JP7374719B2 - Adhesive composition, laminate and manufacturing method thereof, and manufacturing method of electronic components - Google Patents

Description

The present invention relates to an adhesive composition, a laminate and its manufacturing method, an electronic component manufacturing method, and a polymer.

Semiconductor packages (electronic components) including semiconductor elements have various forms depending on the corresponding size, such as WLP (Wafer Level Package) and PLP (Panel Level Package).
Semiconductor package technologies include fan-in technology and fan-out technology. Known semiconductor packages based on fan-in technology include fan-in WLP (Fan-in Wafer Level Package), in which terminals at the ends of bare chips are relocated within the chip area. As a semiconductor package based on fan-out technology, a fan-out WLP (Fan-out Wafer Level Package), in which the terminals are relocated outside the chip area, is known.

In recent years, fan-out technology has been applied to fan-out PLP (Fan-out Panel Level Package), in which semiconductor elements are placed on a panel and packaged. This method is attracting attention as a method that can achieve thinner and more compact designs.

In order to reduce the size of semiconductor packages, it is important to reduce the thickness of the substrate in which elements are incorporated. However, reducing the thickness of the substrate reduces its strength, making it more likely to be damaged during semiconductor package manufacturing. On the other hand, a laminate in which a support is bonded to a substrate is used.

Here, when bonding the substrate and the support, 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 that is compatible with the polymer.

Japanese Patent Application Publication No. 2014-105316

Incidentally, when manufacturing a semiconductor package, after a substrate and a support are bonded together with an adhesive, high-temperature treatments such as sealing, thin film formation, and baking are performed. With conventional adhesive compositions, due to the effects of high-temperature treatment as described above, the position of the substrate may shift, for example, before and after the sealing operation. Although it is possible to use a high temperature resistant adhesive composition, the high temperature resistant adhesive composition may not have sufficient adhesion to the substrate or support.

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

In order to solve the above problems, the present invention employs the following configuration.
That is, a first aspect of the present invention is an adhesive composition for bonding a support and a substrate, which comprises a polymer (p1) having a structural unit (p1) represented by the following general formula (p1-1). 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 each independently represent an organic group having 1 to 30 carbon atoms or a hydrogen atom. However, at least one of R ^u11 to R ^u14 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 together via an adhesive layer, the adhesive layer being formed using the adhesive composition of the first aspect. A laminate including a first adhesive composition layer.

A third aspect of the present invention is a method for manufacturing a laminate in which a support and a substrate are bonded together via an adhesive layer, wherein the first aspect is applied to at least one of the support and the substrate. an adhesive layer forming step of forming the adhesive layer including a first adhesive composition layer formed using the adhesive composition; and the adhesive layer formed in the adhesive layer forming step. This is a method for manufacturing a laminate, comprising 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 through the support base to change the quality of the separation layer. A method for manufacturing an electronic component, comprising: a separating step of separating the support base from the substrate included in the laminate; and a removing step of removing the adhesive layer adhering to the substrate after the separating step. It is.

A fifth aspect of the present invention is a polymer used in an adhesive composition for bonding a support and a substrate, which 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 each independently represent an organic group having 1 to 30 carbon atoms or a hydrogen atom. However, at least one of R ^u11 to R ^u14 is an organic group containing an alkoxysilyl group. n is an integer from 0 to 2. ]

According to the present invention, there is provided an adhesive composition for bonding a support and a substrate, which has heat resistance and is capable of forming an adhesive layer with excellent adhesion to the substrate or the support. The present invention can provide a product, a laminate using the same, a method for manufacturing the same, a method for manufacturing an electronic component, and a polymer used in the adhesive composition.

FIG. 1 is a schematic diagram showing an embodiment of a laminate to which the present invention is applied. It is a schematic process diagram explaining one embodiment of the manufacturing method of a laminated body. FIG. 2(a) is a diagram illustrating the process of producing a support, FIG. 2(b) is a diagram illustrating the adhesive layer forming process, and FIG. 2(c) is a diagram illustrating the bonding process. This is a diagram. It is a schematic process diagram explaining other embodiments of the manufacturing method of a laminated body. FIG. 3(a) is a diagram showing a laminate manufactured by the manufacturing method of the first embodiment, and FIG. 3(b) is a diagram illustrating a sealing process. It is a schematic process diagram explaining other embodiments of the manufacturing method of a laminated body. FIG. 4(a) is a diagram showing the sealed body manufactured by the manufacturing method of the second embodiment, FIG. 4(b) is a diagram explaining the grinding process, and FIG. It is a figure explaining a wiring formation process. FIG. 1 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 manufactured by the manufacturing method of the third embodiment, FIG. 5(b) is a diagram illustrating the separation process, and FIG. It is a figure explaining a process. FIG. 1 is a diagram illustrating an example of a method of using an adhesive composition to which the present invention is applied. FIG. 1 is a diagram illustrating an example of a method of using an adhesive composition to which the present invention is applied. FIG. 1 is a diagram illustrating an example of a method of using an adhesive composition to which the present invention is applied.

In this specification and the claims, the term "aliphatic" is a relative concept to aromatic, and is defined to mean groups, compounds, etc. that do not have aromaticity.
Unless otherwise specified, "alkyl group" includes 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" includes linear, branched, and cyclic divalent saturated hydrocarbon groups.
A "halogenated alkyl group" is a group in which some or all of the hydrogen atoms of an alkyl group are 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.
"Fluorinated alkyl group" or "fluorinated alkylene group" refers to a group in which some or all of the hydrogen atoms of an alkyl group or alkylene group are substituted with fluorine atoms.
"Constituent unit" means a monomer unit (monomer unit) that constitutes a high molecular compound (resin, polymer, copolymer).
When describing "may have a substituent" or "may have a substituent", there are two cases in which a hydrogen atom (-H) is substituted with a monovalent group, and a case in which a methylene group (-CH ₂ -) is substituted with a divalent group.
“Exposure” is a concept that includes radiation irradiation in general.

"Structural unit derived from styrene" means a structural unit formed by cleavage of the ethylenic double bond of styrene. "A structural unit derived from a styrene derivative" means a structural unit formed by cleavage of an ethylenic double bond of a styrene derivative.
The term "styrene derivative" is a concept that includes styrene in which the hydrogen atom at the α-position is substituted with another substituent such as an alkyl group or a halogenated alkyl group, as well as derivatives thereof. These derivatives include those in which the hydrogen atom of the hydroxyl group of styrene is replaced with an organic group; the hydrogen atom at the α position may be substituted with a substituent. Examples include those in which a substituent other than a hydroxyl group is bonded to the benzene ring of styrene. Note that the α-position (α-position carbon atom) refers to the carbon atom to which a benzene ring is bonded, unless otherwise specified.
Examples of the substituent for substituting the hydrogen atom at the α-position of styrene include the same substituents as those listed as the substituent at the α-position in the α-substituted acrylic ester.

The alkyl group as the substituent at the α-position is preferably a linear or branched alkyl group, 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).
In addition, examples of the halogenated alkyl group as a substituent at the α-position include a group in which part or all of the hydrogen atoms of the above-mentioned "alkyl group as a substituent at the α-position" are substituted with a halogen atom. It will be done. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and the like, with a fluorine atom being particularly preferred.
Further, specific examples of the hydroxyalkyl group as a substituent at the α-position include a group in which part or all of the hydrogen atoms of the above-mentioned "alkyl group as a substituent at the α-position" are substituted with a hydroxyl group. The number of hydroxyl groups in the hydroxyalkyl group is preferably 1 to 5, and most preferably 1.

(Adhesive composition)
The adhesive composition according to the first aspect of the present invention is for bonding a support and a substrate together. 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 laminate to which the present invention is applied.
The laminate 10 shown in FIG. 1 includes a separation layer 2 and an adhesive layer 3 between a support base 1 and a substrate 4. They are stacked in this order.
The support base 1 is made of a material that transmits light. In the laminate 10, when the separation layer 2 is irradiated with light from the support base 1 side, the separation layer 2 changes in quality and decomposes, so that the support base 1 is separated from the substrate 4.
In this laminate 10, a support 12 and a substrate 4 are bonded together with an adhesive layer 3 interposed therebetween. This adhesive layer 3 can be formed using the adhesive composition of this embodiment.

<Polymer component (P)>
In this embodiment, the polymer component (P) (hereinafter also referred to as "component (P)") contains at least the polymer (P1). In addition to polymer (P1), component (P) may also contain polymers other than these.
The polymer component (P) in this embodiment includes, in addition to the polymer, a monomer that can serve as a matrix constituting the adhesive layer, such as a curable monomer described below.

≪Polymer (P1)≫
In this embodiment, the polymer (P1) (hereinafter also referred to as "component (P1)") has at least a structural unit (p1).

[Constituent unit (p1)]
The structural unit (p1) is a structural unit represented by the following general formula (p1-1). Since the polymer (P1) has the structural unit (p1), it is possible to form an adhesive layer with high adhesiveness 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 each independently represent an organic group having 1 to 30 carbon atoms or a hydrogen atom. However, at least one of R ^u11 to R ^u14 is an organic group containing an alkoxysilyl group. n is an integer from 0 to 2. ]

In the formula (p1-1), examples of the organic group in R ^u11 to R ^u14 include an alkyl group, an alkenyl group, an alkynyl group, an alkylidene group, an aryl group, an aralkyl group, an alkaryl group, a cycloalkyl group, and a carboxy group. Examples include organic groups and organic groups having a heterocycle.
The alkyl group in R ^u11 to R ^u14 is preferably an alkyl group having 1 to 10 carbon atoms, such as a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, Examples include tert-butyl group, pentyl group, neopentyl group, hexyl group, heptyl group, octyl group, nonyl group, and decyl group.
Examples of the alkenyl group for R ^u11 to R ^u14 include an allyl group, a pentenyl 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 for 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 anthracenyl group.
Examples of the aralkyl group for R ^u11 to R ^u14 include a benzyl group and a phenethyl group.
Examples of the alkaryl group in R ^u11 to R ^u14 include tolyl group and xylyl group.
Examples of the cycloalkyl group for 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 R ^u11 to R ^u14 include an organic group having an epoxy group and an organic group having an oxetanyl group.

The organic groups in R ^u11 to R ^u14 are preferably alkyl groups from the viewpoint of improving the solubility in hydrocarbon solvents 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 even more preferable, since it is easy to maintain a high glass transition point.

In the organic groups R ^u11 to R ^u14 , one or more hydrogen atoms may be substituted with a halogen atom. Examples of the 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 each independently an alkyl group having 1 to 30 carbon atoms; m is an integer of 1 to 3 ). Examples of the alkyl group for R ¹ and R ² include the same alkyl groups as those listed for R ^u11 to R ^u14 above. In order to improve the adhesion to the substrate, the alkyl group of R ¹ and R ² preferably has 1 to 8 carbon atoms, more preferably 1 to 6 carbon atoms, even more preferably 1 to 3 carbon atoms, and has 1 or 3 carbon atoms. 2 is particularly preferred.
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 includes an alkyl group, an alkenyl group, an alkynyl group, an alkylidene group, an aryl group, an aralkyl group, an alkaryl group, a cycloalkyl group, a divalent linking group having a carboxy group, and a heterocycle. Examples include divalent linking groups. 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, even more preferably 1 to 3 carbon atoms, and particularly preferably 1 or 2 carbon atoms. Among these, Y is preferably a single bond.
m is an integer of 1 to 3, preferably 2 or 3, and more preferably 3.

The organic group containing an alkoxysilyl group may be all of R ^u11 to R ^u14 , any three of R ^u11 to R ^u14 , or any two of R ^u11 to R ^u14 . It may be any one of R ^u11 to R ^u14 . From a synthetic standpoint, any one of R ^u11 to R ^u14 is preferably an organic group containing an alkoxysilyl group.

From the viewpoint of increasing the light transmittance of the adhesive layer formed using the adhesive composition, it is preferable that at least one of R ^u11 to R ^u14 is a hydrogen atom.

Among the above, the organic group in R ^u11 to R ^u14 is 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 these, it is preferable that any one of R ^u11 to R ^u14 is an alkoxysilyl group and the remaining three are hydrogen atoms.

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

Specific examples of the structural unit (p1) are shown below.

The number of structural units (p1) that the component (P1) has may be one type or two or more types.
The proportion 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 the amount is equal to or more than the lower limit, the adhesion of the adhesive layer to the substrate is further improved. The proportion of the structural unit (p1) in the component (P1) is preferably 5 mol% or more, and 8 mol% or more with respect to the total (100 mol%) of all the structural units constituting the (P1) component. The content is more preferably 10 mol% or more, even more preferably 12 mol% or more, and particularly preferably 14 mol% or more. The upper limit of the ratio of the structural unit (p1) in the component (P1) is not particularly limited, but from the viewpoint of solubility, the upper limit of the ratio of the structural unit (p1) in the component (P1) is 30 It is preferably at most mol%, more preferably at most 25 mol%, even more preferably at most 20 mol%, particularly preferably at most 17 mol%. The proportion of the structural unit (p1) in the component (P1) is, for example, 3 to 30 mol%, 5 to 25 mol%, It can be 8 to 20 mol%, or 14 to 17 mol%, etc.

[Other constituent units]
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) is mentioned.

・Constituent unit (p2)
The structural unit (p2) is a structural unit derived from a cycloolefin (excluding those corresponding to the structural unit (p1)). It is preferable that the polymer (P1) 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 that can form an adhesive layer that is easily dissolved and removed in a hydrocarbon solvent has been created. easier to obtain.

Preferred structural units (p2) include, for example, structural units represented by the following general formula (p1-2).

［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 each 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 groups R ^u21 to R ^u24 include those mentioned as the organic groups R ^u11 to R ^u14 in the formula (p1-1). However, the organic groups in R ^u21 to R ^u24 do not include an alkoxysilyl group.
The organic groups in R ^u21 to R ^u24 are preferably alkyl groups from the viewpoint of improving the solubility in hydrocarbon solvents 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 even more preferable, since it is easy to maintain a high glass transition point.

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

From the viewpoint of increasing the light transmittance of the adhesive layer formed using the adhesive composition, it is preferable that at least one of R ^u21 to R ^u24 is a hydrogen atom.
Among the above, the organic groups in R ^u21 to R ^u24 are preferably a combination of an alkyl group and a hydrogen atom, and it is preferable that any one of R ^u21 to R ^u24 is an alkyl group and the remaining three are hydrogen atoms. .

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

Specific examples of the structural unit (p2) are shown below.

The number of structural units (p2) contained in the component (P1) may be one type or two or more types.
The proportion of the structural unit (p2) in the component (P1) is preferably 10 to 95 mol%, and 20 to 90 mol%, based on the total (100 mol%) of all the structural units constituting the component (P1). It is more preferably 30 to 88 mol%, even more preferably 40 to 86 mol%.
When the proportion of the structural unit (p2) is at least the lower limit of the above-mentioned preferred range, the solubility in hydrocarbon solvents is likely to be increased. When it is below the upper limit of the above-mentioned preferable range, it becomes easier to maintain a balance with other structural units.

・Constituent 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 improved.
Preferred structural units (p3) include, for example, structural units represented by the following general formula (p3-1).

［式中、Ｒ^ｕ１０は、炭素数１～３０の有機基を表す。］

[In the formula, R ^u10 represents an organic group having 1 to 30 carbon atoms. ]

In the formula (p3-1), R ^u10 represents an organic group having 1 to 30 carbon atoms. The organic group in R ^u10 may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group. Aliphatic hydrocarbon group means a hydrocarbon group without aromaticity. Further, the aliphatic hydrocarbon group may be saturated or unsaturated, and is usually preferably saturated.
For example, the organic group in R ^u10 is a cyclic group which may have a substituent, a chain alkyl group which may have a substituent, or a chain alkyl group which may have a substituent. Examples include alkenyl groups.

Cyclic group that 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 R ^u10 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, even more 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 substituents.
Specifically, the aromatic ring possessed by the aromatic hydrocarbon group in R ^u10 is benzene, fluorene, naphthalene, anthracene, phenanthrene, biphenyl, or an aromatic ring in which some of the carbon atoms constituting these aromatic rings are substituted with heteroatoms. Examples include group heterocycles. Examples of the heteroatom in the aromatic heterocycle include an oxygen atom, a sulfur atom, and a nitrogen atom.
Specifically, the aromatic hydrocarbon group in R ^u10 is a group in which one hydrogen atom is removed from the aromatic ring (aryl group: for example, a phenyl group, a naphthyl group, etc.), an alkylene group in which one of the hydrogen atoms in the aromatic ring is (eg, arylalkyl groups such as benzyl group, phenethyl group, 1-naphthylmethyl group, 2-naphthylmethyl group, 1-naphthylethyl group, and 2-naphthylethyl group), and the like. The alkylene group (alkyl chain in the arylalkyl group) preferably has 1 to 4 carbon atoms, more preferably 1 to 2 carbon atoms, and particularly preferably 1 carbon number.

Examples of the cyclic aliphatic hydrocarbon group in R ^u10 include an aliphatic hydrocarbon group containing a ring in its structure.
This aliphatic hydrocarbon group containing a ring in its structure includes an alicyclic hydrocarbon group (a group in which one hydrogen atom is removed from an aliphatic hydrocarbon ring), and an aliphatic hydrocarbon group in which one hydrogen atom of the aliphatic hydrocarbon ring is an alkylene group. Examples include groups substituted with other groups. The alkylene group preferably has 1 to 4 carbon atoms.
The aliphatic hydrocarbon ring preferably has 3 to 20 carbon atoms, more preferably 3 to 12 carbon atoms.
The aliphatic hydrocarbon ring may be polycyclic or monocyclic.
The monocyclic aliphatic hydrocarbon ring preferably has 3 to 8 carbon atoms, and specific examples include cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, and cyclooctane. 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, tetracyclododecane, etc. Polycycloalkane: Polycycloalkane having a polycyclic skeleton of a condensed ring system such as a ring having a steroid skeleton is more preferred.

Among these, the cyclic aliphatic hydrocarbon group in R ^u10 is preferably a group obtained by removing one or more hydrogen atoms from a monocycloalkane or polycycloalkane, and a group obtained by removing one or more hydrogen atoms from a monocycloalkane. More preferred is a group obtained by removing one hydrogen atom from a monocycloalkane, further preferably a group obtained by removing one hydrogen atom from cyclopentane or cyclohexane.

Examples of the substituent in the cyclic group of R ^u10 include an alkyl group, a halogen atom, and a halogenated alkyl group.
The alkyl group as a substituent is preferably an alkyl group having 1 to 5 carbon atoms, and more preferably a methyl group, ethyl group, propyl group, n-butyl group, or tert-butyl group.
Examples of the halogen atom as a substituent include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and the like, with a fluorine atom being preferred.
Examples of the halogenated alkyl group as a substituent include an alkyl group having 1 to 5 carbon atoms, such as a methyl group, ethyl group, propyl group, n-butyl group, and tert-butyl group, in which some or all of the hydrogen atoms are Examples include groups substituted with halogen atoms.

Chain alkyl group which may have a substituent:
The chain alkyl group of R ^u10 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 include pentadecyl group, hexadecyl group, isohexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, icosyl group, henicosyl group, docosyl group, and the like.
The branched alkyl group preferably has 3 to 20 carbon atoms, more preferably 3 to 15 carbon atoms, and 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-methylbutyl group, Examples include methylpentyl group, 2-methylpentyl group, 3-methylpentyl group, and 4-methylpentyl group.

Chain-like alkenyl group which may have a substituent:
The chain alkenyl group of R ^u10 may be linear or branched, and preferably has 2 to 10 carbon atoms, more preferably 2 to 5 carbon atoms, and has 2 to 4 carbon atoms. More preferably, the carbon number is particularly preferably 3. Examples of the linear alkenyl group include a vinyl group, a propenyl group (allyl group), and a butynyl group. Examples of the branched alkenyl group include 1-methylvinyl group, 2-methylvinyl group, 1-methylpropenyl group, and 2-methylpropenyl group.
As the chain alkenyl group, among the above, a straight chain 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 on the chain alkyl group or alkenyl group in R ^u10 include a halogen atom, a halogenated alkyl group, and a cyclic group in R ^u10 above.

Among the above, R ^u10 is preferably a cyclic group that may have a substituent, more preferably a cyclic hydrocarbon group that may have a substituent, and R u10 is preferably a cyclic group that may have a substituent. More preferred is a cyclic aliphatic hydrocarbon group which may be optional.

Specific examples of the structural unit (p3) are shown below.

The structural unit (p3) contained in the component (P1) may be one type or two or more types.
The proportion of the structural unit (p3) in the component (P1) is preferably 0 to 90 mol%, and 0 to 70 mol% with respect to the total (100 mol%) of all the structural units constituting the component (P1). More preferably, 0 to 50 mol% is even more preferable.
When the proportion of the structural unit (u21) is at least 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 below the upper limit of the above-mentioned preferable range, it becomes easier to maintain a balance with other structural units.

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

Preferred specific examples of component (P1) are shown below.

The weight average molecular weight (Mw) of the polymer (P1) (polystyrene conversion standard by gel permeation chromatography (GPC)) can be in the range of, for example, 5.0 × 10 ⁴ to 1.0 × 10 ⁶ , 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 preferable.
When the weight average molecular weight of the polymer (P1) is at least the lower limit of the above-mentioned preferred range, the heat resistance will be better. When it is below the upper limit of the above-mentioned preferred range, it becomes easier to obtain an adhesive composition that can form an adhesive layer that is easily dissolved in a hydrocarbon solvent and removed.

The degree of dispersion (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 is more preferable, and the range of 4.0 to 5.0 is even more preferable. Dispersity indicates the width of molecular weight distribution. Mn indicates number average molecular weight.

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

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

≪Polymer (P2)≫
In addition to component (P1), component (P) may contain another polymer (P2) (hereinafter also referred to as "component (P2)"). Examples of the component (P2) include hydrocarbon polymers. The hydrocarbon polymer may be an aliphatic hydrocarbon polymer or an aromatic hydrocarbon polymer. From the viewpoint of imparting heat resistance or flexibility, the (P2) component includes, for example, an elastomer, a cycloolefin polymer (excluding those falling under polymer (P1)), an acrylic resin, and a matrix constituting the adhesive layer. Examples include curable monomers that can be used.

[Elastomer]
The elastomer in component (P2) preferably has, for example, a structural unit derived from styrene or a structural unit derived from a styrene derivative (these are collectively referred to as "styrene units") as a main chain structural unit. It is mentioned in The elastomer is preferably a styrene thermoplastic elastomer, more preferably a hydrogenated styrene thermoplastic elastomer.

Examples of the elastomer in component (P2) include polystyrene-poly(ethylene/propylene) block copolymer (SEP), styrene-isoprene-styrene block copolymer (SIS), styrene-butadiene-styrene block copolymer (SBS), styrene-butadiene - Butylene-styrene block copolymer (SBBS) or hydrogenated products thereof; styrene-ethylene-butylene-styrene block copolymer (SEBS) (Septon 8004 (manufactured by Kuraray Co., Ltd.)), styrene-ethylene-propylene-styrene block copolymer (styrene- isoprene-styrene block copolymer) (SEPS), styrene-ethylene-ethylene-propylene-styrene block copolymer (SEEPS), styrene-ethylene-ethylene-propylene-styrene block copolymer (Septon V9461 (manufactured by Kuraray Co., Ltd.) in which the styrene blocks are reactively crosslinked) ), Septon V9475 (manufactured by Kuraray Co., Ltd.)), and styrene-ethylene-butylene-styrene block copolymer in which the styrene block is a reactive crosslinking type (having a reactive polystyrene hard block, Septon V9827 (manufactured by Kuraray Co., Ltd.)).

The content ratio of styrene units in the elastomer in component (P2) is preferably 10 to 70 mol%, more preferably 20 to 60 mol%, and 25 to 50 mol% is more preferable, and 30 to 45 mol% is particularly preferable.
When the content of styrene units is at least 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 below the upper limit of the above-mentioned preferable range, the chemical resistance of the adhesive layer formed by the adhesive composition can be suitably maintained.

The weight average molecular weight of the elastomer in component (P2) is preferably in the range of 20,000 to 200,000, more preferably in the range of 50,000 to 150,000, even more preferably in the range of 80,000 to 1,200,000.
When the weight average molecular weight of the elastomer is within the above-mentioned preferred range, an adhesive composition that can form an adhesive layer that is easily dissolved and removed in a hydrocarbon solvent can be easily obtained. Moreover, 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 increased.

The number of elastomers in the component (P2) may be one, or two or more.

The elastomer in component (P2) is more preferably a hydrogenated elastomer. If it is a hydrogenated product, its stability against heat is further improved, and changes in quality such as decomposition and polymerization are less likely to occur. In addition, it is more preferable from the viewpoint of solubility in hydrocarbon solvents and resistance to resist solvents.
Moreover, 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 heat stability, it is easier to obtain higher heat resistance.
More specifically, the elastomer is preferably a hydrogenated block copolymer of styrene and a conjugated diene. This further improves the stability against heat, making deterioration such as decomposition and polymerization less likely to occur. In addition, both ends are blocked with styrene, which has high heat stability, resulting in higher heat resistance. Furthermore, it is more preferable from the viewpoint of solubility in hydrocarbon solvents and resistance to resist solvents.

Commercially available elastomers that can be used as the (P2) component include, for example, "Septon (trade name)" manufactured by Kuraray Co., Ltd., "Hybrur (trade name)" manufactured by Kuraray Co., Ltd., and "Tuftec (trade name)" manufactured by Asahi Kasei Corporation. Examples include "Dynaron (product name)" manufactured by JSR Corporation.

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

[Cycloolefin polymer]
Preferred examples of the cycloolefin polymer include ring-opening polymers of monomer components containing cycloolefin monomers, and addition polymers obtained by addition-polymerizing monomer components containing cycloolefin monomers. However, those corresponding to the polymer (P1) are excluded.

Examples of cycloolefin monomers include bicyclics such as norbornene and norbornadiene, tricyclics such as dicyclopentadiene and hydroxydicyclopentadiene, tetracyclics such as tetracyclododecene, and pentacyclics such as cyclopentadiene trimer. alkyl (methyl, ethyl, propyl, butyl, etc.) substituted products, alkenyl (vinyl etc.) substituted products, alkylidene (ethylidene etc.) substituted products or aryl (phenyl etc.) substituted products of heptacyclic bodies such as tetracyclopentadiene, or these polycyclic bodies. , tolyl, naphthyl, etc.).

Among the above, particularly preferred are polymers having constitutional units derived from monomers having a norbornene structure selected from the group consisting of norbornene, tetracyclododecene, and alkyl substituted products thereof. By using such a cycloolefin polymer with a norbornene structure, it is possible to create an adhesive composition that can form an adhesive layer that is easily dissolved and removed in hydrocarbon solvents while having high chemical resistance to resist solvents. It becomes easier to get things.

The cycloolefin polymer may have as a monomer unit a monomer copolymerizable with the cycloolefin monomer.
Preferred examples of such copolymerizable monomers include alkene monomers. This alkene monomer may be linear or branched, and includes alkene monomers having 2 to 10 carbon atoms, such as ethylene, propylene, 1-butene, isobutene, 1 α-olefins such as -hexene are preferred, and among these, ethylene as the monomer unit is more preferred.

The content of cycloolefin monomer units in the cycloolefin polymer in component (P2) is preferably 10 to 100 mol%, and 20 to 100 mol%, based on the total structural units (100 mol%) constituting the cycloolefin polymer. is more preferable.

The weight average molecular weight of the cycloolefin polymer in component (P2) is preferably in the range of 10,000 to 2,000,000, more preferably in the range of 30,000 to 1,500,000.
When the weight average molecular weight of the cycloolefin polymer is at least the lower limit of the above-mentioned preferred range, the softening temperature of the polymer can be easily controlled to a temperature suitable for bonding the support and the substrate. When it is below the upper limit of the above-mentioned preferred range, it becomes easier to obtain an adhesive composition that can form an adhesive layer that is easily dissolved in a hydrocarbon solvent and removed.

The number of cycloolefin polymers in the component (P2) may be one or two or more.

Cycloolefin polymers are polymers that do not have polar groups, such as polymers formed by polymerizing monomer components consisting of cycloolefin monomers and alkene monomers, and they do not generate gas at high temperatures. It is preferable from the viewpoint of suppressing.
There are no particular limitations on the polymerization method, polymerization conditions, etc. when polymerizing the monomer components, and they may be appropriately set according to conventional methods.

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

The content ratio of the cycloolefin polymer in the (P) component is 0 to 50% by mass based on the total amount (100% by mass) of the (P) component. It is preferably 0 to 30% by weight, more preferably 0 to 25% by weight, and particularly preferably 0 to 20% by weight.

〔acrylic resin〕
(P2) Component may include an acrylic resin. When 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 (homopolymers, copolymers) polymerized using (meth)acrylic esters as monomers. "(Meth)acrylic" means at least one of acrylic or methacrylic.

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

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

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

In the (meth)acrylic acid ester having an aromatic ring, examples of the aromatic ring include a phenyl group, a benzyl group, a tolyl group, a xylyl group, a biphenyl group, a naphthyl group, an anthracenyl group, a phenoxymethyl group, and a phenoxyethyl group. etc. The aromatic ring may have a substituent, and may have a linear or branched alkyl group having 1 to 5 carbon atoms.

In the acrylic resin, the above-mentioned (meth)acrylic esters may be used alone or in combination of two or more.

The acrylic resin is one type selected from the group consisting of (meth)acrylic acid alkyl esters having a chain structure, (meth)acrylic acid esters having an aliphatic ring, and (meth)acrylic acid esters having an aromatic ring. A resin obtained by polymerizing the above is preferable.
Among these, resins obtained by polymerizing a (meth)acrylic acid alkyl ester and a (meth)acrylic ester having an aliphatic ring are 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 therewith.
Examples of such polymerizable monomers include styrene, styrene derivatives, and monomers containing maleimide groups. 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 above-mentioned structural unit (u21).

Moreover, among the acrylic resins, a resin obtained by polymerizing a (meth)acrylic acid ester monomer and styrene is preferable. When the acrylic resin has styrene units, the heat resistance of the acrylic resin is improved. In addition, compatibility with other resins and solubility in hydrocarbon solvents are improved.
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, 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 other resins is increased, and a more stable adhesive composition can be easily obtained.

The weight average molecular weight of the acrylic resin is preferably 2,000 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 preferred range, it is possible to easily provide an adhesive composition having thermal fluidity suitable for bonding, for example, a substrate and a support.

Acrylic resins may be used in combination of two or more types.
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 preferably 0 to 30% by mass, based on the total amount (100% by mass) of the component (P). It is more preferably 25% by weight, even more preferably from 0 to 20% by weight, particularly preferably from 0 to 10% by weight.

[Curable monomer]
Component (P2) may include a curable monomer. When 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, typically a polyfunctional curable monomer, and a polyfunctional (meth)acrylate monomer is particularly preferred.

Examples of polyfunctional (meth)acrylate monomers 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)acrylate. meth)acrylate, butylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexane glycol di(meth)acrylate, 1,4-cyclohexanedimethanol di(meth)acrylate, tricyclodecane di(meth)acrylate Methanol di(meth)acrylate, 9,9-bis[4-(2-(meth)acryloyloxyethoxy)phenyl]fluorene, propoxylated bisphenol A di(meth)acrylate, 1,3-adamantanediol di(meth)acrylate , 5-hydroxy-1,3-adamantanediol di(meth)acrylate, 1,3,5-adamantanetriol tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, glycerin di(meth)acrylate, pentaerythritol di (meth)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, phthalic acid diglycidyl ester di(meth)acrylate, glycerin tri(meth)acrylate, glycerin polyglycidyl ether poly Examples include (meth)acrylate, urethane (meth)acrylate (ie, tolylene diisocyanate), a reaction product of trimethylhexamethylene diisocyanate, hexamethylene diisocyanate, and 2-hydroxyethyl (meth)acrylate, and the like.

These polyfunctional (meth)acrylates may be used alone or in combination of two or more.
The curable monomer preferably contains a cyclic structure, more preferably a polycyclic aliphatic structure. By preferably including a cyclic structure, more preferably a polycyclic aliphatic structure, the curable monomer can further improve its compatibility with the cycloolefin polymer. Furthermore, by polymerizing a curable monomer used in combination with the cycloolefin polymer, the heat resistance of the adhesive layer can be further improved.

Among the curable monomers, (meth)acrylate monomers having a cyclic group are particularly preferred, such as tricyclodecane dimethanol di(meth)acrylate, 1,3-adamantanediol di(meth)acrylate, 5-hydroxy-1,3 -Adamantanediol di(meth)acrylate, 1,3,5-adamantanetrioltri(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 preferred, and tricyclodecane dimethanol di(meth)acrylate is particularly preferred.

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

In the adhesive composition of this embodiment, the content of component (P) may be adjusted depending on the thickness of the adhesive layer to be formed, the type of each resin, etc.

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

≪Polymerization inhibitor≫
The adhesive composition of this embodiment may further contain a polymerization inhibitor.
A polymerization inhibitor is a component that has the function of preventing radical polymerization reactions caused by heat or light. Polymerization inhibitors exhibit high reactivity to radicals. For this reason, for example, when a cycloolefin polymer is used as the component (P2), the reaction between the polymerization inhibitor and the radicals proceeds more preferentially than the reaction between the cycloolefin polymer and the radicals, and the cycloolefin polymers polymerize with each other. prohibited from doing. Thereby, the formed adhesive layer is heated, thereby increasing the chemical resistance of the adhesive layer.

As the polymerization inhibitor, those having a phenol skeleton are preferred. For example, hindered phenol-based antioxidants can be used as such polymerization inhibitors, such as pyrogallol, benzoquinone, hydroquinone, methylene blue, tert-butylcatechol, monobenzyl ether, methylhydroquinone, amylquinone, and 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]ethylidene]bisphenol, 4,4',4''-ethylidene tris(2-methylphenol) , 4,4',4''-ethylidene trisphenol, 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, 5-di-tert-butyl-4-hydroxyphenyl) propionate, pentaerythryl tetrakis [3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (trade name IRGANOX1010, manufactured by BASF), Examples include tris(3,5-di-tert-butylhydroxybenzyl)isocyanurate, thiodiethylenebis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], and the like.

One type of polymerization inhibitor may be used alone, or two or more types may be used in combination.
The content of the polymerization inhibitor may be appropriately determined depending on the type of resin component, the use of the adhesive composition, and the usage environment. Preferably.
If the content of the polymerization inhibitor is within the above-mentioned preferred range, the effect of suppressing polymerization will be well exhibited, and the chemical resistance of the adhesive layer will be further enhanced after the high-temperature process.

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

Examples of the peroxide in the thermal polymerization initiator include ketone peroxide, peroxyketal, hydroperoxide, dialkyl peroxide, and peroxy ester. Specifically, such peroxides include acetyl peroxide, dicumyl peroxide, tert-butyl peroxide, t-butylcumyl peroxide, propionyl peroxide, benzoyl peroxide (BPO), 2-chlorobenzoyl peroxide, 3-chlorobenzoyl peroxide, 4-chlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, 4-bromomethylbenzoyl peroxide, lauroyl peroxide, potassium persulfate, diisopropyl peroxycarbonate, tetralin hydroperoxide, 1-phenyl -2-Methylpropyl-1-hydroperoxide, tert-butyl pertriphenylacetate, tert-butyl hydroperoxide, tert-butyl performate, tert-butyl peracetate, tert-butyl perbenzoate, tert-butyl perphenylacetate Examples include butyl, tert-butyl per-4-methoxyacetate, tert-butyl per-N-(3-tolyl)carbamate, and the like.

The peroxides include, for example, the product name "Percmil (registered trademark)", the product name "Perbutyl (registered trademark)", the product name "Perloil (registered trademark)", and the product name "Perocta" manufactured by NOF Corporation. (registered trademark)" can be used.

Examples of the azo 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'-azobisisobutyramide , 2,2'-azobisisobutyronitrile, methyl 2,2'-azobis-2-methylpropionate, 2,2'-dichloro-2,2'-azobisbutane, 2,2'-azobis-2- Methylbutyronitrile, dimethyl 2,2'-azobisisobutyrate, 1,1'-azobis(1-methylbutyronitrile-3-sodium 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' -Azobiscyclohexanenitrile, 2,2'-azobis-2-propylbutyronitrile, 1,1'-azobis-1-chlorophenylethane, 1,1'-azobis-1-cyclohexanecarbonitrile, 1,1'- Azobis-1-cycloheptanenitrile, 1,1'-azobis-1-phenylethane, 1,1'-azobiscumene, ethyl 4-nitrophenylazobenzylcyanoacetate, phenylazodiphenylmethane, phenylazotriphenylmethane, 4-nitro Phenylazotriphenylmethane, 1,1'-azobis-1,2-diphenylethane, poly(bisphenol A-4,4'-azobis-4-cyanopentanoate), poly(tetraethylene glycol-2,2') -azobisisobutyrate), etc.

Examples of the photopolymerization initiator include 1-hydroxycyclohexylphenylketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy -2-Methyl-1-propan-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 1-(4-dodecylphenyl)-2-hydroxy-2- Methylpropan-1-one, 2,2-dimethoxy-1,2-diphenylethan-1-one, bis(4-dimethylaminophenyl)ketone, 2-methyl-1-[4-(methylthio)phenyl]-2 -morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one, ethanone 1-[9-ethyl-6-(2-methylbenzoyl) -9H-carbazol-3-yl]-1-(o-acetyloxime), 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 4-benzoyl-4'-methyldimethylsulfide, 4-dimethylaminobenzoic acid, 4 -Methyl dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, butyl 4-dimethylaminobenzoate, 4-dimethylamino-2-ethylhexylbenzoic acid, 4-dimethylamino-2-isoamylbenzoic acid, benzyl-β-methoxy Ethyl acetal, benzyl dimethyl ketal, 1-phenyl-1,2-propanedione-2-(o-ethoxycarbonyl) oxime, methyl o-benzoylbenzoate, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4 -dimethylthioxanthone, 1-chloro-4-propoxythioxanthone, thioxanthene, 2-chlorothioxanthene, 2,4-diethylthioxanthene, 2-methylthioxanthene, 2-isopropylthioxanthene, 2-ethylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, 2,3-diphenylanthraquinone, azobisisobutyronitrile, benzoyl peroxide, cumene peroxide, 2-mercaptobenzimidal, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, 2- (o-chlorophenyl)-4,5-diphenylimidazole dimer, 2-(o-chlorophenyl)-4,5-di(methoxyphenyl)imidazole dimer, 2-(o-fluorophenyl)-4,5 -diphenylimidazole dimer, 2-(o-methoxyphenyl)-4,5-diphenylimidazole dimer, 2-(p-methoxyphenyl)-4,5-diphenylimidazole dimer, 2,4,5 - triarylimidazole dimer, benzophenone, 2-chlorobenzophenone, 4,4'-bisdimethylaminobenzophenone (i.e., Michler's ketone), 4,4'-bisdiethylaminobenzophenone (i.e., ethyl Michler's ketone), 4,4 '-dichlorobenzophenone, 3,3-dimethyl-4-methoxybenzophenone, benzyl, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin-n-butyl ether, benzoin isobutyl ether, benzoin-t-butyl ether, acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, dichloroacetophenone, trichloroacetophenone, pt-butylacetophenone, p-dimethylaminoacetophenone, pt-butyltrichloroacetophenone, p- t-Butyldichloroacetophenone, α,α-dichloro-4-phenoxyacetophenone, thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, dibenzosuberone, pentyl-4-dimethylaminobenzoate, 9-phenylacridine, 1,7- Bis-(9-acridinyl)heptane, 1,5-bis-(9-acridinyl)pentane, 1,3-bis-(9-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-(furan-2-yl)ethenyl]-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(4-diethylamino-2-methylphenyl) ethenyl]-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(3,4-dimethoxyphenyl)ethenyl]-4,6-bis(trichloromethyl)-s-triazine, 2-( 4-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-ethoxystyryl)-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-trichloromethyl-6-(3-bromo-4-methoxy)styrylphenyl-s-triazine, 2,4 -bis-trichloromethyl-6-(2-bromo-4-methoxy)styrylphenyl-s-triazine and the like.

Examples of the photopolymerization initiators include "IRGACURE OXE02", "IRGACURE OXE01", "IRGACURE 369", "IRGACURE 651", "IRGACURE 907" (all trade names, manufactured by BASF), and "NCI-831". (trade name, manufactured by ADEKA Co., Ltd.) and other commercially available products can be used.

One type of polymerization initiator 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 depending on the amount of the curable monomer used.
For example, in the adhesive composition of the present embodiment, the content of the polymerization initiator is preferably 0.1 to 10 parts by weight, and 0.5 to 5 parts by weight, based on 100 parts by weight of the curable monomer. It is more preferable that

≪Solvent component≫
The adhesive composition of this embodiment can be prepared by dissolving component (P) and optional components as needed in a solvent component.
As the solvent component, for example, one that can dissolve each component for the adhesive composition and make a uniform solution can be used, and one type may be used alone, or two or more types may be used in combination. May be used.

Examples of the solvent component include hydrocarbon solvents and petroleum solvents.
Note that the hydrocarbon solvent and petroleum solvent are hereinafter also collectively referred to as "component (S1)." Solvent components other than the (S1) component may be referred to as "(S2) component."

Examples of hydrocarbon solvents include linear, branched, or cyclic hydrocarbons, such as hexane, heptane, octane, nonane, methyloctane, decane, undecane, dodecane, tridecane, and the like. Branched hydrocarbons such as isooctane, isononane, isododecane; p-menthane, o-menthane, m-menthane, diphenylmenthane, 1,4-terpine, 1,8-terpine, bornane, norbornane, pinane, thujan, Calan, longifolene, α-terpinene, β-terpinene, γ-terpinene, α-pinene, β-pinene, α-thujone, β-thujone, cyclohexane, cycloheptane, cyclooctane, indene, pentalene, indane, tetrahydroindene, naphthalene , tetrahydronaphthalene (tetralin), decahydronaphthalene (decalin), and other cyclic hydrocarbons.

The petroleum solvent is a solvent refined from heavy oil, and includes, for example, white kerosene, paraffinic solvents, and isoparaffinic solvents.

In addition, the component (S2) includes terpene solvents having an oxygen atom, carbonyl group, or acetoxy group as a polar group, such as geraniol, nerol, linalool, citral, citronellol, menthol, isomenthol, neomenthol, α -Terpineol, β-terpineol, γ-terpineol, terpinen-1-ol, terpinen-4-ol, dihydroterpineyl acetate, 1,4-cineole, 1,8-cineole, borneol, carvone, ionone, thujone, camphor etc.

In addition, as the (S2) component, lactones such as γ-butyrolactone; ketones such as acetone, methyl ethyl ketone, cyclohexanone (CH), methyl-n-pentyl ketone, methyl isopentyl ketone, and 2-heptanone; ethylene glycol, diethylene glycol , polyhydric alcohols such as propylene glycol and dipropylene glycol; compounds having ester bonds such as ethylene glycol monoacetate, diethylene glycol monoacetate, propylene glycol monoacetate, or dipropylene glycol monoacetate; the above polyhydric alcohols or the above esters; Derivatives of polyhydric alcohols such as monoalkyl ethers of compounds having bonds such as monomethyl ether, monoethyl ether, monopropyl ether, monobutyl ether, or compounds having ether bonds such as monophenyl ether (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, cresyl methyl ether, diphenyl ether, dibenzyl ether, phenethol, and butylphenyl ether can also be mentioned.

The content of the solvent component in the adhesive composition of the present embodiment may be adjusted as appropriate depending on the thickness of the adhesive layer to be formed. It is preferably within 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 ingredients excluding the solvent component) concentration within a range of 10 to 80% by mass.
If the content of the solvent component is within the above-mentioned preferred range, the viscosity can be easily adjusted.

The adhesive composition of this embodiment can be prepared by mixing and dissolving or dispersing other components in a solvent component.
From the viewpoint of solubility of component (P), this solvent component preferably contains a hydrocarbon solvent, and more preferably contains a branched hydrocarbon or cyclic hydrocarbon solvent.
By containing a branched or cyclic hydrocarbon solvent in the solvent component, clouding that may occur when the adhesive composition is stored in a liquid state (especially at low temperatures) is easily prevented, further improving storage stability. can be done.

Moreover, it is preferable to use a solvent component containing a condensed polycyclic hydrocarbon or a branched hydrocarbon as a hydrocarbon solvent. In this case, the solvent component may be selected from the group consisting of condensed polycyclic hydrocarbons and branched chain hydrocarbons, or it may also contain other components such as saturated aliphatic hydrocarbons. You can leave it there.
In the solvent component, the content of one selected from the group consisting of fused polycyclic hydrocarbons and branched chain hydrocarbons is preferably 40 parts by mass or more, and 60 parts by mass or more, based on 100 parts by mass of the entire hydrocarbon solvent. It is more preferably at least 80 parts by mass, even more preferably at least 80 parts by mass. When the amount is 40 parts by mass or more of the entire hydrocarbon solvent, the solubility of the component (P) will be better.

When using a polymerization initiator, 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 in which the polymerization initiator or polymerization inhibitor is preliminarily dissolved in the component (S2). The amount of component (S2) to be used may be adjusted appropriately depending on the type of polymerization initiator or polymerization inhibitor, etc., and for example, it is preferably 1 to 50 parts by mass, based on 100 parts by mass of component (S1), ~30 parts by mass is more preferred. If the amount of component (S2) used is within the above-mentioned preferred range, the polymerization initiator or polymerization inhibitor can be sufficiently dissolved.

In the adhesive composition of the present embodiment described above, the component (P) contains the component (P1), thereby forming an adhesive layer with high heat resistance and improved adhesion to the substrate. As a result, the adhesive layer formed using the adhesive composition of the present embodiment is less likely to cause displacement of the substrate, for example, before and after the sealing operation due to the influence of high temperature treatment during semiconductor package manufacturing.

Furthermore, since the adhesive layer formed from the adhesive composition of this embodiment has high gas barrier properties, it can be used as a gas barrier layer.
When a sealing substrate containing resin is used, moisture in the resin evaporates to generate gas. For example, as shown in FIG. 6(A), when the support 12 and the sealing substrate 5 are bonded together using a conventional adhesive composition (for example, an elastomer adhesive), the adhesive composition The formed adhesive layer 3' cannot suppress the transfer of gas generated from the sealing substrate 5, and voids (bubbles) are generated between the sealing substrate 5 and the support 12. The voids cause separation between the sealing substrate 5 and the support body 12.
On the other hand, the adhesive layer formed from the adhesive composition of the present embodiment has high gas barrier properties and good adhesion to the sealing substrate 5, and therefore effectively blocks gas generated from the sealing substrate 5. be able to. Therefore, as shown in FIG. 6(B), the adhesive layer 3 including the first adhesive composition layer 3-1 formed of the adhesive composition of this embodiment is attached to the sealing substrate 5 and the support 12. By forming the first adhesive composition layer 3-1 between the two layers, the first adhesive composition layer 3-1 becomes a gas barrier layer and can suppress the generation of voids.
The adhesive composition of this embodiment may be used alone or in combination with another adhesive composition (an adhesive composition that does not contain the (P1) component). A second adhesive composition layer 3-2 is formed using another adhesive composition, and a second adhesive composition layer 3-2 is formed from the first adhesive composition layer 3-1 and the second adhesive composition layer 3-2. The adhesive layer 3 may be formed. When used in combination with other adhesive compositions, as shown in FIG. 6(B), the sealing substrate 5, the first adhesive adhesive layer 3-1, the second adhesive adhesive layer 3-2, and the support It is preferable that the bodies 12 form a laminate in which the bodies 12 are laminated in this order. By arranging the sealing substrate 5 and the first adhesive bonding layer 3-1 adjacent to each other, the first adhesive bonding layer 3-1 becomes a gas barrier layer, thereby preventing the generation of voids from the sealing substrate 5. can be effectively suppressed.

Furthermore, since the adhesive layer formed from the adhesive composition of this embodiment is less likely to be misaligned, it can be used as a protection layer.
For example, a thin film may be formed on the adhesive layer to form a redistribution layer. FIG. 7A shows an example in which an adhesive layer 3' is formed on a support 12 using a conventional adhesive composition, and a thin film 6 is formed on the adhesive layer 3'. In this case, if the heat resistance of the adhesive layer 3' is low, the adhesive layer 3' may flow due to high temperature treatment, and cracks or wrinkles may occur in the thin film 6.
On the other hand, the adhesive layer formed according to this embodiment has high heat resistance and is less likely to flow due to high temperature treatment. Therefore, as shown in FIG. 7(B), the adhesive layer 3 including the first adhesive composition layer 3-1 formed from the adhesive composition of this embodiment is attached to the support 12 and the thin film 6. By forming the first adhesive composition layer 3-1 in between, the first adhesive composition layer 3-1 becomes a protection layer and can suppress the occurrence of cracks and wrinkles in the thin film 6. Furthermore, 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 this 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 a second adhesive composition layer 3-2 is formed from the first adhesive composition layer 3-1 and the second adhesive composition layer 3-2. The adhesive layer 3 may be formed. When used in combination with other adhesives, as shown in FIG. 7(B), 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 laminate in which the layers are stacked 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, effectively suppressing cracks, wrinkles, peeling, etc. of the thin film 6. be able to.

Furthermore, for example, die bonding may be performed on the bump substrate. FIG. 8A shows an example in which the support 12 and the bump substrate 4 are bonded together 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 from the conventional adhesive composition is low, the adhesive layer 3' will sink during die bonding and the bump will come into contact with the support 12, causing the bump to be deformed. Sometimes.
On the other hand, the adhesive layer formed according to this embodiment has high heat resistance and is unlikely to cause sinking again during die bonding. Therefore, as shown in FIG. 8(B), the adhesive layer 3 including the first adhesive composition layer 3-1 formed of the adhesive composition of this embodiment is attached to the support 12 and the bump substrate 4. By forming the first adhesive composition layer 3-1 between the two layers, the first adhesive composition layer 3-1 becomes a protection layer and can suppress contact between the bump and the support 12 during die bonding. Furthermore, since the first adhesive composition layer 3-1 has high adhesion to the bump substrate 4, peeling of the bump substrate 4 is less likely to occur.
The adhesive composition of this 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 a second adhesive composition layer 3-2 is formed from the first adhesive composition layer 3-1 and the second adhesive composition layer 3-2. The adhesive layer 3 may be formed. When used in combination with other adhesives, as shown in FIG. 8(B), the support 12, the second adhesive composition layer 3-2, the first adhesive composition layer 3-1, and the bump substrate 4 are preferably stacked in this order to form a laminate. 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 preventing the bump substrate from sinking. Can be suppressed.

In the above, other adhesive compositions include, for example, elastomer adhesive compositions, cycloolefin adhesive compositions, maleimide adhesive compositions, and the like.

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

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

<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 supporting substrate has the property of transmitting light. The support base is a member that supports the substrate, and is bonded to the substrate via an adhesive layer. Therefore, the supporting base preferably has the strength necessary to prevent damage or deformation of the substrate during thinning of the sealing body, transportation of the substrate, mounting on the substrate, etc. Further, the supporting substrate is preferably one that transmits light having a wavelength that can alter the quality of the separation layer.
As the material of the supporting base, for example, glass, silicon, acrylic resin, etc. are used. Examples of the shape of the support base include, but are not limited to, rectangular and circular shapes.
Further, as the support base, in order to achieve higher density integration and improve production efficiency, it is also possible to use a circular support base with an enlarged size, or a large panel with a square shape in plan view.

≪Separation layer≫
The separation layer is a layer that is adjacent to the adhesive layer, changes in quality by irradiation with light, and makes it possible to separate the support base from the substrate bonded to the support.
This separation layer can be formed using the composition for forming a separation layer described below, for example, by firing 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 changed in quality by absorbing light transmitted through the support base and irradiated with it.
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 may be blended within a range that does not impair the essential characteristics of the present invention. It may be a layer.

"Deterioration" of the separation layer refers to a phenomenon in which the separation layer can be destroyed by external force, or the adhesive strength between the separation layer and a layer in contact with it is reduced. The separation layer becomes brittle by absorbing light and loses its strength or adhesion before being exposed to light. Such deterioration of the separation layer occurs due to decomposition, change in steric configuration, dissociation of functional groups, etc. due to the energy of absorbed light.

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

It is preferable that the surface of the separation layer in contact with the adhesive layer is flat (no irregularities are formed), so that the adhesive layer can be easily formed and the supporting base and the substrate can be bonded uniformly. Easy to attach.

[Composition for forming separation layer]
The composition for forming a separation layer, which is a material for forming the separation layer, may be, for example, a fluorocarbon, a polymer having a repeating unit containing a structure having light absorption property, an inorganic substance, a compound having an infrared absorption structure. , an infrared absorbing substance, a reactive polysilsesquioxane, or a resin component having a phenol skeleton.
In addition, the composition for forming a separation layer may include a filler, a plasticizer, a thermal acid generator component, a photoacid generator component, an organic solvent component, a surfactant, a sensitizer, or improve the separation of the supporting substrate as optional components. It may contain components that can be used.

- Fluorocarbon The separation layer may contain fluorocarbon. The separation layer made of fluorocarbon is altered by absorbing light, and as a result loses its strength or adhesiveness before being irradiated with light. Therefore, by applying a slight external force (for example, by lifting the support), the separation layer is destroyed and the support and the substrate can be easily separated. The fluorocarbon constituting the separation layer can be suitably formed into a film by plasma CVD.
Fluorocarbons absorb light with a unique range of wavelengths depending on their type. By irradiating the separation layer with light having a wavelength within a range that is absorbed by the fluorocarbon used in 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 may be a solid laser such as a YAG laser, a ruby laser, a glass laser, a YVO ₄ laser, an LD laser, a fiber laser, or a liquid laser such as a dye laser, depending on the wavelength that the fluorocarbon can absorb. , a gas laser such as a CO ₂ laser, an excimer laser, an Ar laser, or a He-Ne laser, a semiconductor laser, a free electron laser, or a non-laser light may be used as appropriate. As the wavelength that can alter the quality of 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 light absorption property The separation layer may contain a polymer having a repeating unit including a structure having light absorption property. The polymer changes in quality upon irradiation with light. .
Examples of the structure having light-absorbing properties include an atomic group containing a conjugated π-electron system consisting of a substituted or unsubstituted benzene ring, a condensed ring, or a heterocycle. More specifically, the structure having light-absorbing properties is a cardo structure, or a benzophenone structure, diphenyl sulfoxide structure, diphenyl sulfone structure (bisphenyl sulfone structure), diphenyl sulfone structure present in the side chain of the polymer. structure or diphenylamine structure.
The above-described light-absorbing structure can absorb light having a wavelength within a desired range, depending on its type. For example, the wavelength of light that can be absorbed by the above-mentioned light-absorbing structure is preferably within the range of 100 to 2000 nm, more preferably within the range of 100 to 500 nm.

Examples of light that can be absorbed by the above-mentioned light-absorbing structure include high-pressure mercury lamps (wavelengths of 254 nm or more and 436 nm or less), KrF excimer lasers (wavelengths of 248 nm), ArF excimer lasers (wavelengths of 193 nm), _F2 Light emitted from an excimer laser (wavelength 157 nm), XeCl laser (wavelength 308 nm), XeF laser (wavelength 351 nm) or solid-state UV laser (wavelength 355 nm), or g-line (wavelength 436 nm), h-line (wavelength 405 nm) or i-line. (wavelength: 365 nm).

- Inorganic material The separation layer may be made of an inorganic material. This inorganic substance may be any substance that changes in quality by absorbing light, and preferably includes one or more types selected from the group consisting of metals, metal compounds, and carbon. A metal compound is a compound containing a metal atom, and includes, for example, a metal oxide and a metal nitride.
Examples of such inorganic substances include one or more selected from the group consisting of gold, silver, copper, iron, nickel, aluminum, titanium, chromium, SiO ₂ , SiN, Si ₃ N ₄ , TiN, and carbon.
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 above-mentioned inorganic substances absorb light having a wavelength within a specific range depending on the type of the inorganic substance.

The light irradiated to the separation layer made of an inorganic material may be a solid laser such as a YAG laser, a ruby laser, a glass laser, a YVO ₄ laser, an LD laser, a fiber laser, or a dye laser, depending on the wavelength that the inorganic material can absorb. Liquid lasers such as _CO2 lasers, excimer lasers, Ar lasers, gas lasers such as He--Ne lasers, semiconductor lasers, free electron lasers, or non-laser light may be used as appropriate.
The separation layer made of an inorganic substance can be formed on the supporting substrate by known techniques such as sputtering, chemical vapor deposition (CVD), plating, plasma CVD, and spin coating.

- 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 changes in quality by absorbing infrared rays.
Examples of structures having infrared absorbing properties or compounds having this structure include alkanes, alkenes (vinyl, trans, cis, vinylidene, trisubstituted, tetrasubstituted, conjugated, cumulene, cyclic), alkynes (monocarbon), (substituted, disubstituted), monocyclic aromatics (benzene, monosubstituted, disubstituted, trisubstituted), 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, oxirane ring ether, peroxide ether, ketone, dialkyl carbonyl, aromatic carbonyl, 1,3 - Enols of diketones, o-hydroxyarylketones, dialkyl aldehydes, aromatic aldehydes, carboxylic acids (dimers, carboxylic acid anions), formate esters, acetate esters, conjugated esters, non-conjugated esters, aromatic esters, lactones (β) -, γ-, δ-), aliphatic acid chlorides, aromatic acid chlorides, acid anhydrides (conjugated, non-conjugated, cyclic, acyclic), primary amides, secondary amides, lactams, Primary amines (aliphatic, aromatic), secondary amines (aliphatic, aromatic), tertiary amines (aliphatic, aromatic), primary amine salts, secondary amine salts, tertiary amines amine salt, ammonium ion, aliphatic nitrile, aromatic nitrile, carbodiimide, aliphatic isonitrile, aromatic isonitrile, isocyanate ester, thiocyanate ester, aliphatic isothiocyanate ester, aromatic isothiocyanate ester, aliphatic nitro compound, Aromatic nitro compounds, nitroamines, nitrosamines, nitrates, nitrites, nitroso bonds (aliphatic, aromatic, monomers, dimers), sulfur compounds such as mercaptans or thiophenols or thiol acids, thiocarbonyl groups, Sulfoxide, sulfone, sulfonyl chloride, primary sulfonamide, secondary sulfonamide, sulfuric acid ester, carbon-halogen bond, Si-A ¹ bond (A ¹ is H, C, O or halogen), PA ² Examples include a bond (A ² is H, C or O) or a Ti--O bond.

Examples of structures containing the above carbon-halogen bonds include -CH ₂ Cl, -CH ₂ Br, -CH ₂ I, -CF ₂ -, -CF ₃ , -CH=CF ₂ , -CF=CF ₂ , Examples include aryl chloride and aryl chloride.

Examples of structures containing the above Si-A ¹ bond include 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 . The structure containing the Si--A ¹ bond preferably has a siloxane skeleton or a silsesquioxane skeleton.

Structures containing the above PA ² bond include, for example, PH, PH ₂ , P-CH ₃ , P-CH ₂ -, PC ₆ H ₅ , A ³ ₃ -P-O (A ³ is fatty 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.

Examples of compounds containing the above Ti-O bond include (i) tetra-i-propoxytitanium, tetra-n-butoxytitanium, tetrakis(2-ethylhexyloxy)titanium, or titanium-i-propoxyoctylene glycolate; (ii) chelated titanium such as di-i-propoxy bis(acetylacetonato)titanium or propanedioxytitanium bis(ethylacetoacetate); (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(O-n-C ₄ H ₉ ) ₂ -O-] _n -n-Titanium polymers such as C ₄ H ₉ ; (iv) tri-n-butoxytitanium monostearate, titanium stearate, di-i-propoxytitanium diisostearate or (2-n-butoxycarbonylbenzoyloxy) Examples include acylate titanium such as tributoxytitanium; and (v) water-soluble titanium compounds such as di-n-butoxy bis(triethanolaminato)titanium.
Among them, compounds containing Ti--O bonds include di-n-butoxy bis(triethanolaminato) titanium (Ti(OC ₄ H ₉ ) ₂ [OC ₂ H ₄ N(C ₂ H ₄ OH) ₂ ] ₂ ) is preferred.

The above-mentioned infrared absorbing structure can absorb infrared rays having a desired range of wavelengths by selecting its type. 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.
Furthermore, when the above structure is a Si--O bond, a Si--C bond, or a Ti--O bond, the thickness is preferably within the range of 9 to 11 μm.

Note that the wavelengths of infrared rays that can be absorbed by each of the above structures can be easily understood by those skilled in the art. For example, as absorption bands in each structure, non-patent literature: SILVERSTEIN, BASSLER, MORRILL, "Spectral Identification Method of Organic Compounds (5th Edition) - Combination of MS, IR, NMR, and UV" (published in 1992), Reference may be made to the description on pages 146 to 151.

Compounds with an infrared absorbing structure used to form the separation layer include compounds with the above-mentioned structure that can be dissolved in a solvent for coating and solidified to form a solid layer. It is not particularly limited as long as it can form. However, in order to effectively change the properties of the compound in the separation layer and facilitate the separation between the supporting base and the substrate, it is necessary to have a large absorption of infrared rays in the separation layer. Preferably, the transmittance is low. Specifically, the infrared transmittance in the separation layer is preferably lower than 90%, and more preferably lower than 80%.

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

- Reactive polysilsesquioxane The separation layer can be formed by polymerizing 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 that can form a silanol group by hydrolysis. . By condensing the silanol groups or functional groups capable of forming silanol groups, they can be polymerized with each other. In addition, if the reactive polysilsesquioxane has a silanol group or a functional group that can form a silanol group, it can have a silsesquioxane skeleton with a random structure, cage structure, ladder structure, etc. A reactive polysilsesquioxane that is equipped can be employed.

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 preferred range, it can be suitably modified by irradiation with infrared rays (preferably far infrared rays, more preferably light with a wavelength of 9 to 11 μm). A separation layer that can be formed can be formed.

The weight average molecular weight (Mw) of the reactive polysilsesquioxane is preferably from 500 to 50,000, more preferably from 1,000 to 10,000.
If the weight average molecular weight (Mw) of the reactive polysilsesquioxane is within the above-mentioned preferred range, it can be suitably dissolved in a solvent and suitably applied onto 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 etc. and increases photoreactivity.
"Having a phenol skeleton" as used herein means containing 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 1,000 to 30,000, even more preferably 1,500 to 20,000, particularly preferably 2,000 to 15,000. When the molecular weight of the resin component is at most the upper limit of the above-mentioned preferred range, the solubility of the composition for forming a separation layer in a solvent is increased.
As the molecular weight of the resin component, the weight average molecular weight (Mw) in terms of polystyrene measured by GPC (gel permeation chromatography) is used.

Examples of resin components having a phenol skeleton include novolak type phenol resin, resol type phenol resin, hydroxystyrene resin, hydroxyphenylsilsesquioxane resin, hydroxybenzylsilsesquioxane resin, phenol skeleton-containing acrylic resin, and general formulas described below. Examples include resins having a repeating unit represented by (P2). Among these, novolac type phenolic resins and resol type phenolic resins are more preferred.

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

The adhesive layer 3 includes a first adhesive composition layer formed using the adhesive composition according to the first embodiment. Further, the adhesive layer 3 may include, in addition to the first adhesive composition layer, a second adhesive composition layer formed using another adhesive composition. In this case, the first adhesive composition layer is preferably adjacent to the substrate 4. By disposing the first adhesive composition layer adjacent to the substrate 4, the adhesion between the adhesive layer 3 and the substrate 4 can be further improved. The adhesive composition forming the second adhesive composition layer is an adhesive composition that does not contain polymer (P1). Such adhesive compositions are not particularly limited, and include, for example, elastomer adhesive compositions, cycloolefin adhesive compositions, maleimide adhesive compositions, and the like.

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 of 5 μm or more and 40 μm or less, even more preferably 10 μm or more and 30 μm or less, and it is preferably 15 μm or more and 25 μm or less. Particularly preferred. When the thickness of the first adhesive composition layer is equal to or greater than the lower limit of the preferable range, gas barrier performance or protection performance for substrates and the like is further improved. Moreover, since the thickness of the first adhesive composition layer is less than or equal to 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 even more 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 preferable range, the support and the substrate can be bonded together better.

When the adhesive layer 3 consists only of the first adhesive composition layer, the thickness of the adhesive layer 3 is preferably in the range of, for example, 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 that it be within. If the thickness of the adhesive layer 3 is within the range of 0.1 μm or more and 50 μm or less, the support base 1 and the substrate 4 can be bonded together better. Furthermore, by having a thickness of the adhesive layer of 1 μm or more, the substrate can be sufficiently fixed on the supporting base, and by having a thickness of the adhesive layer of 10 μm or less, the adhesive layer can be removed in the subsequent removal step. Can be easily removed.

<Substrate>
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, for example.
Although a silicon wafer substrate is typically used as the substrate 4, it is not limited thereto, and a ceramic substrate, a thin film substrate, a flexible substrate, etc. may also be used.

In this embodiment, the element is a semiconductor element or other element, and may have a single-layer or multi-layer structure. Note that when the element is a semiconductor element, the electronic component obtained by dicing the sealing substrate becomes a semiconductor device.

Since the laminate of this 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 the substrate. This makes it difficult for the substrate to be misaligned, for example, before and after the sealing operation due to the influence of high temperature processing during the manufacture of semiconductor packages. Furthermore, peeling of the substrate is less likely to occur.

In the laminate of the embodiment described above, the support base 1 and the separation layer 2 are adjacent to each other, but the present invention is not limited to this, and another layer may be further formed between the support base 1 and the separation layer 2. It's okay. In this case, the other layers may be made of a material that transmits light. According to this, a layer that imparts preferable properties to the laminate 10 can be added as appropriate without hindering the incidence of light into the separation layer 2. The wavelength of light that can be used differs depending on the type of material forming the separation layer 2. Therefore, the materials constituting the other layers do not need to transmit light of all wavelengths, and may be appropriately selected from materials that transmit light of wavelengths that can alter the quality of 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 adhesive layer are the same as those described above.

Moreover, in other embodiments, 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 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 to the case where an adhesive layer is formed by directly applying an adhesive composition onto a support, an adhesive layer with good thickness uniformity and surface smoothness can be easily formed.

Examples of the film include, for example, a release film that allows the adhesive layer formed on the film to be easily peeled off from the film, and preferably allows the adhesive layer to 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 flexible films are more preferred.
It is preferable that the film is subjected to a release treatment, if necessary, to facilitate transfer.
The thickness of the film may be set as appropriate, and is, for example, 15 to 125 μm.

Such adhesive films are manufactured by forming an adhesive layer on the film. The adhesive layer may include a first adhesive composition layer, similar to the laminate of the embodiment, and may include a first adhesive composition layer and a second adhesive composition layer. It may include. For example, a method is used in which the adhesive composition is applied onto the film so that the dry thickness of the adhesive layer is 10 to 1000 μm. At that time, a known method can be used as appropriate depending on the desired thickness and uniformity of the adhesive layer.

The adhesive film may also 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, polyethylene terephthalate film, polypropylene film, and polyethylene film are preferable. Moreover, each protective film is preferably coated with silicone or baked in order to facilitate peeling from the adhesive layer.

For example, when a protective film is used, the adhesive film is peeled off, the exposed adhesive layer is placed on the support surface, and the exposed adhesive layer is placed on the film (the back side of the surface on which the adhesive layer is formed). ) The adhesive layer is thermocompression bonded to the surface of the support by moving a heating roller from ) to the surface of the support.
Note that the protective film peeled off from the adhesive film can be reused by sequentially winding it up into a roll using a roller such as a take-up roller.

(Method for manufacturing laminate)
A third aspect of the present invention is a method for manufacturing a laminate in which a support and a substrate are bonded together via an adhesive layer, which includes an adhesive layer forming step and a bonding step.

<First embodiment>
The method for manufacturing a laminate according to the first embodiment includes a step of producing a support, an adhesive layer forming step, and a bonding step.
FIG. 2 is a schematic process diagram illustrating an embodiment of a method for manufacturing a laminate.
FIG. 2(a) is a diagram illustrating the process of producing a support, FIG. 2(b) is a diagram illustrating the adhesive layer forming process, and FIG. 2(c) is a diagram illustrating the bonding process. This is a diagram.
In the method for manufacturing a laminate of this embodiment, a composition containing fluorocarbon is used as the separation layer forming composition. Further, an adhesive layer including the first adhesive composition layer is formed using a composition containing the component (P1) according to the first aspect as the adhesive layer forming composition.

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

The method for forming the separation layer 2 on the supporting substrate 1 is not particularly limited, and examples thereof include methods such as spin coating, dipping, roller blading, 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 composition for forming a separation layer applied on the support base 1 under a heating environment or a reduced pressure environment, or the support is A support is obtained by forming a film on the base 1 by a vapor deposition method.

≪Adhesive layer formation 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 using the adhesive layer forming composition according to the first aspect.
In FIG. 2(b), an adhesive layer 3 including a first adhesive composition layer formed using the adhesive composition according to the first embodiment is formed on the surface of the support 12 on the separation layer 2 side. (that is, the adhesive layer-attached support 123 has been produced).

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 blading, 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 in a reduced pressure environment.

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

Further, when the adhesive layer contains a curable monomer and a photopolymerization initiator, the curable monomer may be polymerized by exposure in an inert gas atmosphere such as nitrogen gas. The conditions for exposure may be appropriately set depending on the type of photopolymerization initiator and the like.

Adhesive layer 3 may include a second adhesive composition layer formed using another adhesive composition. Other adhesive compositions are adhesive compositions that do not contain the (P1) component. In this case, a second adhesive composition layer is formed using another adhesive composition on the surface of the support 12 on the separation layer 2 side, 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 embodiment.

[Lamination 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. 2(c), a supporting base 1 (supporting body 12) on which a separation layer 2 is formed and a substrate 4 on which no separation layer 2 is formed are laminated with an adhesive layer 3 in between, and the supporting base 1, A laminate 10 is obtained in which the separation layer 2, the adhesive layer 3, and the substrate 4 are stacked in this order.

The method of bonding the support 12 and the substrate 4 via the adhesive layer 3 is to place the substrate 4 at a predetermined position on the adhesive layer 3, and support it with a die bonder or the like while heating it under vacuum (for example, about 100° C.). This is done by pressing the body 12 and the substrate 4 together.

According to the method for manufacturing a laminate of the first embodiment, since the adhesive layer including the first adhesive composition layer formed using the composition for forming an adhesive layer according to the first aspect is provided, the adhesive The layer has high heat resistance and good adhesion to the substrate. Therefore, for example, the substrate is less likely to be misaligned before and after the sealing operation, and the substrate is less likely to peel off.

In the method for manufacturing a laminate of the present embodiment described above, the separation layer 2 is formed on the support base 1, but the separation layer 2 is not limited to this, and may be formed on the substrate 4.
Further, the separation layer 2 may be formed on both the support base 1 and the substrate 4, and in this case, the support base 1 and the substrate 4 are connected to each other via the separation layer 2, the adhesive layer 3, and the separation layer 2. and then pasted together.

In the method for manufacturing a laminate of the present embodiment described above, the adhesive layer 3 is formed on the separation layer 2, but the present invention is not limited thereto, and the adhesive layer 3 may be formed on the substrate 4. When the adhesive layer 3 includes a second adhesive composition layer in addition to the first adhesive composition layer, the adhesive composition according to the first aspect is used on the substrate 4 to form the first adhesive composition. forming an adhesive composition layer, and then forming a second adhesive composition layer on the first adhesive composition layer using another adhesive composition, thereby forming an adhesive layer 3. be able to.

<Second embodiment>
FIG. 3 is a schematic process diagram illustrating another embodiment of the method for manufacturing a laminate.
FIG. 3(a) is a diagram showing a laminate manufactured by the manufacturing method of the first embodiment, and FIG. 3(b) is a diagram illustrating a sealing process.
The method for producing a laminate of this other embodiment further includes a sealing step in addition to the step of producing a support, the adhesive layer forming step, and the bonding step.

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

In the sealing process, a sealing material heated to, for example, 130 to 170°C is supplied onto the adhesive layer 3 so as to cover the substrate 4 while maintaining a high viscosity state, and is compression-molded. , a sealed body 20 (laminate) having a sealing material layer 5 provided on an adhesive layer 3 is produced.
At this 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 .

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

According to the method for manufacturing a laminate of the second embodiment, since the adhesive layer is provided by applying the composition for forming an adhesive layer of the embodiment described above, the heat resistance is further improved, and for example, before and after the sealing operation, the adhesive layer is provided. Less likely to cause substrate misalignment.

<Third embodiment>
FIG. 4 is a schematic process diagram illustrating another embodiment of the method for manufacturing a laminate.
FIG. 4(a) is a diagram showing a sealed body manufactured by the manufacturing method of the second embodiment, FIG. 4(b) is a diagram illustrating a grinding process, and FIG. 4(c) is a diagram illustrating a grinding process. FIG. 3 is a diagram illustrating a rewiring formation process.
The method for producing a laminate according to this other embodiment further includes a grinding process and a rewiring forming process in addition to the process of producing a support, the process of forming an adhesive layer, the process of bonding, and the process of sealing.

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

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

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

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

In this way, when photolithography processing, etching processing, etc. are performed, the sealing body 20 (laminate) is treated with an acid such as hydrofluoric acid, an alkali such as tetramethylammonium hydroxide (TMAH), or a resist material that is dissolved. The resist is exposed to resist solvents and processed at high temperatures.
However, by forming the adhesive layer including the first adhesive composition layer formed using the composition for forming an adhesive layer 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 laminate of the third embodiment, the supporting base 1, the separation layer 2, the adhesive layer 3, the sealing material layer 5 covering the substrate 4, and the rewiring layer 6 are laminated in this order. The laminate 30 can be stably produced.
This laminate 30 is a laminate manufactured in a process based on fan-out technology in which terminals provided on the substrate 4 are mounted on the rewiring layer 6 extending outside the chip area.

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

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

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 manufactured by the manufacturing method of the third embodiment, FIG. 5(b) is a diagram illustrating the separation process, and FIG. 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 (arrow) through the support base 1 to alter the quality of the separation layer 2. It is.

As shown in FIG. 5A, in the separation step, the separation layer 2 is irradiated with light (arrow) through the support base 1 to alter the quality of the separation layer 2.
The wavelength that can alter the quality of the separation layer 2 includes, for example, a range of 600 nm or less.
The type and wavelength of the irradiated light may be appropriately selected depending on the transmittance of the support base 1 and the material of the separation layer 2. For example, YAG laser, ruby laser, glass laser, YVO ₄ laser, LD laser, fiber Solid lasers such as lasers, liquid lasers such as dye lasers, gas lasers such as CO ₂ lasers, excimer lasers, Ar lasers, and He-Ne lasers, laser beams such as semiconductor lasers, free electron lasers, and non-laser beams can be used. can. Thereby, the separation layer 2 can be changed in quality and the support base 1 and the substrate 4 can be easily separated.

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

After the separation layer 2 is irradiated with light (arrow) to alter the quality of the separation layer 2, the supporting base 1 is separated from the substrate 4, as shown in FIG. 5(b).
For example, the supporting base 1 and the substrate 4 are separated by applying force in a direction in which the supporting base 1 and the substrate 4 separate from each other. Specifically, one of the support base 1 or the substrate 4 side (rewiring layer 6) is fixed to the stage, and the other is lifted while being suctioned and held by a separation plate equipped with a suction pad such as a bellows pad. Support base 1 and substrate 4 can be separated.
The force applied to the laminate 30 may be adjusted appropriately depending on the size of the laminate 30, and is not limited to this. By applying a force of about .98 to 49 N), the support base 1 and the substrate 4 can be suitably separated.

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

Examples of a method for removing the adhesive layer 3 and the like adhering to the substrate 4 include a method of removing residues of the adhesive layer 3 and separation layer 2 using a cleaning liquid.
As the cleaning liquid, a cleaning liquid containing an organic solvent is suitably used. As the organic solvent in this cleaning liquid, it is preferable to use an organic solvent included in the composition for forming a separation layer and a solvent component included in the composition for forming an adhesive layer.
The adhesive layer formed using the adhesive layer forming composition of the embodiment described above has enhanced solubility in hydrocarbon solvents. Therefore, in the embodiment, the cleaning removability of the adhesive layer is good.

In the electronic component manufacturing method of the present embodiment, after the above-described removal step, the electronic component 40 may be further subjected to treatments 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 each independently represent an organic group having 1 to 30 carbon atoms or a hydrogen atom. However, at least one of R ^u11 to R ^u14 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).

<Manufacture of polymer>
The polymer of this embodiment can be synthesized, for example, as follows.

≪Polymerization step (processing S1)≫
First, a monomer for inducing the structural unit (p1) is prepared as a monomer. Examples of the monomer include monomers 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。］

[In the formula, R ^u11 to R ^u14 and n are the same as R ^u11 to R ^u14 and n in the general formula (p1-1). ]

When the polymer of this 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 this embodiment has the above structural unit (p2), a cycloolefin monomer that induces the structural unit (p2) is prepared. Moreover, when the polymer of this embodiment has the above-mentioned structural unit (p3), a monomer containing a maleimide skeleton that induces the structural unit (p3) is prepared.

Next, each of the prepared monomers is subjected to addition polymerization to obtain a polymer. Addition polymerization is carried out, for example by coordination polymerization.

In this embodiment, solution polymerization can be performed by dissolving each of the monomers and the organometallic catalyst in a solvent and then heating them for a predetermined period of time. At this time, the heating temperature can be, for example, 30°C to 120°C. Further, the heating time can be, for example, 0.1 hour to 100 hours. It is more preferable to perform solution polymerization after removing dissolved oxygen in the solvent by nitrogen or argon bubbling.

In the polymerization step, a molecular weight regulator, a chain transfer agent, etc. can be used as necessary. Examples of the chain transfer agent include alkylsilane compounds such as trimethylsilane, triethylsilane, and tributylsilane; and organic aluminums such as triethylaluminum, tributylaluminum, and MAO (methylalumoxane). One type of chain transfer agent may be used alone, or two or more types may be used in combination.

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; One or more types of alcohols such as methyl alcohol, ethyl alcohol, and isopropyl alcohol can be used.

The organometallic catalyst is not particularly limited as long as addition polymerization proceeds, but for example, a cationic complex in which a phosphine or diimine ligand is coordinated to a palladium complex or a nickel complex, and a counter anion. You may also use something consisting of the following. 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)(acetonitrile)bis[tris(1-methylethyl)phosphine]palladium(I)tetrakis(2,3,4,5,6-pentafluorophenyl)borate, π - allylpalladium complexes such as allylpalladium chloride dimer; organic carboxylates of palladium such as palladium acetate, propionate, maleate, naphthoate; triphenylphosphine complex of palladium acetate, tri(m) of palladium acetate; Complexes of palladium with organic carboxylic acids such as palladium acetate and tricyclohexylphosphine complex; β-diketone compounds of palladium such as dichlorobis(triphenylphosphine)palladium, bis[tri( m-tolylphosphine)]palladium, dibromobis[tri(m-tolylphosphine)]palladium, palladium halide complexes such as acetonyltriphenylphosphonium complex; and the like.

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

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

≪Cleaning step (processing 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. Next, the polymer is 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, and the like.

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

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

<Polymer synthesis>
(Preparation of catalyst solution)
In a glass container placed in a nitrogen atmosphere from which water has been removed in advance, 0.274 g (0.00075 mol) of allyl palladium (II) chloride (dimer), 0.403 g (0.0015 mol) of diphenylcyclohexylphosphine, and 200 g of dehydrated toluene are added. 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 melt, and the mixture was further stirred for 30 minutes. The obtained solution was filtered under a nitrogen stream to obtain a catalyst solution.

(Synthesis of polymer (P1-1))
In an appropriately sized reaction vessel equipped with a stirrer and cooling tube, add 5-butylbicyclo[2.2.1]hept-2-ene (1,982 g, 13.2 mol), [Bicyclo[2.2.1] hept-5-en-2-yl] triethoxysilane (434 g, 1.80 mol) and triethylsilane (1.0 g, 0.009 mol) were weighed out, 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. Thereafter, the solution was heated while 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 at 60°C. Thereby, [Bicyclo[2.2.1]hept-5-en-2-yl]triethoxysilane, polymer with 5-butylbicyclo[2.2.1]hept-2-ene was obtained. Next, the solution was cooled to room temperature, reprecipitated using a large amount of methyl ethyl ketone, and the precipitate was collected by filtration. The filtered material was washed with a large amount of methyl ethyl ketone, and the polymer was extracted by solid-liquid separation. It was dried in a vacuum dryer to obtain 1,550 g of white powder polymer (P1-2).
The weight average molecular weight (Mw) of the thus obtained polymer (P1-1) was 400,000, and the degree of dispersion (Mw/Mn) was 4.5.

(Synthesis of polymer (P1-2))
5-butylbicyclo[2.2. 1] hept-2-ene and [Bicyclo[2.2.1] hept-5-en-2-yl] triethoxysilane were used in the same manner as in the synthesis of the polymer (P1-1) above. (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 degree of dispersion (Mw/Mn) was 4.4.

(Synthesis of polymer (P1-3))
5-butylbicyclo[2.2. 1] hept-2-ene, [Bicyclo[2.2.1] hept-5-en-2-yl] triethoxysilane was used, but the polymer ( 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 thus obtained polymer (P1-3) was 420,000, and the degree of dispersion (Mw/Mn) was 4.7.

(Synthesis of polymer (P2-1))
Into an appropriately sized reaction vessel equipped with a stirrer and condenser, 5-butylbicyclo[2.2.1]hept-2-ene (2,252 g, 15.0 mol), triethylsilane (1.0 g, 0.5 g, 009 mol) was weighed and added, 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. Thereafter, the solution was heated while 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 4 hours while maintaining the internal temperature at 60°C. Thereby, poly 5-butylbicyclo[2.2.1]hept-2-ene was obtained. Next, the solution was cooled to room temperature, reprecipitated using a large amount of methyl ethyl ketone, and the precipitate was collected by filtration. The filtered material was washed with a large amount of methyl ethyl ketone, and the homopolymer was extracted 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 degree of dispersion (Mw/Mn) was 4.2.

(Examples 1 to 3, 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 numbers in brackets are the amount (parts by mass).

(P1)-1: The polymer (P1-1).
(P1)-2: The polymer (P1-2).
(P1)-3: The above 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) 10,000, dispersity (Mw/Mn) 3.3.

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

<Adhesion evaluation of adhesive layer (1)>
Each adhesive composition of each example was applied onto a silicon substrate (size 6 inches, thickness 675 μm) by spin coating while rotating at 1000 rpm.
Next, each support coated with the adhesive composition of each example was preheated at 90° C. for 4 minutes to form an adhesive layer with a thickness of 35 μm.
Next, the adhesive layer was cut linearly 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 from the cutting line was measured to evaluate the adhesion of the adhesive layer. The results are 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 composition of each example was applied onto a bumped substrate (size 12 inches, thickness 775 μm, bump height 30 μm) by spin coating while rotating at 1000 rpm.
Next, the support coated with the adhesive composition of each example was preheated at 90°C for 4 minutes, then heated at 160°C for 4 minutes and at 220°C for 4 minutes to form an adhesive layer with a thickness of 35 μm. Formed.
The formed adhesive layer was observed with a microscope (VHX-5000, manufactured by Keyence), 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. The results are shown in Table 2 as "adhesion (2)".
Evaluation criteria ◎: Peeling area is 0%.
○: Peeling area is less than 5%.
×: Peeling 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 silicon substrates and bumped substrates than the adhesive composition of Comparative Example 1.

1 supporting base;
2 separation layer,
3 adhesive layer,
4 board,
5 sealing material layer,
6 redistribution layer,
10 laminate,
12 support,
20 sealing body,
30 laminate,
40 Electronic parts,
123 Support with adhesive layer.

Claims (12)

An adhesive composition for forming a laminate in which a support and a substrate are bonded together via an adhesive layer ,
Contains a polymer (P1) having a structural unit (p1) represented by the following general formula (p1-1),
The adhesive layer includes a first adhesive composition layer and a second adhesive composition layer,
The adhesive composition is used to form the first adhesive composition layer,
The second adhesive composition layer is formed of an adhesive composition that does not contain the polymer (P1).
Adhesive composition.

[In the formula, R ^u11 to R ^u14 each independently represent an organic group having 1 to 30 carbon atoms or a hydrogen atom. However, at least one of R ^u11 to R ^u14 is an organic group containing an alkoxysilyl group. n ¹ is an integer from 0 to 2. ] According to claim 1, the proportion of the structural unit (p1) in the polymer (P1) is 3 to 30 mol% with respect to all 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 each 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 adhesive composition according to any one of claims 1 to 3, wherein the polymer (P1) has a weight average molecular weight of 5.0×10 ⁴ to 1.0×10 ⁶ . A laminate in which a support and a substrate are bonded together via an adhesive layer,
The adhesive layer includes a first adhesive composition layer formed using the adhesive composition according to any one of claims 1 to 4 , and an adhesive composition that does not contain the polymer (P1). a second adhesive composition layer formed using . 6. The laminate of claim 5 , wherein the first adhesive composition layer is adjacent to the substrate. The support includes a support base that transmits light and a separation layer provided on the support base,
The separation layer is a layer that is adjacent to the adhesive layer and is changed in quality by irradiation with light so that the support base can be separated from the substrate bonded to the support.
The laminate according to claim 5 or 6 . A method for producing a laminate in which a support and a substrate are bonded together via an adhesive layer, the method comprising:
The adhesive layer comprising a first adhesive composition layer formed using the adhesive composition according to any one of claims 1 to 4 on at least one of the support or the substrate. an adhesive layer forming step;
a bonding step of bonding the support and the substrate via the adhesive layer formed in the adhesive layer forming step;
has
The adhesive layer includes a second adhesive layer formed of an adhesive composition that does not contain the polymer (P1).
Method for manufacturing a laminate. 9. After the bonding step, the method further includes a sealing step of sealing the substrate bonded to the support via the adhesive layer with a sealant to produce a sealed body. A method for manufacturing a laminate. After the sealing step, a grinding step of grinding the sealing material portion of the sealed body so that a part of the substrate is exposed;
After the grinding step, a rewiring formation step of forming rewiring on the exposed substrate;
The method for manufacturing a laminate according to claim 9 , further comprising: Production of the laminate according to any one of claims 8 to 10 , further comprising the step of producing the support by forming a separation layer that changes in quality upon irradiation with light on a support base that transmits light. Method. After obtaining a laminate by the method for manufacturing a laminate according to claim 11 ,
a separation step of separating the support base from the substrate included in the laminate by irradiating the separation layer with light through the support base to alter the quality of the separation layer;
After the separation step, a removal step of removing the adhesive layer adhering to the substrate;
A method for manufacturing an electronic component, comprising:

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