing method of a laminated body. FIG. 2A is a diagram for explaining a process of manufacturing a support, FIG. 2B is a diagram for explaining an adhesive layer forming process, and FIG. 2C is a diagram for explaining a bonding process. It is a figure to do. It is a schematic process diagram explaining another embodiment of the manufacturing method of a laminated body. FIG. 3A is a diagram showing a laminate produced by the production method of the first embodiment, and FIG. 3B is a diagram illustrating a sealing process. It is a schematic process diagram explaining another embodiment of the manufacturing method of a laminated body. FIG. 4 (a) is a diagram showing a sealed body produced by the manufacturing method of the second embodiment, FIG. 4 (b) is a diagram for explaining a grinding process, and FIG. 4 (c) is a diagram showing a re-grinding process. It is a figure explaining the wiring formation process. It is a schematic process diagram explaining one Embodiment of the manufacturing method of a semiconductor package (electronic component). FIG. 5 (a) is a diagram showing a laminate produced by the production method of the third embodiment, FIG. 5 (b) is a diagram for explaining a separation step, and FIG. 5 (c) is a diagram for removing. It is a figure explaining a process. It is a figure explaining an example of the use method of the adhesive composition to which this invention is applied. It is a figure explaining an example of the use method of the adhesive composition to which this invention is applied. It is a figure explaining an example of the use method of the adhesive composition to which this invention is applied.

As used herein and in the claims, "aliphatic" is defined as a relative concept to aromatics, meaning groups, compounds, etc. that do not have aromaticity.
Unless otherwise specified, the "alkyl group" shall include linear, branched and cyclic monovalent saturated hydrocarbon groups. The same applies to the alkyl group in the alkoxy group.
Unless otherwise specified, the "alkylene group" shall include linear, branched and cyclic divalent saturated hydrocarbon groups.
The "alkyl halide group" is a group in which a part or all of the hydrogen atom of the alkyl group is substituted with a halogen atom, and examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
The "fluorinated alkyl group" or "fluorinated alkylene group" refers to a group in which a part or all of hydrogen atoms of an alkyl group or an alkylene group is substituted with a fluorine atom.
The "constituent unit" means a monomer unit (monomer unit) constituting a polymer compound (resin, polymer, copolymer).
When describing "may have a substituent" or "may have a substituent", the case where the hydrogen atom (-H) is substituted with a monovalent group and the case where the methylene group (-CH _{2) is substituted.} Includes both cases where −) is replaced with a divalent group.
"Exposure" is a concept that includes general irradiation of radiation.

The “constituent unit derived from styrene” means a structural unit formed by cleaving the ethylenic double bond of styrene. The “constituent unit derived from the styrene derivative” means a structural unit formed by cleaving the ethylenic double bond of the styrene derivative.
The "styrene derivative" is a concept including a hydrogen atom at the α-position of styrene substituted with another substituent such as an alkyl group or an alkyl halide group, and derivatives thereof. As those derivatives, the hydrogen atom at the α-position may be substituted with a substituent. The hydrogen atom of the hydroxyl group of styrene is substituted with an organic group; the hydrogen atom at the α-position may be substituted with a substituent. Examples thereof include those in which a substituent other than a hydroxyl group is bonded to the benzene ring of styrene. The α-position (carbon atom at the α-position) refers to a carbon atom to which a benzene ring is bonded, unless otherwise specified.
Examples of the substituent substituting the hydrogen atom at the α-position of styrene include the same substituents as those mentioned as the substituent at the α-position in the α-substituted acrylic acid ester.

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

(Adhesive composition)
The adhesive composition according to the first aspect of the present invention is for bonding a support and a substrate. The adhesive composition of this embodiment contains a polymer component (P). This polymer component (P) contains at least the polymer (P1).

FIG. 1 shows an embodiment of a laminated body to which the present invention is applied.
The laminate 10 shown in FIG. 1 is provided with a separation layer 2 and an adhesive layer 3 between the support substrate 1 and the substrate 4, and the separation layer 2, the adhesive layer 3, and the substrate 4 are provided on the support substrate 1. They are stacked in this order.
The support substrate 1 is made of a material that transmits light. In the laminated body 10, when the separation layer 2 is irradiated with light from the support substrate 1 side, the separation layer 2 is denatured and decomposed, so that the support substrate 1 is separated from the substrate 4.
In the laminated body 10, the support 12 and the substrate 4 are bonded to each other via the adhesive layer 3. The adhesive layer 3 can be formed by using the adhesive composition of the present embodiment.

<Polymer component (P)>
In the present embodiment, the polymer component (P) (hereinafter, also referred to as “(P) component”) contains at least the polymer (P1). The component (P) may contain a polymer other than these in addition to the polymer (P1).
The polymer component (P) in the present embodiment includes, in addition to the polymer, a monomer that can be a matrix constituting the adhesive layer, for example, a curable monomer described later.

≪Polymer (P1) ≫
In the present embodiment, the polymer (P1) (hereinafter, also referred to as “(P1) component”) has at least a constituent unit (p1).

[Structural unit (p1)]
The structural unit (p1) is a structural unit represented by the following general formula (p1-1). Since the polymer (P1) has a structural unit (p1), it is possible to form an adhesive layer having high adhesion to the substrate.

［式中、Ｒ^ｕ１１〜Ｒ^ｕ１４は、それぞれ独立に、炭素数１〜３０の有機基又は水素原子を表す。但し、Ｒ^ｕ１１〜Ｒ^ｕ１４の少なくとも１つは、アルコキシシリル基を含む有機基である。ｎは、０〜２の整数である。］

[In the formula, R ^{u11 to} R ^u14 independently represent an organic group or a hydrogen atom having 1 to 30 carbon atoms. However, ^{at least one of Ru11 to Ru14} is an organic group containing an alkoxysilyl group. n is an integer from 0 to 2. ]

In the above formula (p1-1), the ^{organic group in Ru11 to Ru14} has, for example, an alkyl group, an alkenyl group, an alkynyl group, an alkylidene group, an aryl group, an aralkyl group, an alkalil group, a cycloalkyl group and a carboxy group. Examples thereof include an organic group and an organic group having a heterocycle.
The alkyl group in R ^{u11 to} R ^u14 is preferably an alkyl group having 1 to 10 carbon atoms, for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and the like. Examples thereof include a tert-butyl group, a pentyl group, a neopentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group and a decyl group.
^Examples of the alkenyl group in R ^{u11 to} R u14 include an allyl group, a pentaenyl group, and a vinyl group.
^Examples of the alkynyl group in R ^{u11 to} R u14 include an ethynyl group.
^Examples of the alkylidene group in R ^{u11 to} R u14 include a methylidene group and an ethylidene group.
^Examples of the aryl group in R ^{u11 to} R u14 include a phenyl group, a naphthyl group, and an anthrasenyl group.
^Examples of the aralkyl group in R ^{u11 to} R u14 include a benzyl group and a phenethyl group.
^{Examples of the alkaline} group in R u11 to R u14 include a tolyl group and a xsilyl group.
^Examples of the cycloalkyl group in R ^{u11 to} R u14 include an adamantyl group, a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group.
^{Examples of the organic group having a heterocycle in Ru11 to} Ru14 include an organic group having an epoxy group and an organic group having an oxetanyl group.

The organic group in R ^{u11 to} R ^u14 is preferably an alkyl group from the viewpoint of further enhancing the solubility of the hydrocarbon system in the solvent and from the viewpoint of synthesis. In addition, an alkyl group having 1 to 8 carbon atoms is more preferable, and an alkyl group having 2 to 6 carbon atoms is further preferable because it is easy to maintain a high glass transition point.

In the ^{organic groups in R u11 to} R ^u14 , one or more hydrogen atoms may be substituted with halogen atoms. Examples of this halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

At ^{least one of R u11 to} R ^u14 is an organic group containing an alkoxysilyl group. The alkoxysilyl group is a group represented by −Si (OR ¹ ) _m (R ² ) _3-m (R ¹ and R ² are independently alkyl groups having 1 to 30 carbon atoms; m is an integer of 1 to 3). ). ^Examples of the alkyl groups of R ¹ and R ² include those similar to those mentioned as the alkyl groups in R ^{u11 to} R u14. ^{The alkyl groups of R 1} and R ² preferably have 1 to 8 carbon atoms, more preferably 1 to 6 carbon atoms, further preferably 1 to 3 carbon atoms, and 1 or 1 carbon atom, because the adhesion to the substrate is enhanced. 2 is particularly preferable.
The organic group containing an alkoxysilyl group is preferably ^{a group represented by −Y—Si (OR 1} ) _m (R ² ) _3-m (Y is a single bond or a divalent linking group having 1 to 20 carbon atoms. R ¹ , R ² , and m are the same as above). The divalent linking group in Y has an alkyl group, an alkenyl group, an alkynyl group, an alkylidene group, an aryl group, an aralkyl group, an alkalil group, a cycloalkyl group, a divalent linking group having a carboxy group, and a heterocycle. Divalent linking groups and the like can be mentioned. Y is preferably a single bond or an alkylene group. The alkylene group in Y preferably has 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, further preferably 1 to 3 carbon atoms, and particularly preferably 1 or 2 carbon atoms. Among them, Y is preferably a single bond.
m is an integer of 1 to 3, preferably 2 or 3, and more preferably 3.

An organic group containing an alkoxysilyl group ^may be all of R u11 ^{to R u14,} may also be any three of R u11 ^{to R u14,} there are two one of R u11 ^{to R u14} It may be any one of ^{Ru11 to Ru14.} From a synthetic point of view, ^{it is preferable that any one of Ru11 to Ru14} is an organic group containing an alkoxysilyl group.

From the viewpoint of enhancing the light transmission of the adhesive layer formed by using the adhesive composition, it is preferable that any one or more of ^{Ru11 to Ru14 are hydrogen atoms.}

Among the above, the ^{organic groups in Ru11 to Ru14} are preferably a combination of an alkoxysilyl group, an alkyl group and a hydrogen atom, or a combination of an alkoxysilyl group and a hydrogen atom, and a combination of an alkoxysilyl group and a hydrogen atom is preferable. More preferred. Among ^{them, it is preferable that any one of Ru11 to Ru14} is an alkoxysilyl group and the remaining three are hydrogen atoms.

In the above formula (p1-1), n is an integer of 0 to 2, preferably 0 or 1, and more preferably 0.

A specific example of the structural unit (p1) is shown below.

The structural unit (p1) contained in the component (P1) may be one type or two or more types.
The ratio of the structural unit (p1) in the component (P1) can be, for example, 3 mol% or more with respect to the total (100 mol%) of all the structural units constituting the component (P1). When it is at least the above lower limit value, the adhesion of the adhesive layer to the substrate is further improved. The ratio of the structural unit (p1) in the component (P1) is preferably 5 mol% or more, preferably 8 mol% or more, with respect to the total (100 mol%) of all the structural units constituting the component (P1). It is more preferably 10 mol% or more, further preferably 12 mol% or more, and particularly preferably 14 mol% or more. The upper limit of the ratio of the constituent unit (p1) in the component (P1) is not particularly limited, but from the viewpoint of solubility, 30 is obtained with respect to the total (100 mol%) of all the constituent units constituting the component (P1). It is preferably mol% or less, more preferably 25 mol% or less, further preferably 20 mol% or less, and particularly preferably 17 mol% or less. The proportion of the constituent unit (p1) in the component (P1) is, for example, 3 to 30 mol%, 5 to 25 mol%, based on the total (100 mol%) of all the constituent units constituting the component (P1). It can be 8 to 20 mol%, 14 to 17 mol%, or the like.

[Other building blocks]
The component (P1) may have other structural units in addition to the structural unit (p1). Other structural units include, for example, a structural unit (p2) derived from a cycloolefin (excluding those corresponding to the structural unit (p1)), and a structural unit derived from a monomer containing a maleimide skeleton. (P3) can be mentioned.

・ Structural unit (p2)
The structural unit (p2) is a structural unit derived from a cycloolefin (excluding those corresponding to the structural unit (p1)). The polymer (P1) preferably has a structural unit (p2) in addition to the structural unit (p1). By using a cycloolefin, that is, a resin having an unsaturated aliphatic hydrocarbon ring composed of carbon atoms, an adhesive composition capable of forming an adhesive layer that can be easily dissolved and removed in a hydrocarbon solvent can be obtained. It will be easier to obtain.

As a preferable structural unit (p2), for example, a structural unit represented by the following general formula (p1-2) can be mentioned.

［式中、Ｒ^ｕ２１〜Ｒ^ｕ２４は、それぞれ独立に、炭素数１〜３０の有機基（但し、アルコキシシリル基を含むものは除く）又は水素原子を表す。ｎ^２は、０〜２の整数である。］

[In the formula, R ^{u21 to} R ^u24 independently represent an organic group having 1 to 30 carbon atoms (excluding those containing an alkoxysilyl group) or a hydrogen atom. n ² is an integer from 0 to 2. ]

In the formula ^(p2-1), examples of the organic group in R u21 ^{to R u24,} include the same as those of the organic group in ^R u11 ^{to R u14} of the formula (p1-1) in. However, the ^{organic groups in Ru21 to Ru24} do not contain an alkoxysilyl group.
^{The organic group in Ru21 to Ru24} is preferably an alkyl group from the viewpoint of higher solubility in a hydrocarbon solvent and synthetic viewpoint. In addition, an alkyl group having 1 to 8 carbon atoms is more preferable, and an alkyl group having 2 to 6 carbon atoms is further preferable because it is easy to maintain a high glass transition point.

In the ^{organic groups in R u21 to} R ^u24 , one or more hydrogen atoms may be substituted with halogen atoms. Examples of this halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

From the viewpoint of enhancing the light transmission of the adhesive layer formed by using the adhesive composition, it is preferable that any one or more of ^{Ru21 to Ru24 are hydrogen atoms.}
Among the above, the ^{organic group in Ru21 to Ru24} is preferably a combination of an alkyl group and a hydrogen atom, and it is preferable that ^{any one of Ru21 to Ru24} is an alkyl group and the remaining three are hydrogen atoms. ..

In the above formula (p2-2), n ² is an integer of 0 to 2, preferably 0 or 1, and more preferably 0.

A specific example of the structural unit (p2) is shown below.

The structural unit (p2) contained in the component (P1) may be one type or two or more types.
The ratio of the constituent unit (p2) in the component (P1) is preferably 10 to 95 mol%, preferably 20 to 90 mol%, based on the total (100 mol%) of all the constituent units constituting the (P1) component. More preferably, 30 to 88 mol% is further preferable, and 40 to 86 mol% is particularly preferable.
When the ratio of the structural unit (p2) is at least the lower limit of the above-mentioned preferable range, the solubility of the hydrocarbon-based solvent in the solvent is likely to be enhanced. When it is not more than the upper limit value of the above-mentioned preferable range, it becomes easy to balance with other structural units.

・ Structural unit (p3)
The structural unit (p3) is a structural unit derived from a monomer containing a maleimide skeleton. The polymer (P1) may have a structural unit (p3) in addition to the structural unit (p1). By having the structural unit (p3), the glass transition temperature becomes high, and the heat resistance of the adhesive layer can be enhanced.
As a preferable structural unit (p3), for example, a structural unit represented by the following general formula (p3-1) can be mentioned.

［式中、Ｒ^ｕ１０は、炭素数１〜３０の有機基を表す。］

[In the formula, ^Ru10 represents an organic group having 1 to 30 carbon atoms. ]

In the above formula (p3-1), ^Ru10 represents an organic group having 1 to 30 carbon atoms. ^{The organic group in Ru10} may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group. Aliphatic hydrocarbon groups mean hydrocarbon groups that do not have aromaticity. Further, the aliphatic hydrocarbon group may be saturated or unsaturated, and is usually preferably saturated.
For example, ^{as the organic group in Ru10} , a cyclic group which may have a substituent, a chain alkyl group which may have a substituent, or a chain which may have a substituent may be used. Alkenyl group of.

Cyclic group which may have a substituent:
The cyclic group is preferably a cyclic hydrocarbon group, and the cyclic hydrocarbon group may be an aromatic hydrocarbon group or an aliphatic hydrocarbon group.

^{The aromatic hydrocarbon group in Ru10} is a hydrocarbon group having an aromatic ring. The aromatic hydrocarbon group preferably has 3 to 30 carbon atoms, more preferably 5 to 30 carbon atoms, further preferably 5 to 20 carbon atoms, particularly preferably 6 to 15 carbon atoms, and most preferably 6 to 10 carbon atoms. However, the number of carbon atoms does not include the number of carbon atoms in the substituent.
^{Specifically, the aromatic ring contained} in the aromatic hydrocarbon group in Ru10 is benzene, fluorene, naphthalene, anthracene, phenanthrene, biphenyl, or an aromatic in which some of the carbon atoms constituting these aromatic rings are replaced with heteroatoms. Examples include group heterocycles. Examples of the hetero atom in the aromatic heterocycle include an oxygen atom, a sulfur atom, a nitrogen atom and the like.
^{Specifically, as the aromatic hydrocarbon group in Ru10,} a group obtained by removing one hydrogen atom from the aromatic ring (aryl group: for example, a phenyl group, a naphthyl group, etc.), and one of the hydrogen atoms of the aromatic ring is an alkylene group. Examples thereof include a group substituted with (for example, an arylalkyl group such as a benzyl group, a phenethyl group, a 1-naphthylmethyl group, a 2-naphthylmethyl group, a 1-naphthylethyl group, a 2-naphthylethyl group, etc.). The alkylene group (alkyl chain in the arylalkyl group) preferably has 1 to 4 carbon atoms, more preferably 1 to 2 carbon atoms, and particularly preferably 1 carbon atom.

^Examples of the cyclic aliphatic hydrocarbon group in Ru10 include an aliphatic hydrocarbon group containing a ring in the structure.
As the aliphatic hydrocarbon group containing a ring in this structure, an alicyclic hydrocarbon group (a group obtained by removing one hydrogen atom from the aliphatic hydrocarbon ring) and one of the hydrogen atoms of the aliphatic hydrocarbon ring are alkylene. Examples thereof include groups substituted with groups. The alkylene group preferably has 1 to 4 carbon atoms.
The aliphatic hydrocarbon ring preferably has 3 to 20 carbon atoms, and more preferably 3 to 12 carbon atoms.
The aliphatic hydrocarbon ring may be a polycyclic ring or a monocyclic ring.
The monocyclic aliphatic hydrocarbon ring preferably has 3 to 8 carbon atoms, and specific examples thereof include cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, and cyclooctane, and cyclopentane and cyclohexane are used. preferable.
The polycyclic aliphatic hydrocarbon ring preferably has 7 to 30 carbon atoms, and specifically has a polycyclic skeleton of a bridged ring system such as adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane. Polycycloalkane; Polycycloalkane having a polycyclic skeleton of a fused ring system such as a ring having a steroid skeleton is more preferable.

Among them, as ^{the cyclic aliphatic hydrocarbon group in Ru10} , a group in which one or more hydrogen atoms are removed from monocycloalkane or polycycloalkane is preferable, and a group in which one or more hydrogen atoms are removed from monocycloalkane is preferable. More preferably, a group obtained by removing one hydrogen atom from monocycloalkane is further preferable, and a group obtained by removing one hydrogen atom from cyclopentane or cyclohexane is particularly preferable.

^Examples of the substituent in the cyclic group of Ru10 include an alkyl group, a halogen atom, an alkyl halide group and the like.
As the alkyl group as the substituent, an alkyl group having 1 to 5 carbon atoms is preferable, and a methyl group, an ethyl group, a propyl group, an n-butyl group and a tert-butyl group are more preferable.
Examples of the halogen atom as the substituent include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like, and a fluorine atom is preferable.
As the alkyl halide group as a substituent, a part or all of hydrogen atoms such as an alkyl group having 1 to 5 carbon atoms, for example, a methyl group, an ethyl group, a propyl group, an n-butyl group, and a tert-butyl group are described above. Examples include groups substituted with halogen atoms.

Chain-like alkyl group which may have a substituent:
The chain-like alkyl group of ^{Ru10 may be either linear or branched.}
The linear alkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, and even more preferably 1 to 12 carbon atoms. Specifically, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decanyl group, undecyl group, dodecyl group, tridecyl group, isotridecyl group, tetradecyl group, Examples thereof include a pentadecyl group, a hexadecyl group, an isohexadecyl group, a heptadecyl group, an octadecyl group, a nonadecil group, an icosyl group, a henicosyl group and a docosyl group.
The branched-chain alkyl group preferably has 3 to 20 carbon atoms, more preferably 3 to 15 carbon atoms, and even more preferably 3 to 10 carbon atoms. Specifically, 1-methylethyl group, 1-methylpropyl group, 2-methylpropyl group, 1-methylbutyl group, 2-methylbutyl group, 3-methylbutyl group, 1-ethylbutyl group, 2-ethylbutyl group, 1- Examples thereof include a methylpentyl group, a 2-methylpentyl group, a 3-methylpentyl group, and a 4-methylpentyl group.

Chain alkenyl group which may have a substituent:
^{The chain alkenyl group of Ru10} may be either linear or branched, preferably having 2 to 10 carbon atoms, more preferably 2 to 5 carbon atoms, and 2 to 4 carbon atoms. More preferably, 3 carbon atoms are particularly preferable. Examples of the linear alkenyl group include a vinyl group, a propenyl group (allyl group), a butynyl group and the like. Examples of the branched alkenyl group include a 1-methylvinyl group, a 2-methylvinyl group, a 1-methylpropenyl group, a 2-methylpropenyl group and the like.
Among the above, as the chain alkenyl group, a linear alkenyl group is preferable, a vinyl group and a propenyl group are more preferable, and a vinyl group is particularly preferable.

^{Examples of the substituent in} the chain alkyl group or alkenyl group of Ru10 include a halogen atom, an alkyl halide group, and a cyclic group in ^Ru10 .

Among the above, ^Ru10 is preferably a cyclic group which may have a substituent, more preferably a cyclic hydrocarbon group which may have a substituent, and has a substituent. A cyclic aliphatic hydrocarbon group may be more preferable.

A specific example of the structural unit (p3) is shown below.

The structural unit (p3) contained in the component (P1) may be one type or two or more types.
The ratio of the constituent units (p3) in the (P1) component is preferably 0 to 90 mol%, preferably 0 to 70 mol%, based on the total (100 mol%) of all the constituent units constituting the (P1) component. More preferably, 0 to 50 mol% is further preferable.
When the ratio of the structural unit (u21) is equal to or higher than the lower limit of the above-mentioned preferable range, the glass transition temperature becomes high and the heat resistance of the adhesive layer is further improved. When it is not more than the upper limit value of the above-mentioned preferable range, it becomes easy to balance with other structural units.

In the adhesive composition of the present embodiment, one type of the component (P1) may be used alone, or two or more types may be used in combination.
The component (P1) has enhanced adhesion to the substrate and can form an adhesive layer that can be easily dissolved and removed in a hydrocarbon solvent. Therefore, a polymer having a structural unit (p1) and a structural unit (p2). Is preferable.

A preferable specific example of the component (P1) is shown below.

The weight average molecular weight of the polymer (P1) (Mw) (the polystyrene equivalent value determined by gel permeation chromatography (GPC)) is, for example, be a 5.0 × ¹⁰ 4 ~1.0 × ^{10 6} range, The range of 8.0 × 10 ^{4 to} 9.0 × 10 ⁵ is preferable, the range of 1.0 × 10 ^{5 to} 8.0 × 10 ⁵ is more preferable, and the range of 2.0 × 10 ^{5 to} 6.0 × 10 ^{5 is preferable.} The range of is more preferred.
When the weight average molecular weight of the polymer (P1) is at least the lower limit of the above-mentioned preferable range, the heat resistance becomes better. When it is not more than the upper limit of the above preferable range, it becomes easy to obtain an adhesive composition capable of forming an adhesive layer which is easily dissolved in a hydrocarbon solvent and removed.

The dispersity (Mw / Mn) of the polymer (P1) can be, for example, in the range of 1.5 to 9.0, preferably in the range of 2.5 to 7.0, and preferably in the range of 3.5 to 5.5. The range of is more preferable, and the range of 4.0 to 5.0 is further preferable. Dispersity indicates the width of the molecular weight distribution. Mn indicates a number average molecular weight.

For the weight average molecular weight (Mw), the number average molecular weight (Mn), and the molecular weight distribution (Mw / Mn), for example, polystyrene-equivalent values obtained from the calibration curve of standard polystyrene (PS) obtained by GPC measurement are used. The measurement conditions for GPC measurement are as follows, for example.
Tosoh gel permeation chromatography device HLC-8320GPC
Column: Tosoh TSK-GEL Supermultipore HZ-M
Detector: RI detector for liquid chromatogram Measurement temperature: 40 ° C
Solvent: THF
Sample concentration: 2.0 mg / ml

The content ratio of the component (P1) to the component (P) can be 50% by mass or more, or 60% by mass or more, based on the total amount (100% by mass) of the component (P). , 70% by mass or more, 80% by mass or more, 90% by mass or more, or 100% by mass.
When the content ratio of the component (P1) is at least the lower limit of the above-mentioned preferable range, both the heat resistance and the adhesion to the substrate are further improved.
The component (P1) can be synthesized by the method described in the section <Production of Polymer> in (Polymer) described later.

≪Polymer (P2) ≫
The component (P) may contain another polymer (P2) (hereinafter, also referred to as “component (P2)”) in addition to the component (P1). Examples of the component (P2) include hydrocarbon-based polymers. The hydrocarbon-based polymer may be an aliphatic hydrocarbon-based polymer or an aromatic hydrocarbon-based polymer. The component (P2) includes, for example, an elastomer, a cycloolefin polymer (excluding those corresponding to the polymer (P1)), an acrylic resin, and a matrix constituting the adhesive layer from the viewpoint of imparting heat resistance or flexibility. Examples thereof include curable monomers that can serve as.

[Elastomer]
The elastomer in the component (P2) preferably has, for example, a structural unit derived from styrene or a structural unit derived from a styrene derivative (collectively referred to as "styrene unit") as a structural unit of the main chain. Listed in. The elastomer is preferably a styrene-based thermoplastic elastomer, and more preferably a hydrogenated styrene-based thermoplastic elastomer.

Examples of the elastomer in the component (P2) include polystyrene-poly (ethylene / propylene) block copolymer (SEP), styrene-isoprene-styrene block copolymer (SIS), styrene-butadiene-styrene block copolymer (SBS), and styrene-butadiene. -Styrene-Styrene Block Copolymer (SBBS) or hydrogenated products thereof; Styrene-ethylene-Styrene-Styrene Block Copolymer (SEBS) (Septon8004 (manufactured by Kuraray Co., Ltd.)), Styrene-ethylene-propylene-Styrene Block Copolymer (Styrene-) Isoprene-Styrene Block Copolymer) (SEPS), Styrene-Eethylene-Eethylene-propylene-Styrene Block Copolymer (SEEPS), Styrene-Eethylene-Eethylene-Styrene-Styrene Block Copolymer (SeptonV9461 (manufactured by Kuraray Co., Ltd.) ), SeptonV9475 (manufactured by Kuraray Co., Ltd.), Styrene-ethylene-butylene-styrene block copolymer (with a reactive polystyrene-based hard block, SeptonV9827 (manufactured by Kuraray Co., Ltd.)) in which the styrene block is a reaction-bridged type.

The content ratio of the styrene unit in the elastomer in the component (P2) is preferably 10 to 70 mol%, more preferably 20 to 60 mol%, and 25 to 50 mol% with respect to all the constituent units (100 mol%) constituting the elastomer. 50 mol% is more preferable, and 30 to 45 mol% is particularly preferable.
When the content ratio of the styrene unit is equal to or higher than the lower limit of the above-mentioned preferable range, it can be easily subjected to processes such as thinning and mounting without deteriorating the bondability or grindability between the support and the substrate. Become. When it is not more than the upper limit value of the above preferable range, the chemical resistance of the adhesive layer formed by the adhesive composition can be suitably maintained.

The elastomer in the component (P2) preferably has a weight average molecular weight in the range of 20000 to 200,000, more preferably in the range of 50,000 to 150,000, and even more preferably in the range of 80,000 to 1200,000.
When the weight average molecular weight of the elastomer is within the above-mentioned preferable range, it becomes easy to obtain an adhesive composition capable of forming an adhesive layer which is easily dissolved in a hydrocarbon solvent and removed. Further, when the weight average molecular weight of the elastomer is within the above-mentioned preferable range, the chemical resistance of the adhesive layer formed by the adhesive composition is enhanced.

The elastomer in the component (P2) may be one kind or two or more kinds.

As the elastomer in the component (P2), a hydrogenated product is more preferable among the elastomers. If it is a hydrogenated product, its stability against heat is further improved, and deterioration such as decomposition and polymerization is unlikely to occur. In addition, it is more preferable from the viewpoint of solubility in a hydrocarbon solvent and resistance to a resist solvent.
Further, among the elastomers, those which are block polymers having styrene at both ends are more preferable. By blocking both ends with styrene, which has high thermal stability, it is easy to obtain higher heat resistance.
More specifically, the elastomer is more preferably a hydrogenated block copolymer of styrene and conjugated diene. As a result, the stability against heat is further improved, and deterioration such as decomposition and polymerization is unlikely to occur. In addition, it exhibits higher heat resistance because both ends are blocked by styrene, which has high thermal stability. Further, it is more preferable from the viewpoint of solubility in a hydrocarbon solvent and resistance to a resist solvent.

Examples of commercially available elastomer products that can be used as the component (P2) include "Septon (trade name)" manufactured by Kuraray Corporation, "Hybler (trade name)" manufactured by Kuraray Corporation, and "Tough Tech" manufactured by Asahi Kasei Corporation. Product name) ”,“ Dynalon (product name) ”manufactured by JSR Corporation, and the like.

The component (P) preferably contains an elastomer as the component (P2). By containing the elastomer, the adhesion of the adhesive layer to the substrate is further improved.
The content ratio of the elastomer in the component (P) is preferably 1% by mass or more, more preferably 3% by mass or more, still more preferably 5% by mass or more, based on the total amount (100% by mass) of the component (P). .. The upper limit of the content ratio of the elastomer in the component (P) is preferably 50% by mass or less, more preferably 30% by mass or less, still more preferably 20% by mass or less, from the viewpoint of the balance with the component (P1). It is more preferably 10% by mass or less. The range of the content ratio of the elastomer in the component (P) can be, for example, 0 to 50% by mass, preferably 1 to 40% by mass, more preferably 3 to 30% by mass, and 3 to 25% by mass. % Is more preferable, and 5 to 20% by mass or 5 to 10% by mass is particularly preferable.

[Cycloolefin polymer]
Preferable examples of the cycloolefin polymer include a ring-opening polymer having a monomer component containing a cycloolefin monomer and an addition polymer obtained by addition-polymerizing a monomer component containing a cycloolefin monomer. However, those corresponding to the polymer (P1) are excluded.

Examples of the cycloolefin monomer include dicyclics such as norbornene and norbornadiene, tricyclics such as dicyclopentadiene and hydroxydicyclopentadiene, tetracyclics such as tetracyclopentadiene, and pentacycles such as cyclopentadiene trimer. The body, a seven-ring body such as tetracyclopentadiene, or an alkyl (methyl, ethyl, propyl, butyl, etc.) substituent, an alkenyl (vinyl, etc.) substitute, an alkylene (ethylidene, etc.) substitute or an aryl (phenyl) of these polycyclic bodies. , Trill, naphthyl, etc.) Monomers such as substituents can be mentioned.

Among the above, a polymer having a structural unit derived from a monomer having a norbornene structure, which is selected from the group consisting of norbornene, tetracyclododecene and alkyl substituents thereof, is particularly preferable. By using such a cycloolefin polymer having a norbornene structure, for example, an adhesive composition capable of forming an adhesive layer which is easily dissolved in a hydrocarbon solvent and removed while having high chemical resistance to a resist solvent. It becomes easier to obtain things.

The cycloolefin polymer may have a monomer copolymerizable with the cycloolefin monomer as a monomer unit.
As such a copolymerizable monomer, for example, an alkene monomer is preferably mentioned. The alkene monomer may be linear or branched, and examples thereof include alkene monomers having 2 to 10 carbon atoms, for example, ethylene, propylene, 1-butene, isobutene, 1 Α-olefins such as −hexene are preferable, and among these, ethylene is more preferably used as a monomer unit.

The content ratio of the cycloolefin monomer unit in the cycloolefin polymer in the component (P2) is preferably 10 to 100 mol% with respect to all the constituent units (100 mol%) constituting the cycloolefin polymer, and is preferably 20 to 100 mol%. Is more preferable.

The cycloolefin polymer in the component (P2) preferably has a weight average molecular weight in the range of 1000 to 200000000, and more preferably in the range of 30000 to 1500000.
When the weight average molecular weight of the cycloolefin polymer is at least the lower limit of the above-mentioned preferable range, it becomes easy to control the softening temperature of the polymer to a temperature suitable for bonding the support and the substrate. When it is not more than the upper limit of the above preferable range, it becomes easy to obtain an adhesive composition capable of forming an adhesive layer which is easily dissolved in a hydrocarbon solvent and removed.

The cycloolefin polymer in the component (P2) may be one kind or two or more kinds.

The cycloolefin polymer is a polymer having no polar group, such as a polymer obtained by polymerizing a monomer component composed of a cycloolefin monomer and an alkene monomer, so that gas is generated at a high temperature. It is preferable from the viewpoint of suppressing.
The polymerization method, polymerization conditions, and the like when polymerizing the monomer component are not particularly limited and may be appropriately set according to a conventional method.

Examples of commercially available cycloolefin polymers that can be used as the component (P2) include "TOPAS (trade name)" manufactured by Polyplastics Corporation, "APEL (trade name)" manufactured by Mitsui Chemicals Co., Ltd., and JSR Corporation. Examples thereof include "ZEONOR (trade name)" manufactured by the company, "ZEONEX (trade name)" manufactured by Nippon Zeon Co., Ltd., and "ARTON (trade name)" manufactured by JSR Corporation.

The content ratio of the cycloolefin polymer in the component (P) is 0 to 50% by mass with respect to the total amount of the component (P) (100% by mass) and the total amount of the component (P) (100% by mass). Is preferable, 0 to 30% by mass is more preferable, 0 to 25% by mass is further preferable, and 0 to 20% by mass or less is particularly preferable.

〔acrylic resin〕
The component (P2) may contain an acrylic resin. Since the component (P2) contains an acrylic resin, the adhesiveness between the support and the substrate can be further improved. Examples of the acrylic resin include resins (monopolymers and copolymers) polymerized using (meth) acrylic acid ester as a monomer. "(Meta) acrylic" means at least one of acrylic and methacrylic.

Examples of the (meth) acrylic acid ester include a (meth) acrylic acid alkyl ester having a chain structure, a (meth) acrylic acid ester having an aliphatic ring, and a (meth) acrylic acid ester having an aromatic ring. .. Among these, it is preferable to use a (meth) acrylic acid ester having an aliphatic ring.

Examples of the (meth) acrylic acid alkyl ester having a chain structure include an acrylic alkyl ester having an alkyl group having 1 to 20 carbon atoms.
The alkyl group having 1 to 20 carbon atoms here may be linear or branched, and may be, for example, a methyl group, an ethyl group, a propyl group, a butyl group, a 2-ethylhexyl group, an isooctyl group, an isononyl group or an isodecyl group. , Dodecyl group, lauryl group, tridecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group (stearyl group), n-nonadecil group, n-eicosyl group, etc., and have 15 carbon atoms. Acrylic alkyl esters having ~ 20 alkyl groups are preferred.

Examples of the (meth) acrylic acid ester having an aliphatic ring include cyclohexyl (meth) acrylate, cyclopentyl (meth) acrylate, 1-adamantyl (meth) acrylate, norbornyl (meth) acrylate, isobornyl (meth) acrylate, and tricyclo. Examples thereof include decanyl (meth) acrylate, tetracyclododecanyl (meth) acrylate, and dicyclopentanyl (meth) acrylate. Among these, 1-adamantyl (meth) acrylate, isobornyl (meth) acrylate, and dicyclopentanyl (meth) acrylate are preferable.

In the (meth) acrylic acid ester having an aromatic ring, the aromatic ring includes, for example, a phenyl group, a benzyl group, a tolyl group, a xsilyl group, a biphenyl group, a naphthyl group, an anthrasenyl group, a phenoxymethyl group, and a phenoxyethyl group. And so on. The aromatic ring may have a substituent and may have a linear or branched alkyl group having 1 to 5 carbon atoms.

Among the acrylic resins, the above-mentioned (meth) acrylic acid ester may be used alone or in combination of two or more.

The acrylic resin is one selected from the group consisting of a (meth) acrylic acid alkyl ester having a chain structure, a (meth) acrylic acid ester having an aliphatic ring, and a (meth) acrylic acid ester having an aromatic ring. A resin obtained by polymerizing the above is preferable.
Among these, a resin obtained by polymerizing a (meth) acrylic acid alkyl ester and a (meth) acrylic acid ester having an aliphatic ring is more preferable.

The acrylic resin may be a resin obtained by polymerizing a (meth) acrylic acid ester monomer and another monomer that can be polymerized with the (meth) acrylic acid ester monomer.
Examples of such polymerizable monomers include styrene, styrene derivatives, and monomers containing a maleimide group. The styrene derivative here is the same as the above-mentioned "styrene derivative". Examples of the monomer containing a maleimide group here include the same monomers as those for inducing the structural unit (u21).

Further, among the acrylic resins, a resin obtained by polymerizing a (meth) acrylic acid ester monomer and styrene is preferable. Since the acrylic resin has a styrene unit, the heat resistance of the acrylic resin is improved. In addition, compatibility with other resins and solubility in hydrocarbon solvents are enhanced.
Among these, as the acrylic resin, a resin obtained by polymerizing a (meth) acrylic acid alkyl ester having a chain structure, a (meth) acrylic acid ester having an aliphatic ring, and styrene is particularly preferable.

The solubility parameter (SP value) of the acrylic resin is preferably 6 or more and 10 or less, and more preferably 6.5 or more and 9.5 or less. When the SP value is within the above-mentioned preferable range, the compatibility between the acrylic resin and the other resin is enhanced, and a more stable adhesive composition can be easily obtained.

The weight average molecular weight of the acrylic resin is preferably 2000 to 100,000, more preferably 5,000 to 50,000.
When the weight average molecular weight of the acrylic resin is within the above-mentioned preferable range, it is possible to easily provide an adhesive composition having heat fluidity suitable for bonding a substrate and a support, for example.

Two or more kinds of acrylic resins may be used in combination.
The content ratio of the acrylic resin in the component (P) can be 0 to 50% by mass, preferably 0 to 30% by mass, and 0 to 0, based on the total amount (100% by mass) of the component (P). 25% by mass is more preferable, 0 to 20% by mass or less is further preferable, and 0 to 10% by mass is particularly preferable.

[Curable monomer]
The component (P2) may contain a curable monomer. Since the component (P2) contains a curable monomer, the heat resistance of the adhesive layer can be further improved.
The curable monomer is preferably a monomer that is polymerized by radical polymerization, and typically includes a polyfunctional curable monomer, and a polyfunctional (meth) acrylate monomer is particularly preferable.

Examples of the polyfunctional (meth) acrylate monomer include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, and polypropylene glycol di (meth). Meta) acrylate, butylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexane glycol di (meth) acrylate, 1,4-cyclohexanedimethanol di (meth) acrylate, tricyclodecandy Methanoldi (meth) acrylate, 9,9-bis [4- (2- (meth) acryloyloxyethoxy) phenyl] fluorene, propoxylated bisphenol A di (meth) acrylate, 1,3-adamantandiol di (meth) acrylate , 5-Hydroxy-1,3-adamantandiol di (meth) acrylate, 1,3,5-adamantan trioltri (meth) acrylate, trimethylpropanthry (meth) acrylate, glycerindi (meth) acrylate, pentaerythritoldi (Meta) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 2-hydroxy-3- (meth) acryloyloxy Propyl (meth) acrylate, ethylene glycol diglycidyl ether di (meth) acrylate, diethylene glycol diglycidyl ether di (meth) acrylate, diglycidyl phthalate di (meth) acrylate, glycerin tri (meth) acrylate, glycerin polyglycidyl ether poly Examples thereof include (meth) acrylate, urethane (meth) acrylate (that is, tolylene diisocyanate), and a reaction product of trimethylhexamethylene diisocyanate, hexamethylene diisocyanate and 2-hydroxyethyl (meth) acrylate.

One of these polyfunctional (meth) acrylates may be used alone, or two or more thereof may be used in combination.
The curable monomer preferably contains a cyclic structure, and more preferably contains a polycyclic aliphatic structure. When the curable monomer preferably contains a cyclic structure, more preferably a polycyclic aliphatic structure, the compatibility with the cycloolefin polymer can be further enhanced. Further, the heat resistance of the adhesive layer can be further enhanced by polymerizing the curable monomer used in combination with the cycloolefin polymer.

Among the curable monomers, a (meth) acrylate monomer having a cyclic group is particularly preferable, and tricyclodecanedimethanol di (meth) acrylate, 1,3-adamantandiol di (meth) acrylate, 5-hydroxy-1,3 − Adamantane diol di (meth) acrylate, 1,3,5-adamantan trioltri (meth) acrylate, 1,4-cyclohexanedimethanol di (meth) acrylate, 9,9-bis [4- (2- (meth)) At least one selected from the group consisting of acryloyloxyethoxy) phenyl] fluorene and propoxylated bisphenol A di (meth) acrylate is more preferable, and tricyclodecanedimethanol di (meth) acrylate is particularly preferable.

The content ratio of the curable monomer in the component (P) is more preferably 0 to 20% by mass, still more preferably 0 to 15% by mass, based on the total amount (100% by mass) of the component (P).

The content of the component (P) in the adhesive composition of the present embodiment may be adjusted according to the thickness of the adhesive layer to be formed, the type of each resin, and the like.

<Arbitrary ingredient>
The adhesive composition of the present embodiment may further contain a component (arbitrary component) other than the above-mentioned component (P).
Examples of such optional components include the following polymerization inhibitors, polymerization initiators, solvent components, plasticizers, adhesive aids, stabilizers, colorants, surfactants and the like.

≪Polymerization inhibitor≫
The adhesive composition of the present embodiment may further contain a polymerization inhibitor.
A polymerization inhibitor refers to a component having a function of preventing a radical polymerization reaction due to heat or light. Polymerization inhibitors are highly reactive with radicals. Therefore, for example, when a cycloolefin polymer is used as the component (P2), the reaction between the polymerization inhibitor and the radical proceeds preferentially over the reaction between the cycloolefin polymer and the radical, and the cycloolefin polymers polymerize with each other. Prohibit doing. As a result, the formed adhesive layer is heated, so that the chemical resistance of the adhesive layer is enhanced.

As the polymerization inhibitor, those having a phenol skeleton are preferable. For example, a hindered phenolic antioxidant can be used as such a polymerization inhibitor, such as pyrogallol, benzoquinone, hydroquinone, methylene blue, tert-butylcatechol, monobenzyl ether, methylhydroquinone, amylquinone, amyloxyhydroquinone. , N-butylphenol, phenol, hydroquinone monopropyl ether, 4,4'-(1-methylethylidene) bis (2-methylphenol), 4,4'-(1-methylethylidene) bis (2,6-dimethylphenol) ), 4,4'-[1- [4- (1- (4-Hydroxyphenyl) -1-methylethyl) phenyl] tert] bisphenol, 4,4', 4 "-ethylidentris (2-methylphenol) , 4,4', 4 "-ethylidentrysphenol, 1,1,3-tris (2,5-dimethyl-4-hydroxyphenyl) -3-phenylpropane, 2,6-di-tert-butyl-4- Methylphenol, 2,2'-methylenebis (4-methyl-6-tert-butylphenol), 4,4'-butylidenebis (3-methyl-6-tert-butylphenol), 4,4'-thiobis (3-methyl- 6-tert-butylphenol), 3,9-bis [2- (3- (3-tert-butyl-4-hydroxy-5-methylphenyl) -propionyloxy) -1,1-dimethylethyl] -2,4 , 8,10-Tetraoxaspiro (5,5) undecane, triethylene glycol-bis-3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate, n-octyl-3- (3,3) 5-Di-tert-butyl-4-hydroxyphenyl) propionate, pentaerythryltetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (trade name IRGANOX1010, manufactured by BASF), Tris (3,5-di-tert-butylhydroxybenzyl) isocyanurate, thiodiethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] and the like can be mentioned.

As the polymerization inhibitor, one type may be used alone, or two or more types may be used in combination.
The content of the polymerization inhibitor may be appropriately determined according to the type of resin component, the use of the adhesive composition, and the environment in which it is used. For example, 0.1 to 10 mass by mass with respect to 100 parts by mass of the component (P). It is preferably a part.
When the content of the polymerization inhibitor is within the above-mentioned preferable range, the effect of suppressing polymerization is satisfactorily exhibited, and the chemical resistance of the adhesive layer is further enhanced after the high temperature process.

≪Polymerization initiator≫
The adhesive composition of the present embodiment may further contain a polymerization initiator.
The polymerization initiator refers to a component having a function of accelerating the polymerization reaction of the above-mentioned curable monomer.
Examples of the polymerization initiator include a thermal polymerization initiator and a photopolymerization initiator.
Examples of the thermal polymerization initiator include peroxides, azo-based polymerization initiators and the like.

Examples of the peroxide in the thermal polymerization initiator include ketone peroxides, peroxyketals, hydroperoxides, dialkyl peroxides, peroxyesters and the like. Specific examples of such peroxides include acetyl peroxide, dicumyl peroxide, tert-butyl peroxide, t-butylcumyl peroxide, propionyl peroxide, benzoyl peroxide (BPO), and 2-chlorobenzoyl peroxide. 3-Chlorobenzoyl peroxide, 4-chlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, 4-bromomethylbenzoyl peroxide, lauroyl peroxide, potassium persulfate, diisopropyl peroxycarbonate, tetraline hydroperoxide, 1-phenyl -2-Methylpropyl-1-hydroperoxide, pertriphenylacetate-tert-butyl, tert-butyl hydroperoxide, tert-butyl peroxide, tert-butyl peracetate, tert-butyl perbenzoate, tert-perphenylacetate Examples thereof include butyl, tert-butyl peroxide, and tert-butyl peroxide N- (3-toluyl) carbamate.

Examples of the peroxide include the trade name "Park Mill (registered trademark)", the trade name "Perbutyl (registered trademark)", the trade name "Parloyl (registered trademark)" and the trade name "Perocta" manufactured by Nippon Oil & Fat Co., Ltd. Commercially available products such as "(registered trademark)" can be used.

Examples of the azo-based polymerization initiator in the thermal polymerization initiator include 2,2'-azobispropane, 2,2'-dichloro-2,2'-azobispropane, and 1,1'-azo (methylethyl). Diacetate, 2,2'-azobis (2-amidinopropane) hydrochloride, 2,2'-azobis (2-aminopropane) nitrate, 2,2'-azobisisobutane, 2,2'-azobisisobutyamide , 2,2'-azobisisobutyronitrile, 2,2'-azobis-2-methylpropionate, 2,2'-dichloro-2,2'-azobisbutane, 2,2'-azobis-2- Methylbutyronitrile, dimethyl 2,2'-azobisisobutyrate, 1,1'-azobis (sodium 1-methylbutyronitrile-3-sulfonate), 2- (4-methylphenylazo) -2-methylmalonodi Nitrile 4,4'-azobis-4-cyanovaleric acid, 3,5-dihydroxymethylphenylazo-2-allylmalonodinitrile, 2,2'-azobis-2-methylvaleronitrile, 4,4'-azobis- Dimethyl 4-cyanovalerate, 2,2'-azobis-2,4-dimethylvaleronitrile, 1,1'-azobiscyclohexanenitrile, 2,2'-azobis-2-propylbutyronitrile, 1,1' -Azobisisobutyoxynitrile, 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'-azobisisobutymen, 4-nitrophenylazobenzylcyanoacetate, phenylazodiphenylmethane, phenylazotriphenylmethane, 4-nitro Phynoazotriphenylmethane, 1,1'-azobis-1,2-diphenylethane, poly (bisphenol A-4,4'-azobis-4-cyanopentanoate), poly (tetraethylene glycol-2,2' -Azobisisobutyrate) and the like.

Examples of the photopolymerization initiator include 1-hydroxycyclohexylphenylketone, 2-hydroxy-2-methyl-1-phenylpropan-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- Methylpropan-1-one, 2,2-dimethoxy-1,2-diphenylethane-1-one, bis (4-dimethylaminophenyl) ketone, 2-methyl-1- [4- (methylthio) phenyl] -2 -Molphorinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butane-1-one, etanone 1- [9-ethyl-6- (2-methylbenzoyl)) -9H-carbazole-3-yl] -1- (o-acetyloxime), 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 4-benzoyl-4'-methyldimethylsulfide, 4-dimethylaminobenzoic acid, 4 -Methyl dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, butyl 4-dimethylaminobenzoate, 4-dimethylamino-2-ethylhexyl benzoic acid, 4-dimethylamino-2-isoamylbenzoic acid, benzyl-β-methoxy Ethyl acetal, benzyl dimethyl ketal, 1-phenyl-1,2-propandion-2- (o-ethoxycarbonyl) oxime, methyl o-benzoyl benzoate, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4 -Dimethylthioxanthone, 1-chloro-4-propoxythioxanthone, thioxanthene, 2-chlorothioxanthene, 2,4-diethylthioxanthene, 2-methylthioxanthene, 2-isopropylthioxanthene, 2-ethylanthraquinone, octamethylanthraquinone, 1,2-Benz anthraquinone, 2,3-diphenylanthraquinone, azobisisobutyronitrile, benzoylperoxide, cumempaoxide, 2-mercaptobenzoimidal, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, 2- (O-Chlorophenyl) -4,5-diphenylimidazole dimer, 2- (o-chlorophenyl) -4,5-di (methoxyphenyl) imidazole dimer, 2- (o-fluorofe) Nyl) -4,5-diphenylimidazole dimer, 2- (o-methoxyphenyl) -4,5-diphenylimidazole dimer, 2- (p-methoxyphenyl) -4,5-diphenylimidazole dimer , 2,4,5-Triarylimidazole dimer, benzophenone, 2-chlorobenzophenone, 4,4'-bisdimethylaminobenzophenone (ie, Michler's ketone), 4,4'-bisdiethylaminobenzophenone (ie, ethyl Michlers) Ketone), 4,4'-dichlorobenzophenone, 3,3-dimethyl-4-methoxybenzophenone, benzyl, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin-n-butyl ether, benzoin isobutyl ether, benzoin- t-Butyl ether, acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, dichloroacetophenone, trichloroacetophenone, pt-butylacetophenone, p-dimethylaminoacetophenone, pt- Butyltrichloroacetophenone, pt-butyldichloroacetophenone, α, α-dichloro-4-phenoxyacetophenone, thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, dibenzosverone, pentyl-4-dimethylaminobenzoate, 9-phenyl Acrydin, 1,7-bis- (9-acridinyl) heptane, 1,5-bis- (9-acridinyl) pentane, 1,3-bis- (9-acridinyl) propane, p-methoxytriazine, 2,4 6-Tris (trichloromethyl) -s-triazine, 2-methyl-4,6-bis (trichloromethyl) -s-triazine, 2- [2- (5-methylfuran-2-yl) ethenyl] -4, 6-bis (trichloromethyl) -s-triazine, 2- [2- (fran-2-yl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (4-diethylamino) -2-Methylphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (3,4-dimethoxyphenyl) ethenyl] -4,6-bis (trichloromethyl) -s -Triazine, 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-ethoxysti) Lil) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-n-butoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2,4-bis-trichloromethyl -6- (3-Bromo-4-methoxy) phenyl-s-triazine, 2,4-bis-trichloromethyl-6- (2-bromo-4-methoxy) phenyl-s-triazine, 2,4-bis- Examples thereof include trichloromethyl-6- (3-bromo-4-methoxy) styrylphenyl-s-triazine and 2,4-bis-trichloromethyl-6- (2-bromo-4-methoxy) styrylphenyl-s-triazine. Be done.

Examples of the photopolymerization initiator include "IRGACURE OXE02", "IRGACURE OXE01", "IRGACURE 369", "IRGACURE 651", "IRGACURE 907" (trade names, all manufactured by BASF) and "NCI-831". Commercially available products such as (trade name, manufactured by ADEKA Corporation) can be used.

As the polymerization initiator, one type may be used alone, or two or more types may be used in combination.
As the polymerization initiator, a thermal polymerization initiator is preferable, and a peroxide is more preferable.
The polymerization initiator is preferably used in combination with a curable monomer. The amount of the polymerization initiator used may be adjusted according to the amount of the curable monomer used.
For example, in the adhesive composition of the present embodiment, the content ratio of the polymerization initiator is preferably 0.1 to 10 parts by mass, and 0.5 to 5 parts by mass with respect to 100 parts by mass of the curable monomer. Is more preferable.

≪Solvent component≫
The adhesive composition of the present embodiment can be prepared by dissolving the component (P) and, if necessary, an arbitrary component in a solvent component.
As the solvent component, for example, one that can dissolve each component for the adhesive composition to form a uniform solution can be used, one type may be used alone, or two or more types may be combined. You may use it.

Examples of the solvent component include hydrocarbon solvents and petroleum-based solvents.
The hydrocarbon solvent and the petroleum-based solvent are also collectively referred to as "(S1) component" below. A solvent component other than the component (S1) may be referred to as a “component (S2)”.

Examples of the hydrocarbon solvent include linear, branched or cyclic hydrocarbons, for example, linear hydrocarbons such as hexane, heptane, octane, nonane, methyloctane, decan, undecane, dodecane and tridecane. Branched chain hydrocarbons such as isooctane, isononan, isododecane; p-menthane, o-menthane, m-menthane, diphenylmenthane, 1,4-terpine, 1,8-terpine, bornan, norbornan, pinan, tsujan, Callan, Longihoren, α-terpinene, β-terpinene, γ-terpinene, α-pinene, β-pinene, α-tujon, β-tujon, cyclohexane, cycloheptane, cyclooctane, inden, pentalene, indan, tetrahydroinden, naphthalene , Tetrahydronaphthalene (tetraline), decahydronaphthalene (decalin) and other cyclic hydrocarbons.

The petroleum-based solvent is a solvent refined from heavy oil, and examples thereof include white kerosene, paraffin-based solvent, and isoparaffin-based solvent.

Examples of the component (S2) include a terpene solvent having an oxygen atom, a carbonyl group, an acetoxy group or the like as a polar group, and examples thereof include geraniol, nerol, linalool, citral, citronellol, menthol, isomenthol, neomenthol and α. -Terpineol, β-terpineol, γ-terpineol, terpinen-1-ol, terpine-4-ol, dihydroterpinyl acetate, 1,4-cineol, 1,8-cineol, borneol, carboxylic, yonon, tuyon, camphor And so on.

In addition, as the component (S2), lactones such as γ-butyrolactone; ketones such as acetone, methyl ethyl ketone, cyclohexanone (CH), methyl-n-pentyl ketone, methyl isopentyl ketone, 2-heptanone; ethylene glycol, diethylene glycol. , Polyvalent alcohols such as propylene glycol and dipropylene glycol; compounds having an ester bond such as ethylene glycol monoacetate, diethylene glycol monoacetate, propylene glycol monoacetate, or dipropylene glycol monoacetate, the polyvalent alcohols or the esters. Derivatives of polyhydric alcohols such as monomethyl ethers, monoethyl ethers, monopropyl ethers, monoalkyl ethers such as monobutyl ethers, and compounds having ether bonds such as monophenyl ethers (among these, propylene glycol). Monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME) are preferred); cyclic ethers such as dioxane; methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate, Esters such as methyl methoxypropionate and ethyl ethoxypropionate; aromatic organic solvents such as anisole, ethylbenzyl ether, cresylmethyl ether, diphenyl ether, dibenzyl ether, phenetol and butylphenyl ether can also be mentioned.

The content of the solvent component in the adhesive composition of the present embodiment may be appropriately adjusted according to the thickness of the adhesive layer to be formed. For example, with respect to the total amount (100% by mass) of the adhesive composition. It is preferably in the range of 20 to 90% by mass.
That is, the adhesive composition of the present embodiment preferably has a solid content (total amount of compounding components excluding the solvent component) concentration in the range of 10 to 80% by mass.
When the content of the solvent component is within the above-mentioned preferable range, the viscosity can be easily adjusted.

The adhesive composition of the present embodiment can be prepared by mixing and dissolving or dispersing each of the other components in the solvent component.
From the viewpoint of the solubility of the component (P), it is preferable to use a solvent component containing a hydrocarbon solvent, and more preferably a solvent component containing a branched chain hydrocarbon or a cyclic hydrocarbon solvent.
When the solvent component contains a branched chain or cyclic hydrocarbon solvent, it is easy to prevent white turbidity that may occur when the adhesive composition is stored in a liquid state (particularly at a low temperature), and the storage stability is further improved. Can be made to.

Further, as the solvent component, it is preferable to use a hydrocarbon solvent containing condensed polycyclic hydrocarbons or branched chain hydrocarbons. In this case, the solvent component may be only one selected from the group consisting of condensed polycyclic hydrocarbons and branched chain hydrocarbons, and may also contain other components such as saturated aliphatic hydrocarbons. May be.
The content of the solvent component selected from the group consisting of condensed polycyclic hydrocarbons and branched chain hydrocarbons is preferably 40 parts by mass or more, preferably 40 parts by mass or more, based on 100 parts by mass of the entire hydrocarbon solvent. It is more preferably parts by mass or more, and even more preferably 80 parts by mass or more. When it is 40 parts by mass or more of the entire hydrocarbon solvent, the solubility of the component (P) becomes better.

When a polymerization initiator is used, the polymerization initiator can be blended by a known method immediately before using the adhesive composition.
Further, the polymerization initiator or polymerization inhibitor may be blended in the form of a solution previously dissolved in the above component (S2). The amount of the component (S2) used may be appropriately adjusted according to the type of the polymerization initiator or the polymerization inhibitor. For example, 1 to 50 parts by mass is preferable with respect to 100 parts by mass of the component (S1). ~ 30 parts by mass is more preferable. When the amount of the component (S2) used is within the above-mentioned preferable range, the polymerization initiator or the polymerization inhibitor can be sufficiently dissolved.

In the adhesive composition of the present embodiment described above, the component (P) contains the component (P1), so that an adhesive layer having high heat resistance and high adhesion to the substrate can be formed. As a result, the adhesive layer formed by the adhesive composition of the present embodiment is less likely to cause misalignment of the substrate before and after the sealing operation, for example, due to the influence of the high temperature treatment during the manufacture of the semiconductor package.

Further, the adhesive layer formed by the adhesive composition of the present embodiment has a high gas barrier property, and therefore can be used as a gas barrier layer.
When a sealing substrate containing a resin is used, the water content in the resin is vaporized to generate gas. For example, as shown in FIG. 6A, when the support 12 and the sealing substrate 5 are bonded together using a conventional adhesive composition (for example, an elastomer-based adhesive), the adhesive composition is used. The formed adhesive layer 3'cannot suppress the migration of gas generated from the sealing substrate 5, and voids (foam) are generated between the sealing substrate 5 and the support 12. The void causes peeling between the sealing substrate 5 and the support 12.
On the other hand, the adhesive layer formed by the adhesive composition of the present embodiment has a high gas barrier property and good adhesion to the sealing substrate 5, and therefore effectively blocks the gas generated from the sealing substrate 5. be able to. Therefore, as shown in FIG. 6B, the adhesive layer 3 containing the first adhesive composition layer 3-1 formed by the adhesive composition of the present embodiment is provided with the sealing substrate 5 and the support 12. By forming between the adhesive composition layer 3-1 and the adhesive composition layer 3-1 as a gas barrier layer, the generation of voids can be suppressed.
The adhesive composition of the present embodiment may be used alone or in combination with another adhesive composition (adhesive composition containing no component (P1)). A second adhesive composition layer 3-2 is formed using another adhesive composition, and the first adhesive composition layer 3-1 and the second adhesive composition layer 3-2 are separated from each other. The adhesive layer 3 may be formed. When used in combination with other adhesive compositions, as shown in FIG. 6B, the sealing substrate 5, the first adhesive adhesive layer 3-1 and the second adhesive adhesive layer 3-2, and the support. It is preferable that the body 12 forms a laminated body in which the bodies 12 are laminated in this order. By arranging the sealing substrate 5 and the first adhesive adhesive layer 3-1 adjacent to each other, the first adhesive adhesive layer 3-1 becomes a gas barrier layer, and voids are generated from the sealing substrate 5. It can be effectively suppressed.

Further, the adhesive layer formed by the adhesive composition of the present embodiment can be used as a protection layer because misalignment is unlikely to occur.
For example, a thin film may be formed on the adhesive layer to form the rewiring layer. FIG. 7A is an example in which the adhesive layer 3'is formed on the support 12 and the thin film 6 is formed on the adhesive layer 3'using the conventional adhesive composition. In this case, if the heat resistance of the adhesive layer 3'is low, the adhesive layer 3'flows due to the high temperature treatment, and cracks or wrinkles may occur in the thin film 6.
On the other hand, the adhesive layer formed by the present embodiment has high heat resistance and is less likely to flow due to high temperature treatment. Therefore, as shown in FIG. 7B, the adhesive layer 3 containing the first adhesive composition layer 3-1 formed by the adhesive composition of the present embodiment is formed by the support 12 and the thin film 6. By forming between them, the first adhesive composition layer 3-1 serves as a protection layer, and the occurrence of cracks and wrinkles in the thin film 6 can be suppressed. Further, since the first adhesive composition layer has high adhesion to the thin film 6, peeling of the thin film 6 is unlikely to occur.
The adhesive composition of the present embodiment may be used alone or in combination with other adhesive compositions. A second adhesive composition layer 3-2 is formed using another adhesive composition, and the first adhesive composition layer 3-1 and the second adhesive composition layer 3-2 are separated from each other. The adhesive layer 3 may be formed. When used in combination with other adhesives, as shown in FIG. 7B, the support 12, the second adhesive composition layer 3-2, the first adhesive composition layer 3-1 and the thin film 6 However, it is preferable to form a laminated body laminated in this order. By arranging the thin film 6 and the adhesive layer 3-1 adjacent to each other, the first adhesive composition layer 3-1 becomes a protection layer and effectively suppresses cracks, wrinkles, peeling, etc. of the thin film 6. be able to.

Further, for example, die bonding may be performed on the bump substrate. FIG. 8A is an example in which the support 12 and the bump substrate 4 are bonded to each other using a conventional adhesive composition, and die bonding is performed on the bump substrate 4. In this case, if the heat resistance of the adhesive layer 3'formed by the conventional adhesive composition is low, the adhesive layer 3'sinks during die bonding, the bumps come into contact with the support 12, and the bumps are deformed. Sometimes.
On the other hand, the adhesive layer formed by the present embodiment has high heat resistance, and re-subduction of die bonding is unlikely to occur. Therefore, as shown in FIG. 8B, the adhesive layer 3 containing the first adhesive composition layer 3-1 formed by the adhesive composition of the present embodiment is provided with the support 12 and the bump substrate 4. By forming between the two, the first adhesive composition layer 3-1 becomes a protection layer, and the contact between the bump and the support 12 at the time of die bonding can be suppressed. Further, since the first adhesive composition layer 3-1 has high adhesion to the bump substrate 4, peeling of the bump substrate 4 is unlikely to occur.
The adhesive composition of the present embodiment may be used alone or in combination with other adhesive compositions. A second adhesive composition layer 3-2 is formed using another adhesive composition, and the first adhesive composition layer 3-1 and the second adhesive composition layer 3-2 are separated from each other. The adhesive layer 3 may be formed. When used in combination with other adhesives, as shown in FIG. 8B, the support 12, the second adhesive composition layer 3-2, the first adhesive composition layer 3-1 and the bump substrate. It is preferable that 4 forms a laminated body laminated in this order. By arranging the bump substrate 4 and the first adhesive composition layer 3-1 adjacent to each other, the first adhesive composition layer 3-1 becomes a protection layer, effectively sinking the bump substrate. It can be suppressed.

In the above, examples of other adhesive compositions include elastomer-based adhesive compositions, cycloolefin-based adhesive compositions, maleimide-based adhesive compositions, and the like.

In FIGS. 6 to 8, the support 12 may be composed of a support substrate that transmits light and a separation layer provided on the support substrate.

(Laminated body)
In the laminate according to the second aspect of the present invention, the support and the substrate are bonded to each other via an adhesive layer.
As shown in FIG. 1, the laminated body 10 of the present embodiment has a support 12 and a substrate 4 bonded together via an adhesive layer 3, that is, a support 123 with an adhesive layer and a support with an adhesive layer. It is provided with a substrate 4 arranged on a surface 3s on the side opposite to the support 12 side of the adhesive layer 3 included in the 123.

<Support>
The support 12 in FIG. 1 includes a support base 1 and a separation layer 2 provided on the support base 1.

≪Supporting base≫
The support substrate has the property of transmitting light. The support substrate is a member that supports the substrate and is attached to the substrate via an adhesive layer. Therefore, it is preferable that the support substrate has the strength necessary to prevent the substrate from being damaged or deformed when the encapsulant is thinned, the substrate is transported, or the substrate is mounted on the substrate. Further, the support substrate preferably transmits light having a wavelength capable of altering the separation layer.
As the material of the support substrate, for example, glass, silicon, acrylic resin and the like are used. Examples of the shape of the support substrate include, but are not limited to, a rectangle, a circle, and the like.
Further, as the support substrate, in order to further increase the density and improve the production efficiency, a circular support substrate with a larger size or a large panel having a quadrangular shape in a plan view can be used.

≪Separation layer≫
The separation layer is a layer adjacent to the adhesive layer, which is altered by irradiation with light to enable the support substrate to be separated from the substrate bonded to the support.
This separation layer can be formed by using the composition for forming a separation layer described later, for example, by calcining the components contained in the composition for forming a separation layer, or by a chemical vapor deposition (CVD) method. It is formed. This separation layer is suitably denatured by absorbing the light transmitted through the support substrate and irradiated.
The separation layer is preferably formed only from a material that absorbs light, but a material that does not have a structure that absorbs light is blended within a range that does not impair the essential properties of the present invention. It may be a layer.

The term "deterioration" of the separation layer means a phenomenon in which the separation layer can be destroyed by receiving an external force or a state in which the adhesive force between the separation layer and the layer in contact with the separation layer is reduced. The separation layer becomes brittle by absorbing light and loses its strength or adhesiveness before being irradiated with light. Such alteration of the separation layer occurs by causing decomposition by the energy of absorbed light, change in configuration, dissociation of functional groups, and the like.

The thickness of the separation layer is preferably in the range of, for example, 0.05 μm or more and 50 μm or less, and more preferably in the range of 0.3 μm or more and 1 μm or less.
When the thickness of the separation layer is within the range of 0.05 μm or more and 50 μm or less, the separation layer can be subjected to desired alteration by short-time light irradiation and low-energy light irradiation. Further, the thickness of the separation layer is particularly preferably in the range of 1 μm or less from the viewpoint of productivity.

The surface of the separation layer on the side in contact with the adhesive layer is preferably flat (no unevenness is formed), whereby the adhesive layer can be easily formed and the support substrate and the substrate are uniformly adhered to each other. It will be easy to attach.

[Composition for forming a separation layer]
The composition for forming a separation layer, which is a material for forming a separation layer, is, for example, fluorocarbon, a polymer having a repeating unit including a structure having light absorption, an inorganic substance, or a compound having an infrared absorption structure. , Inorganic absorbent, reactive polysilsesquioxane, or those containing a resin component having a phenolic skeleton.
Further, the composition for forming a separation layer improves the separability of a filler, a plasticizer, a thermoacid generator component, a photoacid generator component, an organic solvent component, a surfactant, a sensitizer, or a support substrate as optional components. It may contain a possible component or the like.

-The fluorocarbon separation layer may contain fluorocarbon. The separation layer composed of fluorocarbons is adapted to be altered by absorbing light, and as a result, loses strength or adhesiveness before being irradiated with light. Therefore, by applying a slight external force (for example, lifting the support), the separation layer is broken, and the support and the substrate can be easily separated. The fluorocarbon constituting the separation layer can be suitably formed by a plasma CVD method.
Fluorocarbons absorb light with wavelengths in a unique range depending on the type. By irradiating the separation layer with light having a wavelength within the range absorbed by the fluorocarbon used for the separation layer, the fluorocarbon can be suitably altered. The light absorption rate in the separation layer is preferably 80% or more.

The light irradiated to the separation layer, in accordance with the fluorocarbon wavelength absorbable, for example, YAG laser, ruby laser, glass laser, YVO ₄ laser, LD laser, a solid laser such as a fiber laser, a liquid laser dye laser, , CO ₂ laser, excimer laser, Ar laser, gas laser such as He-Ne laser, laser light such as semiconductor laser, free electron laser, or non-laser light may be appropriately used. As the wavelength capable of altering the fluorocarbon, for example, a wavelength in the range of 600 nm or less can be used.

-Polymer having a repeating unit including a structure having a light absorption The separation layer may contain a polymer having a repeating unit including a structure having a light absorption. The polymer is altered by being irradiated with light. ..
Examples of the structure having light absorption include an atomic group containing a conjugated π-electron system composed of a substituted or unsubstituted benzene ring, a condensed ring or a heterocycle. More specifically, the structure having light absorption is a cardo structure, or a benzophenone structure, a diphenyl sulfoxide structure, a diphenyl sulfone structure (bisphenyl sulfone structure), or a diphenyl present in the side chain of the polymer. The structure or the diphenylamine structure can be mentioned.
The above-mentioned structure having light absorption ability can absorb light having a wavelength in a desired range depending on the type thereof. For example, the wavelength of light that can be absorbed by the above-mentioned structure having light absorption is preferably in the range of 100 to 2000 nm, and more preferably in the range of 100 to 500 nm.

The light that can be absorbed by the above-mentioned light-absorbing structure is, for example, a high-pressure mercury lamp (wavelength 254 nm or more and 436 nm or less), KrF excimer laser (wavelength 248 nm), ArF excimer laser (wavelength 193 nm), F ₂ Light emitted from an excimer laser (wavelength 157 nm), XeCl laser (wavelength 308 nm), XeF laser (wavelength 351 nm) or solid UV laser (wavelength 355 nm), or g-line (wavelength 436 nm), h-line (wavelength 405 nm) or i-line. (Wavelength 365 nm) and the like.

-Inorganic substance The separation layer may be made of an inorganic substance. The inorganic substance may be any one that is altered by absorbing light, and for example, one or more kinds selected from the group consisting of metals, metal compounds and carbons are preferably mentioned. The metal compound is a compound containing a metal atom, and examples thereof include metal oxides and metal nitrides.
Such inorganic, gold, silver, copper, iron, nickel, aluminum, titanium, _{chromium, SiO 2, SiN, Si 3} N 4, TiN, and one or more selected from the group consisting of carbon and the like.
Note that carbon is a concept that may include allotropes of carbon, and includes, for example, diamond, fullerene, diamond-like carbon, carbon nanotubes, and the like.
The inorganic substance absorbs light having a wavelength in a unique range depending on the type.

The light irradiated to the separation layer made of an inorganic substance, depending on the wavelength capable of absorbing the inorganic material, for example, YAG laser, ruby laser, glass laser, YVO ₄ laser, LD laser, a solid laser such as a fiber laser, a dye laser Liquid lasers such as, CO ₂ lasers, excimer lasers, Ar lasers, gas lasers such as He-Ne lasers, laser beams such as semiconductor lasers and free electron lasers, or non-laser lasers may be appropriately used.
The separation layer made of an inorganic substance can be formed on the support substrate by a known technique such as sputtering, chemical vapor deposition (CVD), plating, plasma CVD, spin coating and the like.

-Compound having an infrared absorbing structure The separation layer may contain a compound having an infrared absorbing structure. This compound having an infrared absorbing structure is altered by absorbing infrared rays.
Examples of the structure having infrared absorption or the compound having this structure include alkane, alkene (vinyl, trans, cis, vinylidene, trisubstituted, tetrasubstituted, conjugated, cumlen, cyclic), and alkyne (1). Substitution, di-substituted), monocyclic aromatics (benzene, mono-substituted, di-substituted, tri-substituted), alcohols or phenols (free OH, intramolecular hydrogen bonds, intermolecular hydrogen bonds, saturated secondary, saturated tertiary) Class, unsaturated secondary, unsaturated tertiary), acetal, ketal, aliphatic ether, aromatic ether, vinyl ether, oxylan ring ether, peroxide ether, ketone, dialkylcarbonyl, aromatic carbonyl, 1,3 -Diketone enol, o-hydroxyarylketone, dialkylaldehyde, aromatic aldehyde, carboxylic acid (dimer, carboxylic acid anion), formic acid ester, acetic acid ester, conjugated ester, non-conjugated ester, aromatic ester, lactone (β) -, Γ-, δ-), aliphatic acidate, aromatic acidate, acid anhydride (conjugated, non-conjugated, cyclic, acyclic), primary amide, secondary amide, lactam, Primary amine (aliphatic, aromatic), secondary amine (aliphatic, aromatic), tertiary amine (aliphatic, aromatic), primary amine salt, secondary amine salt, tertiary Secondary amine salts, ammonium ions, aliphatic nitriles, aromatic nitriles, carbodiimides, aliphatic isonitriles, aromatic isonitriles, isocyanic acid esters, thiocyanic acid esters, aliphatic isothiocyanate esters, aromatic isothiocyanate esters, aliphatic nitro compounds, Aromatic nitro compounds, nitroamines, nitrosoamines, nitrates, nitrites, nitroso bonds (aliphatic, aromatics, monomers, dimers), sulfur compounds such as mercaptans or thiophenols or thiolic acids, thiocarbonyl groups, Sulfoxide, sulfone, sulfonyl chloride, primary sulfonamide, secondary sulfonamide, sulfate ester, carbon-halogen bond, Si-A ¹ bond (A ¹ is H, C, O or halogen), PA ² Bonds (A ² is H, C or O) or Ti-O bonds can be mentioned.

Examples of the structure containing a carbon-halogen bond include -CH ₂ Cl, -CH ₂ Br, -CH ₂ I, -CF _{2- , -CF 3} , -CH = CF ₂ , -CF = CF ₂ , and fluorine. Aryl boulders, aryl chlorides and the like can be mentioned.

As a structure containing ^{Si-A 1} bond described above, for _{example, SiH, SiH 2, SiH 3} , Si-CH 3, Si-CH 2 -, Si-C 6 H 5, SiO- aliphatic, Si-OCH ₃ , Si-OCH ₂ CH ₃ , Si-OC ₆ H ₅ , Si-O-Si, Si-OH, SiF, SiF ₂ or SiF _{3 and the} like. As the structure containing the Si—A ¹ bond, it is particularly preferable to form a siloxane skeleton or a silsesquioxane skeleton.

Examples of the ^{structure containing the PA 2} bond include PH, PH ₂ , P-CH ₃ , P-CH _2- , P-C ₆ H ₅ , A ³ ₃ -PO (A ³ is a fat). Group group or aromatic group), (A ⁴ O) _3- P-O (A ⁴ is an alkyl group), P-OCH ₃ , P-OCH ₂ CH ₃ , P-OC ₆ H ₅ , P-O-P , P-OH or O = P-OH and the like.

Examples of the above-mentioned compound containing a Ti—O bond include (i) tetra-i-propoxytitanium, tetra-n-butoxytitanium, tetrakis (2-ethylhexyloxy) titanium, titanium-i-propoxyoctylene glycolate and the like. Alkoxytitanium; (ii) di-i-propoxybis (acetylacetonato) titanium or chelated titanium such as propanedioxytitanium bis (ethylacetacetate); (iii) i-C ₃ H ₇ O-[-Ti ( O-i-C ₃ H ₇ ) _2- O-] _n- i-C ₃ H ₇ or n-C ₄ H ₉ O- [-Ti (On-C ₄ H ₉ ) _2- O-] _n titanium polymers such _{-n-C 4 H 9; (} iv) tri -n- butoxy titanium monostearate, titanium stearate, di -i- propoxytitanium diisostearate or (2-n-butoxycarbonyl benzoyloxy) Achillated titanium such as tributoxytitanium; and water-soluble titanium compounds such as (v) di-n-butoxy-bis (triethanolaminato) titanium can be mentioned.
Among them, as a compound containing a Ti—O bond, di-n-butoxy-bis (triethanolamineto) titanium (Ti (OC ₄ H ₉ ) ₂ [OC ₂ H ₄ N (C ₂ H ₄ OH) ₂ ]] ₂ ) is preferable.

The above-mentioned infrared-absorbing structure can absorb infrared rays having a wavelength in a desired range, depending on the type of selection. Specifically, the wavelength of infrared rays that can be absorbed by the above-mentioned infrared-absorbing structure is, for example, in the range of 1 to 20 μm, and more preferably in the range of 2 to 15 μm.
Further, when the structure is a Si—O bond, a Si—C bond or a Ti—O bond, the range is preferably in the range of 9 to 11 μm.

A person skilled in the art can easily understand the wavelength of infrared rays that can be absorbed by each of the above structures. For example, as an absorption band in each structure, Non-Patent Documents: SILVERSTEIN, BASSLER, MORRRILL, "Identification method by spectrum of organic compounds (5th edition) -Combination of MS, IR, NMR, UV-" (published in 1992) References can be made to the description on pages 146 to 151.

As a compound having an infrared absorbing structure used for forming a separation layer, among the compounds having the above-mentioned structure, the compound can be dissolved in a solvent for coating and solidified to form a solid layer. Is not particularly limited as long as it can form. However, in order to effectively alter the compound in the separation layer and facilitate the separation between the support substrate and the substrate, the absorption of infrared rays in the separation layer is large, that is, the infrared rays when the separation layer is irradiated with infrared rays. It is preferable that the transmittance is low. Specifically, the infrared transmittance in the separation layer is preferably lower than 90%, and the infrared transmittance is more preferably lower than 80%.

-Infrared absorbing substance The separation layer may contain an infrared absorbing substance. The infrared absorbing substance may be any substance that is altered by absorbing light, and for example, carbon black, iron particles, or aluminum particles can be preferably used.
Infrared absorbers absorb light with wavelengths in a unique range depending on the type. By irradiating the separation layer with light having a wavelength within the range absorbed by the infrared absorbing substance used for the separation layer, the infrared absorbing substance can be suitably altered.

-The reactive polysilsesquioxane separation layer can be formed by polymerizing the reactive polysilsesquioxane. The separation layer formed thereby has high chemical resistance and high heat resistance.

"Reactive polysilsesquioxane" refers to polysilsesquioxane having a silanol group at the end of the polysilsesquioxane skeleton or a functional group capable of forming a silanol group by hydrolysis. .. By condensing the silanol group or a functional group capable of forming a silanol group, they can be polymerized with each other. Further, if the reactive polysilsesquioxane has a silanol group or a functional group capable of forming a silanol group, it can form a silsesquioxane skeleton having a random structure, a cage-shaped structure, a ladder structure or the like. Reactive polysilsesquioxane provided can be adopted.

The siloxane content of the reactive polysilsesquioxane is preferably 70 to 99 mol%, more preferably 80 to 99 mol%.
If the siloxane content of the reactive polysilsesquioxane is within the above-mentioned preferable range, it can be suitably altered by irradiating with infrared rays (preferably far-infrared rays, more preferably light having a wavelength of 9 to 11 μm). A possible separation layer can be formed.

The weight average molecular weight (Mw) of the reactive polysilsesquioxane is preferably 500 to 50,000, more preferably 1,000 to 10,000.
If the weight average molecular weight (Mw) of the reactive polysilsesquioxane is within the above-mentioned preferable range, it can be suitably dissolved in a solvent and can be suitably applied on a support plate.

Examples of commercially available products that can be used as the reactive polysilsesquioxane include SR-13, SR-21, SR-23 and SR-33 (trade name) manufactured by Konishi Chemical Industry Co., Ltd.

-Resin component having a phenol skeleton The separation layer may contain a resin component having a phenol skeleton. By having a phenol skeleton, it is easily altered (oxidized, etc.) by heating or the like, and photoreactivity is enhanced.
As used herein, "having a phenol skeleton" means that it contains a hydroxybenzene structure.
The resin component having a phenol skeleton has a film-forming ability, and preferably has a molecular weight of 1000 or more. When the molecular weight of the resin component is 1000 or more, the film forming ability is improved. The molecular weight of the resin component is more preferably 1000 to 30,000, further preferably 1500 to 20000, and particularly preferably 2000 to 15000. When the molecular weight of the resin component is not more than the upper limit of the above-mentioned preferable range, the solubility of the composition for forming a separation layer in a solvent is enhanced.
As the molecular weight of the resin component, the polystyrene-equivalent weight average molecular weight (Mw) by GPC (gel permeation chromatography) is used.

Examples of the resin component having a phenol skeleton include a novolak type phenol resin, a resol type phenol resin, a hydroxystyrene resin, a hydroxyphenyl silsesquioxane resin, a hydroxybenzyl silsesquioxane resin, a phenol skeleton-containing acrylic resin, and a general formula described later. Examples thereof include a resin having a repeating unit represented by (P2). Among these, novolak type phenol resin and resol type phenol resin are more preferable.

<Adhesive layer>
The adhesive layer 3 is a layer for bonding the support 12 and the substrate 4, and can be formed by using the adhesive composition according to the first aspect.

The adhesive layer 3 includes a first adhesive composition layer formed by using the adhesive composition according to the first aspect. Further, the adhesive layer 3 may include, in addition to the first adhesive composition layer, a second adhesive composition layer formed by using another adhesive composition. In this case, the first adhesive composition layer is preferably adjacent to the substrate 4. By arranging the first adhesive composition layer adjacent to the substrate 4, the adhesion between the adhesive layer 3 and the substrate 4 can be further enhanced. The adhesive composition forming the second adhesive composition layer is an adhesive composition containing no polymer (P1). Such an adhesive composition is not particularly limited, and examples thereof include an elastomer-based adhesive composition, a cycloolefin-based adhesive composition, and a maleimide-based adhesive composition.

When the adhesive layer 3 has a first adhesive composition layer and a second adhesive composition layer, the thickness of the first adhesive composition layer is, for example, 0.1 μm or more and 50 μm or less. It is preferably within the range, more preferably within the range of 5 μm or more and 40 μm or less, further preferably within the range of 10 μm or more and 30 μm or less, and further preferably within the range of 15 μm or more and 25 μm or less. Especially preferable. When the thickness of the first adhesive composition layer is at least the lower limit of the preferable range, the gas barrier performance or the protection performance of the substrate or the like is further improved. Further, when the thickness of the first adhesive composition layer is not more than the upper limit of the preferable range, it does not interfere with the subsequent removal step.
When the adhesive layer 3 has a first adhesive composition layer and a second adhesive composition layer, the thickness of the second adhesive composition layer is, for example, 0.1 μm or more and 100 μm or less. It is preferably within the range, more preferably within the range of 1 μm or more and 50 μm or less, and further preferably within the range of 10 μm or more and 40 μm or less. When the thickness of the second adhesive layer is within the above-mentioned preferable range, the support and the substrate can be better bonded to each other.

When the adhesive layer 3 is composed of only the first adhesive composition layer, the thickness of the adhesive layer 3 is preferably in the range of 0.1 μm or more and 50 μm or less, and preferably in the range of 1 μm or more and 10 μm or less. It is more preferable to be inside. When the thickness of the adhesive layer 3 is within the range of 0.1 μm or more and 50 μm or less, the support substrate 1 and the substrate 4 can be better bonded to each other. Further, when the thickness of the adhesive layer is 1 μm or more, the substrate can be sufficiently fixed on the support substrate, and when the thickness of the adhesive layer is 10 μm or less, the adhesive layer is provided in a later removal step. It can be easily removed.

<Board>
The substrate 4 is subjected to processes such as thinning and mounting while being supported by the support 12. Structures such as integrated circuits and metal bumps are mounted on the substrate 4.
As the substrate 4, a silicon wafer substrate is typically used, but the substrate 4 is not limited to this, and a ceramic substrate, a thin film substrate, a flexible substrate, or the like may be used.

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

Since the laminated body of the present embodiment is provided with an adhesive layer to which the composition for forming an adhesive layer according to the first aspect is applied, it has high heat resistance and good adhesion to a substrate. As a result, when manufacturing a semiconductor package, the position of the substrate is less likely to shift before and after the sealing operation due to the influence of the high temperature treatment. Further, the substrate is less likely to be peeled off.

In the laminate of the above-described embodiment, the support substrate 1 and the separation layer 2 are adjacent to each other, but the present invention is not limited to this, and another layer is further formed between the support substrate 1 and the separation layer 2. You may. In this case, the other layer may be composed of a material that transmits light. According to this, it is possible to appropriately add a layer that imparts preferable properties to the laminated body 10 without hindering the incident of light on the separation layer 2. The wavelength of light that can be used differs depending on the type of material constituting the separation layer 2. Therefore, the material constituting the other layer does not need to transmit light of all wavelengths, and can be appropriately selected from the materials transmitting light having a wavelength capable of altering the material constituting the separation layer 2.

In other embodiments, the present invention may be a support with an adhesive layer. The support with an adhesive layer includes a support to which a substrate is bonded and an adhesive layer formed on the support using the adhesive composition according to the first aspect. .. The support and the adhesive layer are the same as those described above.

Further, in another embodiment, the present invention may be a film with an adhesive layer. The film with an adhesive layer includes a film and an adhesive layer formed on the film by using the adhesive composition according to the first aspect. By applying such an adhesive film, an adhesive layer can be suitably formed on the support. Compared with the case where the adhesive composition is directly applied onto the support to form the adhesive layer, the adhesive layer having good film thickness uniformity and surface smoothness can be easily formed.

Examples of the film include a release film in which the adhesive layer formed on the film can be easily peeled off from the film, and the adhesive layer can be transferred onto a surface to be treated such as a support.
Specific examples of the film include synthetic resin films such as polyethylene terephthalate, polyethylene, polypropylene, polycarbonate and polyvinyl chloride, and a flexible film is more preferable.
If necessary, the film is preferably subjected to a mold release treatment so as to facilitate transfer.
The thickness of the film may be appropriately set, for example, 15 to 125 μm.

Such an adhesive film is produced by forming an adhesive layer on the film. The adhesive layer may include a first adhesive composition layer as in the laminate of the above embodiment, and the first adhesive composition layer and the second adhesive composition layer are combined. It may include. For example, a method of applying the adhesive composition on the film is used so that the dry film thickness of the adhesive layer is 10 to 1000 μm. At that time, a known method can be appropriately used depending on the desired film thickness and uniformity of the adhesive layer.

Further, the adhesive film may be protected by covering the exposed surface of the adhesive layer with a protective film. The protective film is not limited as long as it can be peeled off from the adhesive layer, and for example, a polyethylene terephthalate film, a polypropylene film, and a polyethylene film are preferable. Further, each protective film is preferably coated with silicone or baked in order to facilitate peeling from the adhesive layer.

The method of using the adhesive film is, for example, when a protective film is used, the protective film is peeled off, and then an exposed adhesive layer is superposed on the support surface on the film (the back surface of the surface on which the adhesive layer is formed). ), A method of thermocompression bonding the adhesive layer to the surface of the support can be mentioned.
The protective film peeled off from the adhesive film can be reused by sequentially winding it in a roll shape with a roller such as a winding roller.

(Manufacturing method of laminated body)
A third aspect of the present invention is a method for manufacturing a laminated body in which a support and a substrate are bonded to each other via an adhesive layer, and includes an adhesive layer forming step and a bonding step.

<First Embodiment>
The method for producing a laminated body according to the first embodiment includes a step of producing a support, a step of forming an adhesive layer, and a step of laminating.
FIG. 2 is a schematic process diagram illustrating an embodiment of a method for manufacturing a laminated body.
FIG. 2A is a diagram for explaining a process of manufacturing a support, FIG. 2B is a diagram for explaining an adhesive layer forming process, and FIG. 2C is a diagram for explaining a bonding process. It is a figure to do.
In the method for producing a laminate of the present embodiment, a composition containing fluorocarbon is used as the composition for forming a separation layer. Further, as the composition for forming an adhesive layer, a composition containing the component (P1) according to the first aspect is used to form an adhesive layer containing the first adhesive composition layer.

≪Process to make support≫
The step of producing the support in the embodiment is a step of forming a separation layer on one side of the support substrate using the composition for forming a separation layer to obtain the support.
In FIG. 2A, a separation layer 2 is formed on the support substrate 1 by using a composition for forming a separation layer (containing fluorocarbon) (that is, a support substrate with a separation layer is produced). There is).

The method for forming the separation layer 2 on the support substrate 1 is not particularly limited, and examples thereof include methods such as spin coating, dipping, roller blades, spray coating, slit coating, and chemical vapor deposition (CVD).
For example, in the step of producing the support, the solvent component is removed from the coating layer of the separation layer forming composition coated on the support substrate 1 under a heating environment or a reduced pressure environment to form a film or support. A support is obtained by forming a film on the substrate 1 by a vapor deposition method.

≪Adhesive layer forming process≫
The adhesive layer forming step in the embodiment is a step of forming an adhesive layer on one side of the support. The adhesive layer includes a first adhesive composition layer formed by using the adhesive layer forming composition according to the first aspect.
In FIG. 2B, an adhesive layer 3 including a first adhesive composition layer formed by using the adhesive composition according to the first aspect is formed on the surface of the support 12 on the separation layer 2 side. (That is, the support 123 with an adhesive layer is made).

The method for forming the adhesive layer 3 on the support 12 is not particularly limited, and examples thereof include methods such as spin coating, dipping, roller blades, spray coating, and slit coating. Then, the adhesive composition is applied onto the support 12 and heated, or the solvent component contained in the adhesive composition is removed under a reduced pressure environment.

After that, when the adhesive layer contains a curable monomer and a thermal polymerization initiator, it is preferable to polymerize the curable monomer by heating. The conditions for heating the adhesive layer 3 may be appropriately set based on the 1-minute half-temperature and the 1-hour half-temperature of the thermal polymerization initiator. For example, at a temperature in the range of 50 to 300 ° C., under vacuum or nitrogen. It is preferably performed in an inert gas atmosphere such as gas, and more preferably in an inert gas atmosphere.

When the adhesive layer contains a curable monomer and a photopolymerization initiator, it is preferable to polymerize the curable monomer by exposing it in an atmosphere of an inert gas such as nitrogen gas. The exposure conditions may be appropriately set according to the type of photopolymerization initiator and the like.

The adhesive layer 3 may include a second adhesive composition layer formed by using another adhesive composition. The other adhesive composition is an adhesive composition that does not contain the component (P1). In this case, a second adhesive composition layer is formed on the surface of the support 12 on the separation layer 2 side using another adhesive composition, and then a second adhesive composition layer is formed on the second adhesive composition layer. The adhesive layer 3 can be formed by forming the first adhesive composition layer using the adhesive composition according to the first aspect.

[Lasting process]
The bonding step in the embodiment is a step of bonding the support and the substrate via the adhesive layer formed in the adhesive layer forming step.
In FIG. 2C, the support base 1 (support 12) on which the separation layer 2 is formed and the substrate 4 on which the separation layer 2 is not formed are laminated via the adhesive layer 3, and the support base 1 A laminated body 10 in which the separation layer 2, the adhesive layer 3, and the substrate 4 are stacked in this order is obtained.

In the method of bonding the support 12 and the substrate 4 via the adhesive layer 3, the substrate 4 is placed at a predetermined position on the adhesive layer 3 and supported by a die bonder or the like while being heated under vacuum (for example, about 100 ° C.). This is done by crimping the body 12 and the substrate 4.

According to the method for producing a laminated body of the first embodiment, an adhesive layer including a first adhesive composition layer formed by using the adhesive layer forming composition according to the first aspect is provided, so that the adhesive layer is adhered. The layer has high heat resistance and good adhesion to the substrate. Therefore, for example, the position of the substrate is less likely to shift before and after the sealing operation, and the substrate is less likely to be peeled off.

In the method for producing a laminated body of the present embodiment described above, the separation layer 2 is formed on the support substrate 1, but the present invention is not limited to this, and the separation layer 2 may be formed on the substrate 4.
Further, the separation layer 2 may be formed on both the support substrate 1 and the substrate 4, and in this case, the support substrate 1 and the substrate 4 are interposed via the separation layer 2, the adhesive layer 3 and the separation layer 2. Will be pasted together.

In the method for producing a laminated body of the present embodiment described above, the adhesive layer 3 is formed on the separation layer 2, but the present invention is not limited to this, and the adhesive layer 3 may be formed on the substrate 4. When the adhesive layer 3 contains a second adhesive composition layer in addition to the first adhesive composition layer, the first adhesion is performed on the substrate 4 using the adhesive composition according to the first aspect. The adhesive layer 3 is formed by forming an agent composition layer and then forming a second adhesive composition layer on the first adhesive composition layer using another adhesive composition. be able to.

<Second Embodiment>
FIG. 3 is a schematic process diagram illustrating another embodiment of the method for manufacturing a laminated body.
FIG. 3A is a diagram showing a laminate produced by the production method of the first embodiment, and FIG. 3B is a diagram illustrating a sealing process.
The method for producing a laminated body of the other embodiment further includes a sealing step in addition to a step of producing a support, a step of forming an adhesive layer, and a step of laminating.

[Sealing process]
The sealing step in the embodiment is a step of producing a sealed body by sealing the substrate bonded to the support via the adhesive layer with a sealing material after the bonding step.
In FIG. 3B, a sealing body 20 (laminated body) is obtained in which the entire substrate 4 arranged on the adhesive layer 3 is sealed with a sealing material.

In the sealing step, for example, a sealing material heated to 130 to 170 ° C. is supplied onto the adhesive layer 3 so as to cover the substrate 4 while maintaining a high viscosity state, and is compression-molded. , A sealing body 20 (laminated body) in which the sealing material layer 5 is provided on the adhesive layer 3 is produced.
At that time, the temperature condition is, for example, 130 to 170 ° C.
The pressure applied to the substrate 4 is, for example, 50 to 500 N / cm ² .

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

According to the method for producing a laminate of the second embodiment, since the adhesive layer is provided by applying the adhesive layer forming composition of the above-described embodiment, the heat resistance is further enhanced, for example, before and after the sealing operation. The position of the substrate is less likely to shift.

<Third Embodiment>
FIG. 4 is a schematic process diagram illustrating another embodiment of the method for manufacturing a laminated body.
FIG. 4A is a diagram showing a sealed body produced by the production method of the second embodiment, FIG. 4B is a diagram for explaining a grinding process, and FIG. 4C is a diagram showing a grinding process. It is a figure explaining the rewiring formation process.
The method for producing a laminated body of the other embodiment includes a grinding step and a rewiring forming step in addition to a support manufacturing step, an adhesive layer forming step, a bonding step and a sealing step.

≪Grinding process≫
The grinding step in the embodiment is a step of grinding the sealing material portion (sealing material layer 5) in the sealing body 20 so that a part of the substrate 4 is exposed after the sealing step.
The encapsulant portion is ground by, for example, as shown in FIG. 4 (b), the encapsulant layer 5 is ground to a thickness substantially equal to that of the substrate 4.

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

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

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

As described above, when performing the photolithography treatment, the etching treatment, etc., the sealing body 20 (laminated body) dissolves an acid such as hydrofluoric acid, an alkali such as tetramethylammonium hydroxide (TMAH), or a resist material. It is exposed to a resist solvent and processed at a high temperature.
However, by forming the adhesive layer including the first adhesive composition layer formed by using the adhesive layer forming composition according to the first aspect, the adhesive layer has high heat resistance. Therefore, the rewiring layer 6 can be suitably formed on the sealing material layer 5.

According to the method for manufacturing a laminated body of the third embodiment, the support substrate 1, the separation layer 2, the adhesive layer 3, the sealing material layer 5 covering the substrate 4, and the rewiring layer 6 are laminated in this order. It is possible to stably manufacture the laminated body 30.
The laminate 30 is a laminate produced in a process based on a fan-out type technology, in which terminals provided on the substrate 4 are mounted on a rewiring layer 6 extending outside the chip area.

In the method for manufacturing a laminated body of the present embodiment, bumps can be further formed on the rewiring layer 6 or elements can be mounted. The element can be mounted on the rewiring layer 6 by using, for example, a chip mounter or the like.

(Manufacturing method of electronic parts)
The method for manufacturing an electronic component according to a fourth aspect of the present invention includes a separation step and a removal step after obtaining the laminate by the method for producing a laminate according to the third aspect.

FIG. 5 is a schematic process diagram illustrating an embodiment of a method for manufacturing a semiconductor package (electronic component). FIG. 5 (a) is a diagram showing a laminate produced by the production method of the third embodiment, FIG. 5 (b) is a diagram for explaining a separation step, and FIG. 5 (c) is a diagram for removing. It is a figure explaining a process.

≪Separation process≫
The separation step in the embodiment is a step of separating the support base 1 from the substrate 4 included in the laminate 30 by irradiating the separation layer 2 with light (arrows) via the support base 1 to change the quality of the separation layer 2. Is.

As shown in FIG. 5A, in the separation step, the separation layer 2 is altered by irradiating the separation layer 2 with light (arrows) via the support substrate 1.
Examples of the wavelength at which the separation layer 2 can be altered include a range of 600 nm or less.
The type and wavelength of the light to be irradiated may be appropriately selected according to the transparency of the support substrate 1 and the material of the separation layer 2. For example, a YAG laser, a ruby laser, a glass laser, a YVO ₄ laser, an LD laser, and a fiber. It is possible to use solid-state lasers such as lasers, liquid lasers such as dye lasers _{, gas lasers such as CO 2} lasers, excima lasers, Ar lasers and He-Ne lasers, laser light such as semiconductor lasers and free electron lasers, and non-laser light. it can. As a result, the separation layer 2 can be altered so that the support substrate 1 and the substrate 4 can be easily separated.

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

After irradiating the separation layer 2 with light (arrows) to alter the quality of the separation layer 2, the support substrate 1 is separated from the substrate 4 as shown in FIG. 5 (b).
For example, the support substrate 1 and the substrate 4 are separated by applying a force in a direction in which the support substrate 1 and the substrate 4 are separated from each other. Specifically, one of the support substrate 1 or the substrate 4 side (rewiring layer 6) is fixed to the stage, and the other is lifted while being sucked and held by a separation plate provided with a suction pad such as a bellows pad. The support substrate 1 and the substrate 4 can be separated.
The force applied to the laminated body 30 may be appropriately adjusted depending on the size of the laminated body 30, and is not limited. For example, in the case of a laminated body having a diameter of about 300 mm, 0.1 to 5 kgf (0). By applying a force of about .98 to 49N), the support substrate 1 and the substrate 4 can be suitably separated.

≪Removal process≫
The removal step in the embodiment is a step of removing the adhesive layer 3 adhering to the substrate 4 after the separation step.
In FIG. 5B, the adhesive layer 3 and the separation layer 2 are attached to the substrate 4 after the separation step. In the present embodiment, the electronic component 40 is obtained by removing the adhesive layer 3 and the separation layer 2 adhering to the substrate 4 in the removing step.

Examples of the method for removing the adhesive layer 3 and the like adhering to the substrate 4 include a method for removing the residue of the adhesive layer 3 and the separation layer 2 using a cleaning liquid.
As the cleaning liquid, a cleaning liquid containing an organic solvent is preferably used. As the organic solvent in this cleaning liquid, it is preferable to use the organic solvent blended in the composition for forming the separation layer and the solvent component blended in the composition for forming the adhesive layer.
The adhesive layer formed by using the composition for forming an adhesive layer of the above-described embodiment has increased solubility in a hydrocarbon-based solvent. Therefore, in the embodiment, the cleaning and removing property of the adhesive layer is good.

In the method for manufacturing an electronic component of the present embodiment, after the above removing step, the electronic component 40 may be further subjected to a treatment such as solder ball formation, dicing, or oxide film formation.

(polymer)
The polymer according to the fifth aspect of the present invention has a structural unit (p1) represented by the following general formula (p1-1).

［式中、Ｒ^ｕ１１〜Ｒ^ｕ１４は、それぞれ独立に、炭素数１〜３０の有機基又は水素原子を表す。ただし、Ｒ^ｕ１１〜Ｒ^ｕ１４の少なくとも１つは、アルコキシシリル基を含む有機基である。ｎは、０〜２の整数である。］

[In the formula, R ^{u11 to} R ^u14 independently represent an organic group or a hydrogen atom having 1 to 30 carbon atoms. However, ^{at least one of Ru11 to Ru14} is an organic group containing an alkoxysilyl group. n is an integer from 0 to 2. ]

The polymer of this embodiment is the same polymer as the polymer (P1).

<Manufacturing of polymer>
The polymer of the present embodiment can be synthesized, for example, as follows.

<< Polymerization step (treatment S1) >>
First, as a monomer, a monomer for inducing a constituent unit (p1) is prepared. Examples of the monomer include a monomer represented by the following general formula (p1-1m).

［式中、Ｒ^ｕ１１〜Ｒ^ｕ１４、及びｎは、前記一般式（ｐ１−１）中のＲ^ｕ１１〜Ｒ^ｕ１４、及びｎと同様である。］

^{Wherein, R} u11 ^{~R u14,} and n, ^R u11 ^{to R u14} in the general formula (p1-1), and is the same as n. ]

When the polymer of the present embodiment has other structural units in addition to the structural unit (p1), a monomer for inducing the other structural units is also prepared. For example, when the polymer of the present embodiment has the above-mentioned structural unit (p2), a cycloolefin monomer for inducing the structural unit (p2) is prepared. When the polymer of the present embodiment has the above-mentioned structural unit (p3), a monomer containing a maleimide skeleton for inducing the structural unit (p3) is prepared.

Next, each of the prepared monomers is addition-polymerized to obtain a polymer. For example, addition polymerization is carried out by coordination polymerization.

In the present embodiment, solution polymerization can be carried out by dissolving each of the above-mentioned monomers and an organometallic catalyst in a solvent and then heating for a predetermined time. At this time, the heating temperature can be, for example, 30 ° C. to 120 ° C. The heating time can be, for example, 0.1 hour to 100 hours. It is more preferable to carry out solution polymerization after removing dissolved oxygen in the solvent by nitrogen or argon bubbling.

In the polymerization step, a molecular weight modifier, a chain transfer agent, or the like can be used, if necessary. Examples of the chain transfer agent include alkylsilane compounds such as trimethylsilane, triethylsilane and tributylsilane; and organoaluminum such as triethylaluminum, tributylaluminum and MAO (methylalmoxane). The chain transfer agent may be used alone or in combination of two or more.

Examples of the solvent used in the polymerization reaction include ketones such as methyl ethyl ketone (MEK); ethers such as propylene glycol monomethyl ether, diethyl ether and tetrahydrofuran (THF); toluene; esters such as ethyl acetate and butyl acetate; Alcohols such as methyl alcohol, ethyl alcohol, and isopropyl alcohol; one or more of them can be used.

The organometallic catalyst is not particularly limited as long as the addition polymerization proceeds, but for example, a cationic complex in which a phosphine-based or diimine-based ligand is coordinated with the palladium complex or nickel complex, and a counter anion. And, etc. may be used. One type of organometallic catalyst may be used alone, or two or more types may be used in combination.
Examples of the palladium complex include (acetato-κ0) (acetoform) bis [tris (1-methylethyl) phosphine] palladium (I) tetrakis (2,3,4,5,6-pentafluorophenyl) borate, π. -Allyl palladium complex such as allyl palladium chloride dimer; organic carboxylate of palladium such as acetate, propionate, maleate and naphthoate of palladium; triphenylphosphine complex of palladium acetate, tri (m) of palladium acetate -Trill) phosphine complex, complex of palladium organic carboxylic acid such as tricyclohexylphosphine complex of palladium acetate; organic sulfonate of palladium such as dibutyl subphosphate of palladium, p-toluene sulfonate; bis (acetylacetate) Β-diketone compounds of palladium such as nat) palladium, bis (hexafluoroacetylacetonate) palladium, bis (ethylacetacetate) palladium, bis (phenylacetoacetate) palladium; dichlorobis (triphenylphosphine) palladium, bis [tri (tri (tri (tri) Examples thereof include halide complexes of palladium such as m-tolylphosphine)] palladium, dibromobis [tri (m-tolylphosphine)] palladium, and acetnyltriphenylphosphonium complex.

Examples of the phosphine-based ligand include triphenylphosphine, dicyclohexylphosphine, cyclohexyldiphenylphosphine, and tricyclohexylphosphine.

Examples of the counter anion include triphenylcarbenium tetrakis (pentafluorophenyl) borate, triphenylcarbenium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, and triphenylcarbenium tetrakis (2,4). 6-Trifluorophenyl) borate, triphenylcarbenium tetraphenylborate, tributylammonium tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, N, N-diethylanilinium tetrakis ( Examples thereof include pentafluorophenyl) borate, N, N-diphenylanilinium tetrakis (pentafluorophenyl) borate, and lithium tetrakis (pentafluorophenyl) borate.

<< Cleaning process (treatment S2) >>
The reaction solution containing the polymer obtained in the polymerization step is added to an organic solvent to precipitate the polymer. Examples of the organic solvent for precipitation include ketones such as acetone and methyl ethyl ketone; alcohols such as methanol, ethyl alcohol and isopropyl alcohol. The polymer is then collected by filtration, washed with an organic solvent and then dried. Examples of the organic solvent for cleaning include ketones such as acetone and methyl ethyl ketone; alcohols such as methanol, ethyl alcohol and isopropyl alcohol.

The polymer of this embodiment can be synthesized, for example, in this way.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these examples.

<Synthesis of polymer>
(Preparation of catalyst solution)
0.274 g (0.00075 mol) of allylpalladium (II) chloride (dimer), 0.403 g (0.0015 mol) of diphenylcyclohexylphosphine, and 200 g of dehydrated toluene in a glass container that has been preliminarily dehydrated and has a nitrogen atmosphere. Was added and stirred at room temperature for 1 hour to dissolve. Next, 1.502 g (0.0019 mol) of N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate was added to the lysate, and the mixture was further stirred for 30 minutes. The obtained solution was filtered under a nitrogen stream to obtain a catalytic solution.

(Synthesis of polymer (P1-1))
In an appropriately sized reaction vessel equipped with a stirrer and a cooling tube, 5-butylbiciclo [2.2.1] hept-2-ene (1,982 g, 13.2 mol), [Biciclo [2.2.1] Hept-5-en-2-yl] triethoxysilane (434 g, 1.80 mol) and triethylsilane (1.0 g, 0.009 mol) were weighed and added, and 8,000 g of dehydrated toluene was added thereto. Dissolved. Nitrogen bubbling was performed on this solution to remove dissolved oxygen in the system. Then, the solution was warmed with stirring, and when the temperature reached 60 ° C., the catalyst solution prepared as described above was added under a nitrogen stream. The reaction was carried out for 3 hours while maintaining the internal temperature under the condition of 60 ° C. As a result, [Biciclo [2.2.1] hept-5-en-2-yl] triethoxysilane and polymer with 5-butylbiciclo [2.2.1] hept-2-ene were obtained. Then, the solution was cooled to room temperature, reprecipitated with a large amount of methyl ethyl ketone, and then the precipitate was collected by filtration. The filtrate was washed with a large amount of methyl ethyl ketone, and the polymer was taken out by solid-liquid separation. It was dried in a vacuum dryer to obtain 1,550 g of a white powder polymer (P1-2).
The weight average molecular weight (Mw) of the polymer (P1-1) thus obtained was 400,000, and the dispersity (Mw / Mn) was 4.5.

(Synthesis of polymer (P1-2))
5-butylviciclo [2.2.] So that the ratio of the structural unit (p1) to the total structural unit (100 mol%) constituting the polymer (P1-2) is 10% (l / m = 90/10). 1] Polymers similar to the synthesis of the polymer (P1-1), except that hept-2-ene and [Biciclo [2.2.1] hept-5-en-2-yl] triethoxysilane were used. (P1-2) was synthesized. As a result, 1,620 g of white powder polymer (P1-2) was obtained.
The weight average molecular weight (Mw) of the polymer (P1-2) thus obtained was 390,000, and the dispersity (Mw / Mn) was 4.4.

(Synthesis of polymer (P1-3))
5-butylviciclo [2.2.] So that the ratio of the structural unit (p1) to the total structural unit (100 mol%) constituting the polymer (P1-3) is 14% (l / m = 86/14). 1] Polymer (Similar to the synthesis of the above polymer (P1-1), except that hept-2-ene and [Biciclo [2.2.1] hept-5-en-2-yl] triethoxysilane were used. P1-3) was synthesized. As a result, 1,450 g of white powder polymer (P1-3) was obtained.
The weight average molecular weight (Mw) of the polymer (P1-3) thus obtained was 420,000, and the dispersity (Mw / Mn) was 4.7.

(Synthesis of polymer (P2-1))
In an appropriately sized reaction vessel equipped with a stirrer and a condenser, 5-butylbiciclo [2.2.1] hept-2-ene (2,252 g, 15.0 mol), triethylsilane (1.0 g, 0. 009 mol) was weighed and charged, and 8,000 g of dehydrated toluene was added and dissolved therein. Nitrogen bubbling was performed on this solution to remove dissolved oxygen in the system. Then, the solution was warmed with stirring, and when the temperature reached 60 ° C., the catalyst solution prepared as described above was added under a nitrogen stream. The reaction was carried out at 60 ° C. for 4 hours while maintaining the internal temperature. As a result, poly 5-butylbiciclo [2.2.1] hept-2-ene was obtained. Then, the solution was cooled to room temperature, reprecipitated with a large amount of methyl ethyl ketone, and then the precipitate was collected by filtration. The filtrate was washed with a large amount of methyl ethyl ketone, and homopolymer was taken out by solid-liquid separation. It was dried in a vacuum dryer to obtain 1,800 g of white powder homopolymer (P2-1).
The weight average molecular weight (Mw) of the homopolymer (P2-1) thus obtained was 450,000, and the dispersity (Mw / Mn) was 4.2.

(Examples 1 to 3 and Comparative Example 1)
Each component shown in Table 1 was mixed and dissolved to prepare an adhesive composition (resin component concentration 20% by mass) of each example.

In Table 1, each abbreviation has the following meaning. The value in [] is the blending amount (part by mass).

(P1) -1: The polymer (P1-1).
(P1) -2: The polymer (P1-2).
(P1) -3: The polymer (P1-3).
(P2) -1: The polymer (P2-1).
(P2) -2: Acrylic resin represented by the following formula (P2-2). Weight average molecular weight (Mw) 10000, dispersity (Mw / Mn) 3.3.

(P2) -3: SEBS resin Septon 8004 (Kuraray Co., Ltd.). Weight average molecular weight (Mw) 100,000.

<Evaluation of adhesion of adhesive layer (1)>
The adhesive compositions of each example were applied onto a silicon substrate (size 6 inches, thickness 675 μm) by a spin coating method while rotating at 1000 rpm.
Next, the support coated with the adhesive composition of each example was preheated at 90 ° C. for 4 minutes to form an adhesive layer having a thickness of 35 μm.
The adhesive layer was then linearly cut using a cutter. The cutting line of the adhesive layer formed above was made to cross the silicon substrate. The distance at which the adhesive layer was peeled off from the cutting line was measured, and the adhesion of the adhesive layer was evaluated. This result is shown in Table 2 as "adhesion (1)". The shorter the peeling distance, the better the adhesion of the adhesive layer to the silicon substrate.

<Adhesion evaluation of adhesive layer (2)>
The adhesive compositions of each example were applied onto a bumped substrate (size 12 inches, thickness 775 μm, bump height 30 μm) while rotating at 1000 rpm by a spin coating method.
Next, the support coated with the adhesive composition of each example was preheated at 90 ° C. for 4 minutes, and then heated at 160 ° C. for 4 minutes and 220 ° C. for 4 minutes to form an adhesive layer having a thickness of 35 μm. Formed.
The formed adhesive layer was observed with a microscope (manufactured by KEYENCE, VHX-5000), and the ratio of the area where the adhesive layer was peeled off from the bumped substrate was evaluated based on the following evaluation criteria. This result is shown in Table 2 as "adhesion (2)".
Evaluation criteria ◎: The peeled area is 0%.
〇: The peeled area is less than 5%.
X: The peeled area is 5% or more.

From the results shown in Table 2, it can be confirmed that the adhesive compositions of Examples 1 to 7 have better adhesion to the silicon substrate and the bumped substrate than the adhesive compositions of Comparative Example 1.

1 Supporting substrate,
2 Separation layer,
3 Adhesive layer,
4 board,
5 Encapsulant layer,
6 Rewiring layer,
10 laminated body,
12 support,
20 Encapsulation,
30 laminates,
40 electronic components,
123 Support with adhesive layer.

Claims (17)

An adhesive composition for bonding a support and a substrate.
An adhesive composition containing a polymer (P1) having a structural unit (p1) represented by the following general formula (p1-1).

[In the formula, R ^{u11 to} R ^u14 independently represent an organic group or a hydrogen atom having 1 to 30 carbon atoms. However, ^{at least one of Ru11 to Ru14} is an organic group containing an alkoxysilyl group. n ¹ is an integer from 0 to 2. ] The first aspect of the present invention, wherein the proportion of the structural unit (p1) in the polymer (P1) is 3 to 30 mol% with respect to all the structural units (100 mol%) constituting the polymer (P1). Adhesive composition. The adhesive composition according to claim 1 or 2, wherein the polymer (P1) has a structural unit (p2) represented by the following general formula (p2-1).

[In the formula, R ^{u21 to} R ^u24 independently represent an organic group having 1 to 30 carbon atoms (excluding those containing an alkoxysilyl group) or a hydrogen atom. n ² is an integer from 0 to 2. ] The weight average molecular weight of the polymer (P1) is, 5.0 × a ¹⁰ 4 ^~1.0 × ^{10 6,} the adhesive composition according to any one of claims 1 to 3. A laminated body in which a support and a substrate are bonded together via an adhesive layer.
The adhesive layer is a laminate containing a first adhesive composition layer formed by using the adhesive composition according to any one of claims 1 to 4. The adhesive layer further comprises a second adhesive composition layer formed of the polymer (P1) -free adhesive composition.
The laminate according to claim 5. The laminate according to claim 6, wherein the first adhesive composition layer is adjacent to the substrate. The support includes a support substrate that transmits light and a separation layer provided on the support substrate.
The separation layer is a layer adjacent to the adhesive layer, which is altered by irradiation with light to enable the support substrate to be separated from the substrate bonded to the support.
The laminate according to any one of claims 5 to 7. A method for manufacturing a laminated body in which a support and a substrate are bonded together via an adhesive layer.
The adhesive layer containing the first adhesive composition layer formed by using the adhesive composition according to any one of claims 1 to 4 on the support or at least one of the substrates. Adhesive layer forming process to be formed and
A bonding step of bonding the support and the substrate via the adhesive layer formed in the adhesive layer forming step.
A method for producing a laminated body. The ninth aspect of the present invention further comprises a sealing step of forming a sealed body by sealing the substrate bonded to the support via the adhesive layer with a sealing material after the bonding step. Method of manufacturing a laminate of. After the sealing step, a grinding step of grinding the sealing material portion of the sealing body so that a part of the substrate is exposed, and
After the grinding step, a rewiring forming step of forming a rewiring on the exposed substrate, and
The method for producing a laminate according to claim 10, further comprising. The production of the laminate according to any one of claims 9 to 11, further comprising a step of forming a separation layer that is altered by irradiation with light on a support substrate that transmits light to prepare the support. Method. After obtaining the laminate by the method for producing the laminate according to claim 12,
A separation step of separating the support substrate from the substrate included in the laminate by irradiating the separation layer with light through the support substrate to alter the separation layer.
After the separation step, a removal step of removing the adhesive layer adhering to the substrate, and
A method for manufacturing electronic components. A polymer used in an adhesive composition for bonding a support and a substrate.
A polymer having a structural unit (p1) represented by the following general formula (p1-1).

[In the formula, R ^{u11 to} R ^u14 independently represent an organic group or a hydrogen atom having 1 to 30 carbon atoms. However, ^{at least one of Ru11 to Ru14} is an organic group containing an alkoxysilyl group. n is an integer from 0 to 2. ] The polymer according to claim 14, wherein the proportion of the structural unit (p1) is 3 to 30 mol% with respect to all the structural units (100 mol%) constituting the polymer. The polymer according to claim 14 or 15, further comprising a structural unit (p2) represented by the following general formula (p2-1).

[In the formula, R ^{u21 to} R ^u24 independently represent an organic group having 1 to 30 carbon atoms (excluding those containing an alkoxysilyl group) or a hydrogen atom. n ² is an integer from 0 to 2. ] Weight average molecular weight is ^{5.0 × 10 4 ~1.0 × 10 6} , the polymer according to any one of claims 14 to 16.

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