JP7033915B2 - Adhesive composition, laminate and its manufacturing method, and manufacturing method of electronic parts - Google Patents

Description

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

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

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

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

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

Japanese Unexamined Patent Publication No. 2014-105316

By the way, in the manufacture of semiconductor packages, after the substrate and the support are bonded together with an adhesive, high-temperature treatment such as sealing, thin film formation, and firing is performed, or a lithography operation is performed when forming a rewiring layer. It may be treated with a chemical solution.
When the substrate and the support are bonded to each other by the adhesive described in Patent Document 1, there is a problem that the position of the substrate is displaced before and after the sealing operation due to the influence of the high temperature treatment. Further, during the high temperature treatment, moisture and the like in the resin contained in the encapsulant vaporize to generate gas, a void is generated between the encapsulant layer and the support, and the support is peeled off. There is concern about the occurrence of problems such as ease of use. Further, there is a concern that the adhesiveness between the substrate and the support may be lowered due to the influence of the chemical treatment.
The present invention has been made in view of the above circumstances, and is an adhesive composition, a laminate, and an adhesive composition having higher heat resistance and chemical resistance and capable of forming an adhesive layer that is not easily affected by high temperature treatment and chemical treatment. An object of the present invention is to provide a manufacturing method thereof and a manufacturing method of electronic parts.

In order to solve the above problems, the present invention has adopted the following configuration.
That is, the first aspect of the present invention is an adhesive composition comprising an elastomer having a structural unit (u1) represented by the following general formula (u1-1).

［一般式（ｕ１－１）中、Ｒ^α１は、炭素数１～５のアルキル基又は水素原子を表す。Ｒ^０１は、脂環式基を含む基を表す。Ｒ^０２は、ハロゲン原子、ハロゲン原子で置換されていてもよい炭素数１～８のアルキル基、ハロゲン原子で置換されていてもよい炭素数６～１２のアリール基、シアノ基、ニトロ基、水酸基、カルボキシ基、－ＯＲで表される基及び－ＣＯＯＲで表される基（但し、Ｒは、炭素数１～８のハロゲン原子で置換されていてもよいアルキル基である。）からなる群より選ばれる、Ｒ^０１に該当しない基である。ｍは１～５の自然数であり、ｎ１は０以上の整数である。但し、ｍとｎ１との和は５を超えることはない。］

[In the general formula (u1-1), R ^α1 represents an alkyl group or a hydrogen atom having 1 to 5 carbon atoms. R ⁰¹ represents a group containing an alicyclic group. R ⁰² is a halogen atom, an alkyl group having 1 to 8 carbon atoms which may be substituted with a halogen atom, an aryl group having 6 to 12 carbon atoms which may be substituted with a halogen atom, a cyano group, a nitro group, and a hydroxyl group. , A carboxy group, a group represented by -OR and a group represented by -COOR (where R is an alkyl group which may be substituted with a halogen atom having 1 to 8 carbon atoms). It is a group that is selected and does not correspond to R ⁰¹ . m is a natural number from 1 to 5, and n1 is an integer of 0 or more. However, the sum of m and n1 does not exceed 5. ]

The second aspect of the present invention is a laminated body in which a support, an adhesive layer and a device layer are laminated in this order, and the adhesive layer is a dried body of the adhesive composition according to the first aspect. It is a laminated body characterized by.

A third aspect of the present invention is a method for producing a laminated body in which a support, an adhesive layer and a device layer are laminated in this order, and the adhesive composition according to the first aspect is used on the support. A device layer that is a composite of an adhesive layer forming step for forming the adhesive layer, a member composed of a metal or a semiconductor, and a resin that seals or insulates the member is formed on the adhesive layer. It is a method for manufacturing a laminated body, which comprises a device layer forming step.

A fourth aspect of the present invention is to obtain a laminate by the method for producing a laminate according to the third aspect, and then irradiate the separation layer with light via the support substrate to alter the separation layer. It is characterized by having a separation step of separating the support substrate from the device layer, and a removal step of removing the adhesive layer and the separation layer adhering to the device layer after the separation step. It is a manufacturing method of electronic parts.

According to the invention, an adhesive composition, a laminate and a method for producing the same, and a method for producing an electronic component, which have higher heat resistance and chemical resistance and can form an adhesive layer which is not easily affected by high temperature treatment and chemical treatment. Can be provided.

It is sectional drawing which shows one Embodiment of the laminated body to which this invention was applied. It is sectional drawing which shows the other embodiment of the laminated body to which this invention was applied. It is sectional drawing which shows the other embodiment of the laminated body to which this invention was applied. It is sectional drawing which shows the other embodiment of the laminated body to which this invention was applied. It is a schematic process diagram explaining a part of one Embodiment of the manufacturing method of a laminated body. FIG. 5A is a diagram showing a support substrate composed of a support substrate and a separation layer, and FIG. 5B is a diagram illustrating an adhesive layer forming step. It is a schematic process diagram explaining one Embodiment of the method of manufacturing a laminated body 100 from a support 123 with an adhesive layer. 6 (a) is a diagram showing a support 123 with an adhesive layer, FIG. 6 (b) is a diagram showing a substrate fixing process, and FIG. 6 (c) is a diagram illustrating a sealing process. be. It is a schematic process diagram explaining one Embodiment of the method of manufacturing a laminated body 200 from a laminated body 100. 7 (a) is a diagram showing the laminated body 100, FIG. 7 (b) is a diagram for explaining a grinding process, and FIG. 7 (c) is a diagram for explaining a rewiring forming process. It is a schematic process diagram explaining one Embodiment of the method of manufacturing a semiconductor package (electronic component) from a laminated body 200. 8 (a) is a diagram showing the laminated body 200, FIG. 8 (b) is a diagram for explaining a separation step, and FIG. 8 (c) is a diagram for explaining a removal step. It is a graph which shows the behavior of the complex elastic modulus with respect to the temperature about the adhesive layer formed by using the adhesive composition of an Example and a comparative example.

In the present specification and claims, "aliphatic" is defined as a relative concept to aromatics and means non-aromatic groups, compounds and the like.
Unless otherwise specified, the "alkyl group" shall include linear, branched and cyclic monovalent saturated hydrocarbon groups. The same applies to the alkyl group in the alkoxy group.
Unless otherwise specified, the "alkylene group" includes linear, branched and cyclic divalent saturated hydrocarbon groups.
The "alkyl halide group" is a group in which a part or all of the hydrogen atom of the alkyl group is substituted with a halogen atom, and examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
The “constituent unit” means a monomer unit (monomer unit) constituting a polymer compound (resin, polymer, copolymer).
"Exposure" is a concept that includes general irradiation of radiation.

In the present specification and the scope of the present patent claim, there are some structures represented by chemical formulas in which an asymmetric carbon is present and an enantiomer or a diastereomer may be present. In the case, one formula is used to represent those isomers. These isomers may be used alone or as a mixture.

(Adhesive composition)
The adhesive composition according to the first aspect of the present invention contains an elastomer having a structural unit (u1) represented by the general formula (u1-1).

<Resin component (P)>
The adhesive composition of the present embodiment contains a resin component (P) (hereinafter, also referred to as “(P) component”). The component (P) contains at least an elastomer having the structural unit (u1) (hereinafter, also referred to as “component (EP1)”).
The component (P) may contain other resins in addition to the component (EP1). In addition to the resin, the component (P) in the present embodiment includes a monomer that can be a matrix constituting the adhesive layer, for example, a curable monomer described later.

≪Elastomer: (EP1) component≫
In the present embodiment, the component (EP1) has a structural unit (u1) represented by the following general formula (u1-1).

-Regarding the structural unit (u1) The structural unit (u1) represented by the general formula (u1-1) has at least one R ⁰¹ (a group containing an alicyclic group) bonded to a benzene ring.
By containing the elastomer having the structural unit (u1), the complex elastic modulus E * and the glass transition temperature (Tg) of the adhesive layer to be formed are increased, and the heat resistance and the chemical resistance are further enhanced.

［一般式（ｕ１－１）中、Ｒ^α１は、炭素数１～５のアルキル基又は水素原子を表す。Ｒ^０１は、脂環式基を含む基を表す。Ｒ^０２は、ハロゲン原子、ハロゲン原子で置換されていてもよい炭素数１～８のアルキル基、ハロゲン原子で置換されていてもよい炭素数６～１２のアリール基、シアノ基、ニトロ基、水酸基、カルボキシ基、－ＯＲで表される基及び－ＣＯＯＲで表される基（但し、Ｒは、炭素数１～８のハロゲン原子で置換されていてもよいアルキル基である。）からなる群より選ばれる、Ｒ^０１に該当しない基である。ｍは１～５の自然数であり、ｎ１は０以上の整数である。但し、ｍとｎ１との和は５を超えることはない。］

[In the general formula (u1-1), R ^α1 represents an alkyl group or a hydrogen atom having 1 to 5 carbon atoms. R ⁰¹ represents a group containing an alicyclic group. R ⁰² is a halogen atom, an alkyl group having 1 to 8 carbon atoms which may be substituted with a halogen atom, an aryl group having 6 to 12 carbon atoms which may be substituted with a halogen atom, a cyano group, a nitro group, and a hydroxyl group. , A carboxy group, a group represented by -OR and a group represented by -COOR (where R is an alkyl group which may be substituted with a halogen atom having 1 to 8 carbon atoms). It is a group that is selected and does not correspond to R ⁰¹ . m is a natural number from 1 to 5, and n1 is an integer of 0 or more. However, the sum of m and n1 does not exceed 5. ]

In the above formula (u1-1), R ^α1 represents an alkyl group having 1 to 5 carbon atoms or a hydrogen atom.
Examples of the alkyl group having 1 to 5 carbon atoms in R ^α1 include a linear or branched alkyl group having 1 to 5 carbon atoms, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, and n-butyl. Examples thereof include a group, an isobutyl group, a tert-butyl group, a pentyl group, an isopentyl group, a neopentyl group and the like. Among them, R ^α1 is preferably a methyl group or a hydrogen atom, and more preferably a hydrogen atom.

In the formula (u1-1), R ⁰¹ represents a group containing an alicyclic group.
The alicyclic group in R ⁰¹ may be a polycyclic group or a monocyclic group.
As the monocyclic alicyclic group, a group obtained by removing one or more hydrogen atoms from a monocycloalkane is preferable. The monocycloalkane preferably has 3 to 6 carbon atoms, and specific examples thereof include cyclopentane and cyclohexane.
As the polycyclic alicyclic group, a group obtained by removing one or more hydrogen atoms from a polycycloalkane is preferable. The polycycloalkane preferably has 7 to 30 carbon atoms, and specifically, a polycycloalkane having a polycyclic skeleton of a cross-linked carbon ring system such as adamantan, norbornane, isobornane, tricyclodecane, and tetracyclododecane. Examples include polycycloalkanes having a polycyclic skeleton of a fused ring system such as a cyclic group having a steroid skeleton. That is, examples of the polycyclic alicyclic group include a crosslinked carbocyclic group and a fused ring group.

Examples of the group containing an alicyclic group in R ⁰¹ include a group in which one of the hydrogen atoms in the monocycloalkane or polycycloalkane is substituted with an alkylene group. The alkylene group preferably has 1 to 4 carbon atoms, and more preferably 1 or 2 carbon atoms.

R ⁰¹ is preferably a group containing a crosslinked carbon ring type group because the complex elastic modulus E * and the glass transition temperature (Tg) of the adhesive layer to be formed can be more easily increased. Among these, R ⁰¹ is particularly preferably a group in which the crosslinked carbon moiety in the crosslinked carbon ring type group is directly bonded to the carbon atom constituting the benzene ring in the general formula (u1-1).

Specific examples of R ⁰¹ (group containing an alicyclic group) are shown below. In the chemical formula, * indicates that the bond is a bond to the carbon atom constituting the benzene ring in the general formula (u1-1).

In the above formula (u1-1), R ⁰² is a halogen atom, an alkyl group having 1 to 8 carbon atoms which may be substituted with a halogen atom, and an aryl having 6 to 12 carbon atoms which may be substituted with a halogen atom. Group, cyano group, nitro group, hydroxyl group, carboxy group, group represented by -OR and group represented by -COOR (where R may be substituted with a halogen atom having 1 to 8 carbon atoms). It is a group that does not correspond to R ⁰¹ and is selected from the group consisting of (group).
Examples of the halogen atom in R ⁰² include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
The alkyl group in R ⁰² has 1 to 8 carbon atoms, preferably 1 to 5 carbon atoms, and examples thereof include linear or branched alkyl groups.
The aryl group in R ⁰² has 6 to 12 carbon atoms, and a phenyl group and a naphthyl group are preferable.
Examples of the halogen atom in R include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
The alkyl group in R has 1 to 8 carbon atoms, preferably 1 to 5 carbon atoms, and examples thereof include linear or branched alkyl groups.

In the above equation (u1-1), m is a natural number from 1 to 5, and n1 is an integer of 0 or more. However, the sum of m and n1 does not exceed 5.
m is a natural number of 1 to 5, preferably 1 or 2, and more preferably 1.
n1 is an integer of 0 or more, preferably 0 or 1, and more preferably 0.

A specific example of the structural unit (u1) is shown below. In each of the following formulas, R ^α10 represents a hydrogen atom or a methyl group.

The structural unit (u1) contained in the component (EP1) may be one kind or two or more kinds.
The ratio of the constituent unit (u1) in the (EP1) component is preferably 1 to 40 mol%, preferably 5 to 35 mol%, based on the total (100 mol%) of all the constituent units constituting the (EP1) component. More preferably, 10 to 30 mol% is further preferable.
When the ratio of the structural unit (u1) is not less than the lower limit of the above-mentioned preferable range, the heat resistance and chemical resistance are more likely to be enhanced, while when it is not more than the upper limit of the above-mentioned preferable range, other It becomes easier to balance with the constituent units.

-Other constituent units The (EP1) component may have a constituent unit other than the constituent unit (u1).
The component (EP1) has, for example, a structural unit (u2) represented by the general formula (u2-1) in addition to the structural unit (u1) from the viewpoint of imparting flexibility to the adhesive layer. Elastomers are preferred.

-About the structural unit (u2) The structural unit (u2) is a structural unit represented by the following general formula (u2-1).

［一般式（ｕ２－１）中、Ｒ^α２は、炭素数１～５のアルキル基又は水素原子を表す。Ｒ^０３は、ハロゲン原子、ハロゲン原子で置換されていてもよい炭素数１～８のアルキル基、ハロゲン原子で置換されていてもよい炭素数６～１２のアリール基、シアノ基、ニトロ基、水酸基、カルボキシ基、－ＯＲで表される基及び－ＣＯＯＲで表される基（但し、Ｒは、炭素数１～８のハロゲン原子で置換されていてもよいアルキル基である。）からなる群より選ばれる基であり、前述したＲ^０１に該当しない基である。ｎ２は０以上５以下の整数である。］

[In the general formula (u2-1), R ^α2 represents an alkyl group or a hydrogen atom having 1 to 5 carbon atoms. R ⁰³ is a halogen atom, an alkyl group having 1 to 8 carbon atoms which may be substituted with a halogen atom, an aryl group having 6 to 12 carbon atoms which may be substituted with a halogen atom, a cyano group, a nitro group, and a hydroxyl group. , A carboxy group, a group represented by -OR and a group represented by -COOR (where R is an alkyl group which may be substituted with a halogen atom having 1 to 8 carbon atoms). It is a group to be selected and does not correspond to the above-mentioned R ⁰¹ . n2 is an integer of 0 or more and 5 or less. ]

In the above formula (u2-1), R ^α2 represents an alkyl group having 1 to 5 carbon atoms or a hydrogen atom. As for R ^α2 , the same as R ^α1 in the above formula (u1-1) can be mentioned.

In the above formula ( ^u2-1 ), R03 is a halogen atom, an alkyl group having 1 to 8 carbon atoms which may be substituted with a halogen atom, and an aryl having 6 to 12 carbon atoms which may be substituted with a halogen atom. Group, cyano group, nitro group, hydroxyl group, carboxy group, group represented by -OR and group represented by -COOR (where R may be substituted with a halogen atom having 1 to 8 carbon atoms). It is a group selected from the group consisting of (), and does not correspond to the above-mentioned ^R01 . As for R ⁰³ , the same as R ⁰² in the above formula (u1-1) can be mentioned.

In the above formula (u2-1), n2 is an integer of 0 or more and 5 or less, preferably 0 or 1, and more preferably 0.

A specific example of the structural unit (u2) is shown below. In each of the following formulas, R ^α20 represents a hydrogen atom or a methyl group.

The structural unit (u2) contained in the component (EP1) may be one kind or two or more kinds.
The ratio of the constituent units (u2) in the (EP1) component is preferably 1 to 50 mol%, preferably 5 to 40 mol%, based on the total (100 mol%) of all the constituent units constituting the (EP1) component. More preferably, 10 to 40 mol% is further preferable.
When the ratio of the structural unit (u2) is not less than the lower limit of the above-mentioned preferable range, the flexibility to the adhesive layer is likely to be enhanced, while when it is not more than the upper limit of the above-mentioned preferable range, other configurations are made. It becomes easier to balance with the unit.

The molar ratio of the structural unit (u1) to the structural unit (u2) contained in the component (EP1) in the present embodiment is that the structural unit (u1) / structural unit (u2) = 0.2 to 5. It is preferably 0.3 to 5, more preferably 0.4 to 5, and even more preferably 0.4 to 5.
When the molar ratio is not less than the lower limit of the above-mentioned preferable range, the heat resistance and chemical resistance are more likely to be enhanced, while when it is not more than the upper limit of the above-mentioned preferable range, the flexibility to the adhesive layer is obtained. Is easy to increase.

Examples of the structural unit other than the structural unit (u1) include the structural unit (u2) and, for example, a structural unit derived from an olefin-based monomer.
The "olefin-based monomer" refers to an aliphatic hydrocarbon having one or more double bonds between carbon atoms (between C and C) in the molecule.
The “constituent unit derived from the olefin-based monomer” means a structural unit formed by cleaving the ethylenic double bond of the olefin-based monomer.
As the olefin-based monomer, for example, ethylene, propylene, 1-butene, 1,3-butadiene and the like are preferable.
The constituent unit derived from the olefin-based monomer (EP1) may be one kind or two or more kinds.
The ratio of the structural units derived from the olefin-based monomer in the component (EP1) is preferably 10 to 90 mol% with respect to the total of all the structural units constituting the component (EP1) (100 mol%). 20-90 mol% is more preferable, and 30-90 mol% is even more preferable.

In the present embodiment, the component (EP1) is an elastomer having a structural unit (u1), and is a structural unit (u1) and a structural unit (u2) in terms of heat resistance, chemical resistance, and flexibility as an adhesive layer. ) And is preferred. Among these, preferred (EP1) components include copolymers having a structural unit (u1), a structural unit (u2), and a structural unit derived from an olefin-based monomer.
Specifically, as the component (EP1), a copolymer having a constituent unit (u1), a constituent unit (u2), a constituent unit derived from ethylene, and a constituent unit derived from propylene; Preferable examples thereof include a copolymer having a unit (u1), a constituent unit (u2), a constituent unit derived from 1,3-butadiene, and a constituent unit derived from 1-butene.

The weight average molecular weight (Mw) (polystyrene conversion standard by gel permeation chromatography (GPC)) of the component (EP1) is preferably 10,000 to 500,000, more preferably 30,000 to 300,000, still more preferably 50,000 to 250,000.
When the Mw of the component (EP1) is not more than the upper limit value of the above-mentioned preferable range, the solubility in a solvent is further improved, while when it is not more than the lower limit value of the above-mentioned preferable range, the strength as an adhesive layer is increased. It is easier to be maintained and maintained.
The molecular weight dispersion (Mw / Mn) of the component (EP1) is not particularly limited, and is preferably 1.0 to 3.0, more preferably 1.0 to 2.5, and particularly preferably 1.0 to 2.0. preferable. Mn indicates a number average molecular weight.

The component (EP1) can be synthesized by a known synthetic method, and is produced, for example, in the same manner as the method described in Akinori Toyoda's document "Synthesis of Bulky Hydrocarbon Group-Containing Polymer by Polymer Reaction Method and Its Properties". ..

The component (EP1) contained in the component (P) may be one kind or two or more kinds.
The content ratio of the component (EP1) to the component (P) is preferably 20% by mass or more, more preferably 20 to 100% by mass, and 25 to 100 with respect to the total amount (100% by mass) of the component (P). The mass% is more preferable, and 50 to 100% by mass is particularly preferable. When the content ratio of the component (EP1) is within the above-mentioned preferable range, the heat resistance and the chemical resistance are more likely to be enhanced.

≪Resin other than (EP1) component≫
Examples of the resin other than the component (EP1) that may be contained in the component (P) in the present embodiment include an elastomer having no structural unit (u1) (hereinafter, this is also referred to as “component (EP2)”). Examples thereof include cycloolefin polymers, acrylic resins, and curable monomers that can serve as a matrix constituting the adhesive layer.

-About the elastomer ((EP2) component) having no constituent unit (u1) The elastomer ((EP2) component) having no constituent unit (u1) is, for example, a constituent unit derived from styrene as a constituent unit of the main chain. , Or a polymer having a structural unit derived from a styrene derivative (collectively referred to as "styrene unit") can be mentioned.

Here, the term "styrene derivative" is a concept including a hydrogen atom at the α-position of styrene substituted with another substituent such as an alkyl group or an alkyl halide group, and derivatives thereof. Examples of these derivatives include those in which a substituent is bonded to a benzene ring of styrene in which a hydrogen atom at the α-position may be substituted with a substituent.
The alkyl group as the substituent at the α-position is preferably a linear or branched alkyl group, and specifically, an alkyl group having 1 to 5 carbon atoms (methyl group, ethyl group, propyl group, isopropyl group). , N-butyl group, isobutyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group) and the like.
Further, the alkyl halide group as the substituent at the α-position is specifically a group in which a part or all of the hydrogen atom of the “alkyl group as the substituent at the α-position” is substituted with a halogen atom. Be done. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like, and a fluorine atom is particularly preferable.
Examples of the substituent that may be bonded to the benzene ring of styrene include an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an alkoxyalkyl group having 1 to 5 carbon atoms, an acetoxy group, and a carboxy group. And so on.
The α-position (carbon atom at the α-position) refers to a carbon atom to which a benzene ring is bonded, unless otherwise specified.
“Constituent unit derived from styrene” and “constituent unit derived from a styrene derivative” mean a structural unit formed by cleavage of an ethylenic double bond of styrene or a styrene derivative.

Examples of the (EP2) component include polystyrene-poly (ethylene / propylene) block copolymer (SEP), styrene-isoprene-styrene block copolymer (SIS), styrene-butadiene-styrene block copolymer (SBS), and styrene-butadiene-. Butylene-Styrene Block Copolymer (SBBS) or its hydroxides; Styrene-Ethene-Styrene-Styrene Block Copolymer (SEBS), Styrene-Ethethylene-Styrene-Styrene Block Copolymer (Styrene-Isoprene-Styrene Block Copolymer) (SEPS), Styrene-ethylene-ethylene-propylene-styrene block copolymer (SEEPS), styrene block reaction cross-linked styrene-ethylene-ethylene-propylene-styrene block copolymer (SeptonV9461 (manufactured by Kuraray Co., Ltd.), SeptonV9475 (manufactured by Kuraray Co., Ltd.)) , Styrene V9827 (manufactured by Kuraray Co., Ltd.) having a reactive polystyrene-based hard block, etc., in which the styrene block is a reaction-crosslinked styrene-ethylene-butylene-styrene block copolymer.

The ratio of the styrene unit in the component (EP2) is preferably 10 to 70 mol%, more preferably 20 to 60 mol%, based on the total (100 mol%) of all the component units constituting the component (EP2). , 25-50 mol% is more preferred, and 30-45 mol% is particularly preferred.
When the ratio of the styrene unit is not less than the lower limit of the above-mentioned preferable range, it becomes easy to be subjected to a process such as thinning and mounting without deteriorating the bondability or grindability between the support and the substrate. .. When it is not more than the upper limit of the above 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 component (EP2) is preferably in the range of 20,000 to 200,000, more preferably in the range of 50,000 to 150,000.
When the weight average molecular weight of the component (EP2) is within the above-mentioned preferable range, it becomes easy to obtain an adhesive composition capable of forming an adhesive layer which is easily dissolved in a hydrocarbon solvent and removed. Further, when the weight average molecular weight of the component (EP2) is within the above-mentioned preferable range, the chemical resistance of the adhesive layer formed by the adhesive composition is enhanced.

The component (P) may be contained. The component (EP2) may be one kind or two or more kinds.
Examples of commercially available elastomer products that can be used as the component (EP2) include "Septon (trade name)" manufactured by Kuraray Corporation, "Hybler (trade name)" manufactured by Kuraray Corporation, and Asahi Kasei Co., Ltd. "Tough Tech (trade name)", "Dynaron (trade name)" manufactured by JSR Corporation, etc. can be mentioned.

The content ratio of the component (EP2) to the component (P) is preferably 80% by mass or less, more preferably 0 to 80% by mass, and 0 to 0 to the total amount (100% by mass) of the component (P). 75% by mass is more preferable, and 0 to 50% by mass is particularly preferable.

When the component (P) contains the component (EP1) and the component (EP2), the mass ratio of the component (EP1) and the component (EP2) is (EP1) component / (EP2) component = 1/4 to 3 /. 1 is preferable, 1/3 to 2/1 is more preferable, and 1/3 to 1/1 is further preferable.
When the mass ratio is not less than the lower limit of the above-mentioned preferable range, the heat resistance and chemical resistance are more likely to be enhanced, while when it is not more than the upper limit of the above-mentioned preferable range, the flexibility of the adhesive layer becomes flexible. It is enhanced and the adhesiveness is further improved.

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

-About the cycloolefin polymer As the cycloolefin polymer, for example, a ring-opening polymer having a monomer component containing a cycloolefin monomer and an addition polymer obtained by addition-polymerizing a monomer component containing a cycloolefin monomer are preferable. ..

Examples of the cycloolefin monomer include dicyclics such as norbornene and norbornadiene, tricyclics such as dicyclopentadiene and hydroxydicyclopentadiene, tetracyclics such as tetracyclopentadiene, and cyclopentadiene trimers. Rings, seven rings such as tetracyclopentadiene, or alkyl (methyl, ethyl, propyl, butyl, etc.) substitutions, alkenyl (vinyl, etc.) substitutions, alkylidene (ethylidene, etc.) substitutions or aryls (such as ethylidene) of these polycyclics. Monomers such as phenyl, trill, naphthyl, etc.) substituents can be mentioned.

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

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

The ratio of the cycloolefin monomer unit in the cycloolefin polymer is preferably 10 to 100 mol%, more preferably 20 to 100 mol%, based on the total (100 mol%) of all the constituent units constituting the cycloolefin polymer.

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

The cycloolefin polymer preferably has a weight average molecular weight in the range of 10,000 to 2000000, more preferably in the range of 30,000 to 1500,000.
When the weight average molecular weight of the cycloolefin polymer is at least the lower limit of the above-mentioned preferable range, it becomes easy to control the softening temperature of the polymer to a temperature suitable for bonding the support and the substrate. When it is not more than the upper limit of the above-mentioned preferable range, it becomes easy to obtain an adhesive composition capable of forming an adhesive layer which is easily dissolved in a hydrocarbon solvent and removed.

The cycloolefin polymer that may contain the component (P) may be one kind or two or more kinds.
Examples of commercially available products that can be used as the cycloolefin polymer include "TOPAS (trade name)" manufactured by Polyplastics Corporation, "APEL (trade name)" manufactured by Mitsui Chemicals Corporation, and Nippon Zeon Co., Ltd. "ZEONOR (trade name)" manufactured by JSR Corporation, "ZEONEX (trade name)" manufactured by Japan Zeon Co., Ltd., "ARTON (trade name)" manufactured by JSR Corporation, and the like.

-Acrylic resin In the present embodiment, the component (P) may contain an acrylic resin in addition to the component (EP1). When the component (P) contains an acrylic resin, the adhesiveness between the support and the substrate can be further improved.
Examples of the acrylic resin include resins (monopolymers and copolymers) polymerized using (meth) acrylic acid ester as a monomer.
"(Meta) acrylic" means at least one of acrylic or methacrylic.

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

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

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

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

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

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

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

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

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

The weight average molecular weight of the acrylic resin is preferably 2000 to 100,000, more preferably 5000 to 50,000.
When the weight average molecular weight of the acrylic resin is within the above-mentioned preferable range, it is possible to easily provide an adhesive composition having heat fluidity suitable for bonding a substrate and a support, for example.
The acrylic resin which may contain the component (P) may be one kind or two or more kinds.

-Curable Monomer In the present embodiment, the component (P) may contain a curable monomer in addition to the component (P1) described above. When the component (P) contains a curable monomer, the heat resistance of the adhesive layer can be further improved.
The curable monomer is preferably a monomer that is polymerized by radical polymerization, and typically includes a polyfunctional curable monomer, and a polyfunctional (meth) acrylate monomer is particularly preferable.

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

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

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

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

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

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

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

Examples of the hydrocarbon solvent include linear, branched or cyclic hydrocarbons, and examples thereof include linear hydrocarbons such as hexane, heptane, octane, nonane, methyloctane, decane, undecane, dodecane, and tridecane. Branched chain hydrocarbons such as isooctane, isononan, isododecane; p-menthane, o-menthane, m-menthane, diphenylmenthane, 1,4-terpinene, 1,8-terpinene, bornan, norbornan, pinan, tsujan, Karan, Longihoren, α-Terpinene, β-Terpinene, γ-Terpinene, α-Pinen, β-Pinen, α-Tsjon, β-Tsjon, Cyclohexane, Cycloheptane, Cyclooctane, Inden, Pentalene, Indan, Tetrahydroinden, Naphthalene , Tetrahydronaphthalene (tetraline), decahydronaphthalene (decalin) and other cyclic hydrocarbons.

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

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

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

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

≪Polymerization inhibitor≫
The adhesive composition of the present embodiment may further contain a polymerization inhibitor.
A polymerization inhibitor refers to a component having a function of preventing a radical polymerization reaction due to heat or light.
As the polymerization inhibitor, those having a phenol skeleton are preferable. For example, a hindered phenol-based antioxidant can be used as the polymerization inhibitor.

≪Polymer initiator≫
The adhesive composition of the present embodiment may further contain a polymerization initiator.
The polymerization initiator refers to a component having a function of accelerating the polymerization reaction of the above-mentioned curable monomer. Examples of the polymerization initiator include known thermal polymerization initiators, photopolymerization initiators and the like.
The polymerization initiator is preferably used in combination with a curable monomer. The amount of the polymerization initiator used may be adjusted according to the amount of the curable monomer used.

In the adhesive composition of the present embodiment, when the test piece (adhesive layer) is obtained by applying the adhesive composition and drying it, the glass transition temperature (Tg) of the test piece is 100 ° C. The above is preferable, 110 to 250 ° C. is more preferable, 120 to 240 ° C. is further preferable, and 150 to 220 ° C. is particularly preferable.
When the Tg of the test piece is not less than the lower limit of the above-mentioned preferable range, an adhesive layer having higher heat resistance can be easily formed, while when it is not more than the upper limit of the above-mentioned preferable range, the adhesive layer can be easily formed. It becomes easier to maintain the flexibility of.

The glass transition temperature (Tg / ° C.) of the test piece (adhesive layer) is determined by dynamic viscoelasticity measurement. For example, using a dynamic viscoelasticity measuring device Rheogel-E4000 (manufactured by UBM Co., Ltd.), measurement is performed by raising the temperature from 25 ° C to 300 ° C at a heating rate of 5 ° C / min under the condition of a frequency of 1 Hz. The glass transition temperature can be determined based on the change in viscoelasticity.

In the adhesive composition of the present embodiment, the adhesive composition is applied and dried to prepare a test piece (adhesive layer) having a thickness of 500 μm, starting temperature: 25 ° C., temperature rising rate: 5 ° C. When subjected to dynamic viscoelasticity measurement under the conditions of / min and frequency: 1 Hz, the complex elastic modulus E * ₁₅₀ at 150 ° C. of the test piece is preferably 0.1 MPa or more, preferably 1 to 150 MPa. More preferably, 10 to 140 MPa is further preferable, and 20 to 120 MPa is particularly preferable.
When the complex elastic modulus E * ₁₅₀ of the test piece is not less than the lower limit of the above-mentioned preferable range, an adhesive layer having higher heat resistance can be easily formed, while it is not more than the upper limit of the above-mentioned preferable range. If there is, it becomes easy to maintain the flexibility of the adhesive layer.

In the adhesive composition of the present embodiment, the adhesive composition is applied and dried to prepare a test piece (adhesive layer) having a thickness of 500 μm, starting temperature: 25 ° C., temperature rising rate: 5 ° C. When subjected to dynamic viscoelasticity measurement under the conditions of / min and frequency: 1 Hz, the complex elastic modulus E * ₅₀ at 50 ° C. of the test piece is preferably 30 MPa or more, more preferably 50 to 300 MPa. , 70 to 250 MPa is more preferable, and 80 to 240 MPa is particularly preferable.
When the complex elastic modulus E * ₅₀ of the test piece is not less than the lower limit of the above-mentioned preferable range, an adhesive layer having higher heat resistance can be easily formed, while it is not more than the upper limit of the above-mentioned preferable range. If there is, it becomes easy to maintain the flexibility of the adhesive layer.

In the adhesive composition of the present embodiment, the ratio (E *) of the complex elastic modulus E * ₅₀ at 50 ° C. and the complex elastic modulus E * ₁₅₀ at 150 ° C. when the dynamic viscoelasticity measurement is performed under the above conditions. ₅₀ / E * ₁₅₀ ) is preferably 5000 or less, more preferably 3000 or less, particularly preferably 1000 or less, further preferably 500 or less, further preferably 2 to 200, and particularly preferably 2 to 100. ~ 10 is the most preferable.
When the ratio (E * ₅₀ / E * ₁₅₀ ) is equal to or higher than the lower limit of the above-mentioned preferable range, an adhesive layer having higher heat resistance can be easily formed, while it is equal to or less than the upper limit of the above-mentioned preferable range. Then, the flexibility of the adhesive layer is easily maintained.

The complex elastic modulus E * ₅₀ and the complex elastic modulus E * ₁₅₀ of the test piece (adhesive layer) are, for example, using a dynamic viscoelasticity measuring device Rheogel-E4000 (manufactured by UBM Co., Ltd.) under the condition of a frequency of 1 Hz. The change in viscoelasticity is measured by raising the temperature from 50 ° C. to 300 ° C. at a heating rate of 5 ° C./min, and each complex elastic modulus at 50 ° C. and 150 ° C. is read.

The adhesive composition of the present embodiment is useful as, for example, an adhesive for manufacturing a semiconductor package. Specifically, it can be suitably used as an adhesive used for forming the adhesive layer in a laminated body in which a support, an adhesive layer and a device layer are laminated in this order. As an example, the device layer may be a composite of a member made of a metal or a semiconductor and a resin that seals or insulates the member.

The adhesive composition of the present embodiment described above contains an elastomer having a structural unit (u1) in which R ⁰¹ (a group containing an alicyclic group) is bonded to a benzene ring in a styrene unit, and therefore has heat resistance. And an adhesive layer with higher chemical resistance can be formed. As a result, the adhesive layer formed by the adhesive composition of the present embodiment is less likely to cause misalignment of the substrate before and after the sealing operation due to the influence of high temperature treatment, for example, when manufacturing a semiconductor package. Further, during the high temperature treatment, moisture and the like in the resin contained in the encapsulant vaporize to generate gas, but voids are less likely to occur between the encapsulant layer and the support, and the support Peeling is prevented. Further, the deterioration of the adhesiveness between the substrate and the support is suppressed due to the influence of the chemical solution treatment in the lithography operation when forming the rewiring layer.

In addition, according to the adhesive composition of the present embodiment, the formed adhesive layer has high solubility in a hydrocarbon solvent. As a result, the adhesive layer can be easily cleaned and removed from the substrate during the manufacture of the semiconductor package.
Further, the adhesive layer formed by the adhesive composition of the present embodiment is difficult for the gas generated from the resin contained in the encapsulant to pass through during the high temperature treatment, and the outgassing from the device layer is suppressed. To.

(Laminated body)
In the laminated body according to the second aspect of the present invention, the support, the adhesive layer and the device layer are laminated in this order.

FIG. 1 shows an embodiment of a laminated body according to a second aspect.
The laminate 100 shown in FIG. 1 includes a support 12 in which a support substrate 1 and a separation layer 2 are laminated, an adhesive layer 3, and a device layer 45 composed of a substrate 4 and a sealing material layer 5. In the laminated body 100, the support 12, the adhesive layer 3, and the device layer 45 are laminated in this order.
In the example of FIG. 1, the support 12 is composed of the support base 1 and the separation layer 2, but the support is not limited to this, and the support may be formed only from the support base.

FIG. 2 shows another embodiment of the laminate according to the second aspect.
The laminate 200 shown in FIG. 2 has the same configuration as the laminate 100 except that the device layer is the device layer 456 composed of the substrate 4, the encapsulant layer 5, and the wiring layer 6.

FIG. 3 shows yet another embodiment of the laminate according to the second aspect.
The laminated body 300 shown in FIG. 3 has the same configuration as the laminated body 100 except that the device layer is composed of the wiring layer 6.

FIG. 4 shows yet another embodiment of the laminate according to the second aspect.
The laminate 400 shown in FIG. 4 has the same configuration as the laminate 100 except that the device layer is the device layer 645 including the wiring layer 6, the substrate 4, and the encapsulant layer 5.

<Adhesive layer>
Each of the adhesive layers 3 in the laminated body 100, the laminated body 200, the laminated body 300, and the laminated body 400 is a dried body of the adhesive composition according to the first aspect described above.
The thickness of the adhesive layer 3 is preferably in the range of, for example, 1 μm or more and 200 μm or less, and more preferably in the range of 5 μm or more and 150 μm or less.

<Support>
The support is a member that supports the substrate, and the substrate is fixed on the support via an adhesive layer. In the examples of FIGS. 1 and 2, the support 12 includes a support base 1 and a separation layer 2 provided on the support base 1. If the separation layer 2 is not provided, the support substrate 1 becomes a support.

≪Supporting substrate≫
The support substrate has a property of transmitting light and is a member that supports the substrate. When the separation layer is provided as shown in FIGS. 1 and 2, the support substrate is attached to the substrate via the separation layer and the adhesive layer. When the separation layer is not provided, the support substrate is bonded to the substrate via the adhesive layer. Therefore, it is preferable that the support substrate has the strength necessary to prevent the substrate from being damaged or deformed when the device is thinned, the substrate is transported, or the substrate is mounted on the substrate. Further, the support substrate is preferably one that transmits light having a wavelength that can change the quality of the separation layer.
As the material of the support substrate, for example, glass, silicon, acrylic resin and the like are used. Examples of the shape of the support substrate include, but are not limited to, a rectangle, a circle, and the like.
Further, as the support substrate, in order to further increase the density and improve the production efficiency, it is possible to use a support substrate having a larger size, which is circular, or a large panel having a quadrangular shape in a plan view.

≪Separation layer≫
The separation layer is a layer adjacent to the adhesive layer, which is altered by irradiation with light and enables the support substrate to be separated from the substrate bonded to the support.
This separation layer can be formed by using the composition for forming a separation layer described later, for example, by calcining the components contained in the composition for forming a separation layer, or by a chemical vapor deposition (CVD) method. It is formed. This separation layer is suitably denatured by absorbing the light transmitted through the support substrate and irradiated.
The term "deterioration" of the separation layer means a phenomenon in which the separation layer can be destroyed by an external force or a state in which the adhesive force between the separation layer and the layer in contact with the separation layer is reduced. The separation layer becomes brittle by absorbing light and loses its strength or adhesiveness before being irradiated with light. The alteration of the separation layer occurs by causing decomposition by the energy of absorbed light, change in configuration, dissociation of functional groups, and the like.
The separation layer is preferably formed only from a material that absorbs light, but is a layer containing a material that does not have a structure that absorbs light to the extent that the essential properties of the present invention are not impaired. There may be.

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

It is preferable that the surface of the separation layer on the side in contact with the adhesive layer is flat (no unevenness is formed), whereby the adhesive layer can be easily formed, and the substrate or wiring layer and the support substrate can be used. Can be easily applied evenly.

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

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

The light to irradiate the separation layer is, for example, a YAG laser, a ruby laser, a glass laser, a _YVO4 laser, an LD laser, a solid laser such as a fiber laser, or a liquid laser such as a dye laser, depending on the wavelength that fluorocarbon can absorb. , CO ₂ laser, excima laser, Ar laser, gas laser such as He-Ne laser, laser light such as semiconductor laser, free electron laser, or non-laser light may be appropriately used. As the wavelength capable of altering the fluorocarbon, for example, a wavelength in the range of 600 nm or less can be used.

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

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

-The inorganic substance separation layer may be made of an inorganic substance. The inorganic substance may be any substance that is altered by absorbing light, and for example, one or more selected from the group consisting of a metal, a metal compound, and carbon is preferably mentioned. The metal compound is a compound containing a metal atom, and examples thereof include metal oxides and metal nitrides.
Examples of such an inorganic substance include one or more selected from the group consisting of gold, silver, copper, iron, nickel, aluminum, titanium, chromium, SiO ₂ , SiN, Si _{3N 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 inorganic substance absorbs light having a wavelength in a unique range depending on the type.

The light irradiating the separation layer made of an inorganic substance may be, for example, a solid laser such as a YAG laser, a ruby laser, a glass laser, a _YVO4 laser, an LD laser, or a fiber laser, or a dye laser, depending on the wavelength that the inorganic substance can absorb. Liquid lasers such as, CO ₂ lasers, excima lasers, Ar lasers, gas lasers such as He-Ne lasers, laser light such as semiconductor lasers and free electron lasers, or non-laser light may be appropriately used.
The separation layer made of an inorganic substance can be formed on a support substrate by a known technique such as sputtering, chemical vapor deposition (CVD), plating, plasma CVD, spin coating and the like.

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

Examples of the structure containing a carbon-halogen bond include -CH ₂ Cl, -CH ₂ Br, -CH ₂ I, -CF _2- , -CF ₃ , -CH = CF ₂ , -CF = CF ₂ , and fluorine. Aryl carbonate, aryl chloride and the like can be mentioned.

Examples of the structure including the above Si—A ¹ bond include SiH, SiH ₂ , SiH ₃ , Si—CH ₃ , Si—CH _2- , Si—C 6H ₅ , SiO—aliphatic, Si _— OCH ₃ , Si-OCH ₂ CH ₃ , Si-OC ₆ H ₅ , Si-O-Si, Si-OH, SiF, SiF ₂ or SiF ₃ and the like. As the structure containing the Si—A ¹ bond, it is particularly preferable to form a siloxane skeleton or a silsesquioxane skeleton.

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

Examples of the compound containing the Ti—O bond include (i) tetra-i-propoxytitanium, tetra-n-butoxytitanium, tetrakis (2-ethylhexyloxy) titanium, titanium-i-propoxyoctylene glycolate and the like. Alkoxytitanium; (iii) Di-i-propoxy-bis (acetylacetonato) titanium or chelated titanium such as 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 (On-C ₄ H ₉ ) ₂ -O-] _n -Titanium polymers such as n-C 4H ₉ ; ( _iv ) tri-n-butoxytitanium monostearate, titanium stearate, di-i-propoxytitanium diisostearate or (2-n-butoxycarbonylbenzoyloxy). Achilled titanium such as tributoxytitanium; (v) water-soluble titanium compounds such as di-n-butoxy-bis (triethanolaminato) titanium and the like can be mentioned.
Among these, compounds containing a Ti—O bond include di-n-butoxy-bis (triethanolaminet) titanium (Ti (OC ₄ H ₉ ) ₂ [OC ₂ H ₄ N (C ₂ H ₄ OH)). ₂ ] ₂ ) is preferable.

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

Those skilled in the art can easily understand the wavelength of infrared rays that can be absorbed by each of the above structures. For example, as an absorption band in each structure, Non-Patent Documents: SILVERSTEIN, BASSLER, MORRRILL, "Identification Method by Spectrum of Organic Compounds (5th Edition) -Combination of MS, IR, NMR, UV-" (Published in 1992). References can be made to the description on pages 146 to 151.

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

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

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

"Reactive polysilsesquioxane" refers to polysilsesquioxane having a silanol group at the end of the polysilsesquioxane skeleton or a functional group capable of forming a silanol group by hydrolysis. .. By condensing the silanol group or the functional group capable of forming the silanol group, they can be polymerized with each other. Further, if the reactive polysilsesquioxane has a silanol group or a functional group capable of forming a silanol group, it can form a silsesquioxane skeleton having a random structure, a cage-shaped structure, a ladder structure or the like. The provided reactive polysilsesquioxane 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 preferable range, it can be suitably altered by irradiating with infrared rays (preferably far infrared rays, more preferably light having a wavelength of 9 to 11 μm). A possible separation layer can be formed.

The weight average molecular weight (Mw) of the reactive polysilsesquioxane is preferably 500 to 50,000, more preferably 1000 to 10000.
If the weight average molecular weight (Mw) of the reactive polysilsesquioxane is within the above-mentioned preferable range, it can be suitably dissolved in a solvent and can be suitably applied on a support plate.

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

-Resin component having a phenol skeleton The separation layer may contain a resin component having a phenol skeleton. By having a phenol skeleton, it is easily altered (oxidized, etc.) by heating or the like, and the photoreactivity is enhanced.
As used herein, "having a phenol skeleton" means that it contains a hydroxybenzene structure.
The resin component having a phenol skeleton has a film-forming ability, and preferably has a molecular weight of 1000 or more. When the molecular weight of the resin component is 1000 or more, the film forming ability is improved. The molecular weight of the resin component is more preferably 1000 to 30000, still more preferably 1500 to 20000, and particularly preferably 2000 to 15000. When the molecular weight of the resin component is not more than the upper limit of the above-mentioned preferable range, the solubility of the composition for forming a separation layer in a solvent is enhanced.
As the molecular weight of the resin component, the polystyrene-equivalent weight average molecular weight (Mw) by GPC (gel permeation chromatography) is used.

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

<Device layer>
The device layer is a composite of a member made of a metal or a semiconductor and a resin that seals or insulates the member. Specifically, the device layer includes at least one of a sealing material layer and a wiring layer, and may further include a substrate.
In the laminate 100 shown in FIG. 1, the device layer 45 is composed of a substrate 4 and a sealant layer 5. In the laminate 200 shown in FIG. 2, the device layer 456 is composed of a substrate 4, a sealing material layer 5, and a wiring layer 6. In the laminated body 300 shown in FIG. 3, the device layer is composed of the wiring layer 6. In the laminated body 400 shown in FIG. 4, the device layer 645 is composed of a wiring layer 6, a substrate 4, and a sealing material layer 5.

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

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

≪Encapsulant layer≫
The encapsulant layer is provided for encapsulating the substrate, and is formed by using the encapsulant. As the sealing material, a member capable of insulating or sealing a member made of metal or a semiconductor is used.
In the present embodiment, a resin composition containing a resin is used as the sealing material. The resin used for the encapsulant is not particularly limited as long as it can encapsulate and / or insulate the metal or semiconductor, and examples thereof include epoxy resins and polyimides.
The encapsulant may contain other components such as a filler in addition to the resin. Examples of the filler include spherical silica particles and the like.

The resin used for the encapsulant has hygroscopicity and may generate gas as the temperature rises. In this case, most of the gas generated from the encapsulant is water vapor.
Such generation of water vapor in the heat treatment process during the electronic component manufacturing process causes voids in the adhesive layer. In the laminate of the present embodiment, an adhesive composition containing an elastomer having a structural unit (u1) is used as the material of the adhesive layer. As a result, the elastic modulus of the adhesive layer is increased, and a harder film is formed. Therefore, the generation of voids between the device layer and the support is suppressed.

≪Wiring layer≫
The wiring layer is also called an RDL (Revision Layer: rewiring layer), and is a thin film wiring body constituting a wiring connected to a substrate, and may have a single layer or a plurality of layers. The wiring layer is composed of conductors (eg, metals such as aluminum, copper, titanium, nickel, gold and silver, and silver) between patterned resin materials (such as photosensitive polyimide and photosensitive acrylic resin). -The wiring may be formed of an alloy such as a tin alloy), but the wiring is not limited to this.

When a layer containing a resin material is provided adjacent to the adhesive layer in the device layer, gas is released from the resin material by the heat treatment step, which causes voids. In the laminated body of the present embodiment, since the adhesive composition containing the elastomer having the structural unit (u1) is used as the material of the adhesive layer, the generation of voids can be reduced.

In the laminated body of FIGS. 1 to 4, the support substrate 1 and the separation layer 2 are adjacent to each other, but the present invention is not limited to this, and another layer is further formed between the support substrate 1 and the separation layer 2. It may have been done. In this case, the other layer may be composed of a material that transmits light. According to this, it is possible to appropriately add a layer that imparts preferable properties to the laminated body without hindering the incident of light on the separation layer 2. The wavelength of light that can be used differs depending on the type of material constituting the separation layer 2. Therefore, the material constituting the other layer does not need to transmit light of all wavelengths, and can be appropriately selected from the materials transmitting light having a wavelength that can change the material constituting the separation layer 2.

(Manufacturing method of laminated body)
A third aspect of the present invention is a method for manufacturing a laminate in which a support, an adhesive layer, and a device layer are laminated in this order, and includes an adhesive layer forming step and a device layer forming step. The method for producing the laminate may further include a separation layer forming step. The device layer forming step can include any one of a substrate fixing step, a sealing step, a grinding step and a wiring layer forming step.

<First Embodiment>
The method for manufacturing a laminated body according to the first embodiment includes a step of manufacturing a support, a step of forming an adhesive layer, and a step of forming a device layer.
FIG. 5 is a schematic process diagram illustrating a part of an embodiment of a method for manufacturing a laminated body. FIG. 5A is a diagram illustrating a step of manufacturing a support, and FIG. 2B is a diagram illustrating a step of forming an adhesive layer.
FIG. 6 is a schematic process diagram illustrating an embodiment of a method for manufacturing a laminated body 100 from a support 123 with an adhesive layer. 6 (a) is a diagram showing a support 123 with an adhesive layer, FIG. 6 (b) is a diagram showing a substrate fixing process, and FIG. 6 (c) is a diagram illustrating a sealing process. be.
FIG. 7 is a schematic process diagram illustrating an embodiment of a method for manufacturing a laminated body 200 from a laminated body 100. 7 (a) is a diagram showing the laminated body 100, FIG. 7 (b) is a diagram for explaining a grinding process, and FIG. 7 (c) is a diagram for explaining a rewiring forming process.

In the method for producing a laminate of the present embodiment, a composition containing fluorocarbon is used as a composition for forming a separation layer. Further, as the composition for forming an adhesive layer, a composition containing the component (EP1) according to the above-mentioned embodiment is used.

[Step of manufacturing the support]
The step of producing the support in the embodiment is a step of forming a separation layer on one side of the support substrate using the composition for forming a separation layer to obtain a support.
In FIG. 5A, a separation layer 2 is formed on the support substrate 1 by using a composition for forming a separation layer (which contains fluorocarbon) (that is, a support substrate with a separation layer is produced. Yes).

The method for forming the separation layer 2 on the support substrate 1 is not particularly limited, and examples thereof include spin coating, dipping, roller blades, spray coating, slit coating, and chemical vapor deposition (CVD).
For example, in the step of producing the support, the solvent component is removed from the coating layer of the separation layer forming composition coated on the support substrate 1 under a heating environment or a reduced pressure environment to form a film (separation layer 2). (Forming) or forming a film on the support substrate 1 by a vapor deposition method (forming a separation layer 2) to obtain a support 12.

[Adhesive layer forming process]
The adhesive layer forming step in the embodiment is a step of forming an adhesive layer on one side of the support using the adhesive layer forming composition of the above-described embodiment.
In FIG. 5B, the adhesive layer 3 is formed on the surface of the support 12 on the separation layer 2 side by using the composition for forming an adhesive layer of the above-described embodiment (that is, the support 123 with an adhesive layer). Has been produced).

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

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

When the adhesive layer 3 contains a curable monomer and a photopolymerization initiator, it is preferable to polymerize the curable monomer by exposing it to an atmosphere of an inert gas such as nitrogen gas. The exposure conditions may be appropriately set according to the type of the photopolymerization initiator and the like.

[Device layer forming process]
In the device layer forming step of the present embodiment, a device layer which is a composite of a member made of a metal or a semiconductor and a resin that seals or insulates the member is formed. The device layer forming step can include any of a substrate fixing step, a sealing step, a grinding step, and a wiring layer forming step.
In one embodiment, the device layer forming step includes a substrate fixing step and a sealing step. In this case, the device layer forming step may further include a grinding step and a wiring layer forming step.
In another embodiment, the device layer forming step includes a wiring layer forming step. In this case, the device layer forming step may further include a substrate fixing step, a sealing step, and a grinding step.

-About the substrate fixing process The substrate fixing process is a process of fixing the substrate (bare chip) on the support via the adhesive layer.
In FIG. 6B, the support substrate 1 (support 12) on which the separation layer 2 is formed and the substrate 4 are laminated via the adhesive layer 3, and the support 12, the adhesive layer 3, and the substrate 4 are laminated in this order. The stacked structures 30 are obtained.

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

-About the sealing process The sealing process is a step of sealing the substrate fixed on the support with a sealing material.
In FIG. 6C, a laminated body 100 is obtained in which the entire substrate 4 fixed to the support 12 via the adhesive layer 3 is sealed by the sealing material layer 5. In the laminate 100, the substrate 4 and the encapsulant layer 5 constitute the device layer 45.

In the sealing step, for example, a sealing material heated to 130 to 170 ° C. is supplied onto the adhesive layer 3 so as to cover the substrate 4 while maintaining a high viscosity state, and is compression-molded. A laminated body 100 in which the sealing material layer 5 is provided on the adhesive layer 3 is produced.
At that time, the temperature condition is, for example, 130 to 170 ° C.
The pressure applied to the substrate 4 is, for example, 50 to 500 N / cm ² .

The encapsulant layer 5 is not provided for each individual substrate 4, but is preferably provided so as to cover the entire substrate 4 on the adhesive layer 3.

-Grinding step The grinding step is a step of grinding the sealing material portion (sealing material layer 5) in the sealing body so that a part of the substrate is exposed after the sealing step.
Grinding of the encapsulant portion is performed, for example, by grinding the encapsulant layer 5 to a thickness substantially equal to that of the substrate 4, as shown in FIG. 7 (b).

-About the wiring layer forming step The wiring layer forming step is a step of forming a wiring layer on the exposed substrate after the grinding step.
In FIG. 7C, the wiring layer 6 is formed on the substrate 4 and the encapsulant layer 5. Thereby, the laminated body 200 can be obtained. In the laminated body 200, the substrate 4, the sealing material layer 5, and the wiring layer 6 constitute the device layer 456.

Examples of the method for forming the wiring layer 6 include the following methods.
First, a dielectric layer such as silicon oxide (SiO _x ) or a photosensitive resin is formed on the encapsulant layer 5. The dielectric layer made of silicon oxide can be formed by, for example, a sputtering method, a vacuum vapor deposition method, or the like. The dielectric layer made of the photosensitive resin can be formed by applying the photosensitive resin on the sealing material layer 5 by, for example, spin coating, dipping, roller blades, spray coating, slit coating, or the like. ..

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

As described above, when performing the photolithography treatment, the etching treatment, etc., the sealing body (laminated body 100) dissolves an acid such as hydrofluoric acid, an alkali such as tetramethylammonium hydroxide (TMAH), or a resist material. It is exposed to a resist solvent for processing and is treated at a high temperature.
However, by forming the adhesive layer 3 using the adhesive composition containing the elastomer having the structural unit (u1) described above, the release of gas from the encapsulant layer 5 is suppressed. Therefore, it is possible to prevent the generation of voids between the sealing material layer 5 and the support 12, and the wiring layer 6 can be suitably formed.

According to the method for manufacturing a laminated body according to the present embodiment, the support 12, the adhesive layer 3, the device layer 45 (the substrate 4 and the encapsulant layer 5) or the device layer 456 (the substrate 4, the encapsulant layer 5). The laminated body 100 or the laminated body 200 in which the wiring layer 6) and the wiring layer 6) are laminated in this order can be stably manufactured.
The laminate 100 or the laminate 200 is a laminate manufactured in a process based on a fan-out type technique in which terminals provided on the substrate 4 are mounted on a wiring layer 6 extending outside the chip area.

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

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

FIG. 8 is a schematic process diagram illustrating an embodiment of a method for manufacturing a semiconductor package (electronic component). 8 (a) is a diagram showing the laminated body 200, FIG. 8 (b) is a diagram for explaining a separation step, and FIG. 8 (c) is a diagram for explaining a removal step.

[Separation process]
The separation step in the embodiment is a step of separating the support substrate 1 from the device layer 456 by irradiating the separation layer 2 with light (arrows) via the support substrate 1 to change the quality of the separation layer 2.
As shown in FIG. 8A, in the separation step, the separation layer 2 is altered by irradiating the separation layer 2 with light (arrows) via the support substrate 1.

Examples of the wavelength at which the separation layer 2 can be altered include a range of 600 nm or less.
The type and wavelength of the light to be irradiated may be appropriately selected depending on the transparency of the support substrate 1 and the material of the separation layer 2. For example, a YAG laser, a ruby laser, a glass laser, a YVO ₄ laser, an LD laser, and a fiber. It is possible to use solid lasers such as lasers, liquid lasers such as dye lasers, gas lasers such as CO ₂ lasers, excima lasers, Ar lasers and He-Ne lasers, laser light such as semiconductor lasers and free electron lasers, and non-laser light. can. As a result, the separation layer 2 can be altered so that the support substrate 1 and the device layer 456 can be easily separated.

When irradiating a laser beam, the following conditions can be mentioned as an example of the laser beam irradiation conditions.
The average output value of the laser beam is preferably 1.0 W or more and 5.0 W or less, and more preferably 3.0 W or more and 4.0 W or less. The repetition frequency of the laser beam is preferably 20 kHz or more and 60 kHz or less, and more preferably 30 kHz or more and 50 kHz or less. The scanning speed of the laser beam is preferably 100 mm / s or more and 10,000 mm / s or less.

After irradiating the separation layer 2 with light (arrow) to change the quality of the separation layer 2, the support substrate 1 is separated from the device layer 456 as shown in FIG. 8 (b).
For example, the support substrate 1 and the device layer 456 are separated from each other by applying a force in a direction in which the support substrate 1 and the device layer 456 are separated from each other. Specifically, one of the support substrate 1 or the device layer 456 side (wiring layer 6) is fixed to the stage, and the other is lifted while being sucked and held by a separation plate equipped with a suction pad such as a bellows pad. The support substrate 1 and the device layer 456 can be separated.
The force applied to the laminated body 200 may be appropriately adjusted depending on the size of the laminated body 200 and the like, and is not limited, but for example, in the case of a laminated body having a diameter of about 300 mm, 0.1 to 5 kgf (0). By applying a force of about .98 to 49N), the support substrate 1 and the device layer 456 can be suitably separated.

[Removal process]
The removal step in the embodiment is a step of removing the adhesive layer and the separation layer adhering to the device layer after the separation step.
In FIG. 8B, the adhesive layer 3 and the separation layer 2 are attached to the device layer 456 after the separation step. In the present embodiment, the electronic component 50 is obtained by removing the adhesive layer 3 and the separation layer 2 adhering to the device layer 456 in the removal step.

Examples of the method for removing the adhesive layer 3 and the like adhering to the device layer 456 include a method for removing the residue of the adhesive layer 3 and the separation layer 2 using a cleaning liquid.
As the cleaning liquid, a cleaning liquid containing an organic solvent is preferably used. As the organic solvent in this cleaning liquid, it is preferable to use the organic solvent blended in the composition for forming the separation layer and the solvent component blended in the composition for forming the adhesive layer.
The adhesive layer formed by using the composition for forming an adhesive layer of the above-described embodiment has increased solubility in a hydrocarbon-based solvent. Therefore, in the embodiment, the cleaning and removing property of the adhesive layer is good.

In the method for manufacturing an electronic component of the present embodiment, after the above removing step, the electronic component 50 may be further subjected to a treatment such as solder ball formation, dicing, or oxide film formation.

Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited to these examples.

<Preparation of adhesive composition>
(Examples 1 to 5, Comparative Examples 1 to 2)
The resin components shown in Table 1 were dissolved in a solvent (decahydronaphthalene) to prepare adhesive compositions (resin component concentration 30% by mass) of each example.

In Table 1, each abbreviation has the following meaning. The value in [] is the blending amount (part by mass).
The weight average molecular weight and the degree of dispersion of the resin components shown below were determined using polystyrene-equivalent values by GPC (gel permeation chromatography).
The 1% weight loss temperature (° C) for the resin components shown below is the initial weight when heating is started at 25 ° C in a nitrogen atmosphere and the heating temperature is raised by 10 ° C at 1-minute intervals. This is the temperature when the weight is reduced by 1% by weight. In this example, this 1% weight loss temperature was measured by a thermogravimetric measuring device.

(EP) -1: Septon 2002 (trade name), manufactured by Kuraray Co., Ltd. Styrene content 13 mol%, weight average molecular weight 54000; elastomer (1) having a plurality of structural units represented by the following chemical formula (EP) -1.

(EP) -2: Septon 8004 (trade name), manufactured by Kuraray Co., Ltd. Styrene content 12 mol%, weight average molecular weight 98000; elastomer (2) having a plurality of structural units represented by the following chemical formula (EP) -2.

(EP) -3: The procedure described in Akinori Toyoda's document "Synthesis of Bulky Hydrocarbon Group-Containing Polymer by Polymer Reaction Method and Its Properties" for the Elastomer (1) Represented by Chemical Formula (EP) -1. According to the above, the mixture was reacted with adamantanol and modified to obtain an adamantane-modified elastomer (1). Adamantane groups were added to 53% (molar ratio) of the styrene units in the elastomer (1). Weight average molecular weight 70600, dispersity 1.37; 1% weight loss temperature 365 ° C.

(EP) -4: The procedure described in Akinori Toyoda's document "Synthesis of Bulky Hydrocarbon Group-Containing Polymer by Polymer Reaction Method and Its Properties" for the Elastomer (2) Represented by the Chemical Formula (EP) -2. According to the above, the mixture was reacted with adamantanol and modified to obtain an adamantane-modified elastomer (2). Adamantane groups were added to 60% (molar ratio) of the styrene units in the elastomer (2). Weight average molecular weight 219200, dispersity 1.78; 1% weight loss temperature 365 ° C.

<Evaluation>
For the adhesive composition of each example, the complex elastic modulus (E * ₁₅₀ , E * ₅₀ ) and the glass transition temperature (Tg) were determined by the methods shown below. Further, the adhesive layer formed by using the adhesive composition of each example was evaluated for chemical resistance and cleaning / removing property by the methods shown below. These results are shown in Table 2.

≪Measurement of elastic modulus≫
For the adhesive composition of each example, the complex elastic modulus (E * ₁₅₀ , E * ₅₀ ) at 150 ° C. and 50 ° C. was measured using a dynamic viscoelasticity measuring device Rheogel-E4000 (manufactured by UBM Co., Ltd.). In addition, the ratio of complex elastic moduli (E * ₅₀ / E * ₁₅₀ ) was determined.
First, the adhesive composition was applied onto a PET film with a mold release agent and heated in an oven under atmospheric pressure at 50 ° C. for 60 minutes and then at 150 ° C. for 60 minutes to form test pieces (thickness). 500 μm). Then, the complex elastic modulus of the test piece (size 2 cm × 0.5 cm, thickness 500 μm) peeled off from the PET film was measured using the above-mentioned dynamic viscoelasticity measuring device.
The measurement conditions were set to a tension condition with a frequency of 1 Hz and a temperature rise rate of 5 ° C./min from a start temperature of 25 ° C. to 300 ° C.

FIG. 9 is a graph showing the behavior of the complex elastic modulus with respect to temperature for the test piece (adhesive layer) formed by using the adhesive composition of each example.
The adhesive compositions of Comparative Examples 1 and 2 could not be measured because the test pieces were cut under the tension condition at 150 ° C. When the adhesive compositions of Examples 1 to 5 were used, a higher complex elastic modulus was exhibited at the same temperature as compared with the case where the adhesive compositions of Comparative Examples 1 and 2 were used, and in addition, the temperature was higher. It was possible to measure up to the side.

≪Measurement of glass transition temperature (Tg)≫
For the test piece (adhesive layer) formed by using the adhesive composition of each example in the same manner as above, a dynamic viscoelasticity measuring device Rheogel-E4000 (manufactured by UBM Co., Ltd.) was used under the condition of a frequency of 1 Hz. The glass transition temperature was determined based on the change in viscoelasticity measured by raising the temperature from 25 ° C. to 300 ° C. at a heating rate of 5 ° C./min.

≪Chemical resistance≫
The adhesive composition of each example was applied to a glass substrate and dried to form an adhesive layer having a thickness of 50 μm. Then, the glass substrate on which the adhesive layer was formed was immersed in N-methyl-2-pyrrolidone (NMP) at 70 ° C. for 10 minutes. After that, the rate of change in film thickness (degree of swelling) before and after immersion was determined, and the chemical resistance was evaluated according to the following evaluation criteria.
Evaluation Criteria ◯: The rate of such film thickness change was less than 20%.
X: The rate of such film thickness change was 20% or more.

Using the adhesive compositions of each example, laminates and electronic components were manufactured as follows.

[Adhesive layer forming process]
Separated on a glass support substrate (size 10 cm × 10 cm, thickness 700 μm) by a CVD method using _C4 F ₈ as a reaction gas under the conditions of a flow rate of 400 sccm, a pressure of 700 mTorr, a high frequency power of 2500 W and a film formation temperature of 240 ° C. A fluorocarbon film (thickness 1 μm), which is a layer, was formed to prepare a support.

Next, each of the adhesive compositions of each example was applied onto the separation layer formed on the glass support substrate while rotating at 1500 rpm by a spin coating method.
Then, the support coated with the adhesive composition of each example was preheated at 160 ° C. for 4 minutes to form an adhesive layer having a thickness of 5 μm.

[Device layer forming process]
A sealing substrate (device layer) is placed on the adhesive layer formed as described above, and then a pressing plate (300 mmφ) heated to 215 ° C. is used under a reduced pressure condition of a pressure lower than 10 Pa. And pressed for 3 minutes while applying a force of 4 tons to obtain a laminate.

[Separation process]
The laminate obtained in the device layer forming step was irradiated with a laser beam having a wavelength of 532 nm from the glass support substrate side toward the separation layer (fluorocarbon film). As a result, the separation layer was altered to separate the glass support substrate from the substrate (bare chip) included in the laminate to obtain a sealed substrate with an exposed adhesive layer.
[Removal process]
Next, the obtained sealed substrate was spray-cleaned with p-menthane as a cleaning liquid for 5 minutes to remove the adhesive layer adhering to the sealed substrate to obtain an electronic component.

≪Washing and removing property≫
In the removal step, the wash removability was evaluated according to the evaluation criteria shown below.
Evaluation Criteria ○: No adhesive layer residue was found on the sealing substrate after spray cleaning ×: Adhesive layer residue was found on the sealing substrate after spray cleaning

From the results shown in Table 2, the adhesive compositions of Examples 1 to 5 had higher elastic moduli and glass transition temperatures than the adhesive compositions of Comparative Examples 1 and 2. From this, it was confirmed that the adhesive compositions of Examples 1 to 5 to which the present invention was applied can have higher heat resistance and chemical resistance and can form an adhesive layer that is not easily affected by high temperature treatment and chemical treatment. Was done.

1 Support substrate, 2 Separation layer, 3 Adhesive layer, 4 Substrate, 5 Encapsulant layer, 6 Wiring layer, 50 Electronic components, 100 Laminates, 200 Laminates, 300 Laminates, 400 Laminates.

Claims (15)

An adhesive composition containing a resin component (P).
The resin component (P) is a copolymer having a structural unit (u1) represented by the following general formula (u1-1) and a structural unit (u2) represented by the following general formula (u2-1). Contains an elastomer consisting of
The adhesive composition in which the molar ratio of the structural unit (u1) to the structural unit (u2) contained in the elastomer is structural unit (u1) / structural unit (u2) = 53/47 to 5 .

[In the general formula (u1-1), R ^α1 represents an alkyl group or a hydrogen atom having 1 to 5 carbon atoms. R ⁰¹ represents a group containing an alicyclic group. R ⁰² is a halogen atom, an alkyl group having 1 to 8 carbon atoms which may be substituted with a halogen atom, an aryl group having 6 to 12 carbon atoms which may be substituted with a halogen atom, a cyano group, a nitro group, and a hydroxyl group. , A carboxy group, a group represented by -OR and a group represented by -COOR (where R is an alkyl group which may be substituted with a halogen atom having 1 to 8 carbon atoms). It is a group that is selected and does not correspond to R ⁰¹ . m is a natural number from 1 to 5, and n1 is an integer of 0 or more. However, the sum of m and n1 does not exceed 5. ]

[In the general formula (u2-1), R ^α2 represents an alkyl group or a hydrogen atom having 1 to 5 carbon atoms. R ⁰³ is a halogen atom, an alkyl group having 1 to 8 carbon atoms which may be substituted with a halogen atom, an aryl group having 6 to 12 carbon atoms which may be substituted with a halogen atom, a cyano group, a nitro group, and a hydroxyl group. , A carboxy group, a group represented by -OR and a group represented by -COOR (where R is an alkyl group which may be substituted with a halogen atom having 1 to 8 carbon atoms). It is a group to be selected and does not correspond to the above R ⁰¹ . n2 is an integer of 0 or more and 5 or less. ] The adhesive composition according to claim 1 , wherein the proportion of the structural unit (u1) contained in the elastomer is 1 to 40 mol% with respect to all the structural units (100 mol%) constituting the elastomer. The adhesive composition according to claim 1 or 2 , wherein R ⁰¹ in the general formula (u1-1) is a group containing a crosslinked carbocyclic group. The adhesive composition according to claim 3 , wherein the crosslinked carbon moiety in the crosslinked carbon ring type group is directly bonded to the carbon constituting the benzene ring in the general formula (u1-1). The adhesive composition according to any one of claims 1 to 4, wherein the content of the elastomer is 20% by mass or more with respect to 100% by mass of the total amount of the resin component (P). The adhesive composition according to any one of claims 1 to 5 , which is used for forming the adhesive layer in a laminated body in which a support, an adhesive layer and a device layer are laminated in this order. The adhesive composition according to claim 6 , wherein the device layer is a composite of a member made of a metal or a semiconductor and a resin that seals or insulates the member. According to any one of claims 1 to 7 , the glass transition temperature (Tg) of the test piece becomes 100 ° C. or higher when the test piece is obtained by applying the adhesive composition and drying it. The adhesive composition according to description. By applying the adhesive composition and drying it, a test piece having a thickness of 500 μm is prepared, and dynamic viscoelasticity is measured under the conditions of a starting temperature of 25 ° C., a heating rate of 5 ° C./min, and a frequency of 1 Hz. The adhesive composition according to any one of claims 1 to 8 , wherein the complex elastic modulus E * ₁₅₀ at 150 ° C. of the test piece is 0.1 MPa or more. By applying the adhesive composition and drying it, a test piece having a thickness of 500 μm is prepared, and dynamic viscoelasticity is measured under the conditions of a starting temperature of 25 ° C., a heating rate of 5 ° C./min, and a frequency of 1 Hz. The adhesive composition according to any one of claims 1 to 9 , wherein the complex elastic modulus E * ₅₀ at 50 ° C. of the test piece is 30 MPa or more when attached to. The ratio (E * ₅₀ / E * ₁₅₀ ) of the complex elastic modulus E * ₅₀ at 50 ° C. and the complex elastic modulus E * ₁₅₀ at 150 ° C. when the dynamic viscoelasticity measurement was performed under the above conditions is 5000 or less. The adhesive composition according to claim 9 or 10 . A laminate in which a support, an adhesive layer, and a device layer are laminated in this order.
The adhesive layer is a laminated body which is a dried body of the adhesive composition according to any one of claims 1 to 11 . A method for manufacturing a laminate in which a support, an adhesive layer, and a device layer are laminated in this order.
An adhesive layer forming step of forming the adhesive layer on the support using the adhesive composition according to any one of claims 1 to 11 .
A device layer forming step of forming a device layer, which is a composite of a member made of a metal or a semiconductor and a resin that seals or insulates the member, on the adhesive layer.
A method for manufacturing a laminated body. The support is composed of a support substrate and a separation layer that is altered by irradiation with light.
The method for manufacturing a laminate according to claim 13 , wherein the adhesive layer forming step is a step of forming an adhesive layer on the separation layer. After obtaining the laminate by the method for producing the laminate according to claim 14 ,
A separation step of separating the support substrate from the device layer by irradiating the separation layer with light through the support substrate to alter the separation layer.
After the separation step, a removal step of removing the adhesive layer and the separation layer adhering to the device layer, and
A method for manufacturing electronic components.

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