TWI764981B - Adhesive composition, adhesive-attached support, adhesive film, laminate, method for producing the same, and method for producing electronic parts - Google Patents

Abstract

An object of the present invention is to provide an adhesive composition for bonding a support and a substrate, a support with an adhesive layer using the same, an adhesive film, a laminate, a method for producing the same, and a method for producing an electronic component The adhesive composition used can form an adhesive layer with higher heat resistance. The solution of the present invention is to use an adhesive composition, which is an adhesive composition for laminating the support (12) and the substrate (4), and contains a hydrocarbon resin (P1) and a resin with a glass transition temperature of 180°C or higher. (P2) (however, the aforementioned hydrocarbon resin (P1) is not included) as the resin component (P).

Description

Adhesive composition, adhesive-attached support, adhesive film, laminate, method for producing the same, and method for producing electronic parts

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

In semiconductor packages (electronic parts) including semiconductor elements, there are various forms according to the corresponding size, such as WLP (Wafer Level Package, wafer level package), PLP (Panel Level Package, panel level package) Wait. As a technology of semiconductor packaging, fan-in technology and fan-out technology can be cited. As a semiconductor package formed by a fan-in type technology, a fan-in type WLP (Fan-in Wafer Level Package, fan-in wafer level package) in which terminals at the end of a bare chip are rearranged in a chip area is known. As a semiconductor package formed by the fan-out technology, a fan-out WLP (Fan-out Wafer Level Package, fan-out wafer level package) in which the terminal is relocated outside the chip area is known.

In recent years, in particular, fan-out technology is used as a fan-out PLP (Fan-out Panel Level Package, fan-out panel level package), which is used to arrange semiconductor elements on a panel and encapsulate them. Among the semiconductor packages, more advanced technologies can be realized. Methods for further high integration, thinning, and miniaturization are attracting attention.

In order to reduce the size of the semiconductor package, it is important to reduce the thickness of the substrate in the device to be incorporated. However, when the thickness of the substrate is reduced, the strength of the substrate is reduced, and breakage of the substrate is likely to occur at the time of semiconductor package manufacture. On the other hand, the laminated body which bonded the support body to a board|substrate is employ|adopted.

Here, when bonding a substrate and a support, conventionally, from the viewpoint of being excellent in light transmittance, an adhesive containing a polymer having a cycloolefin structure has been widely used. Patent Document 1 discloses an adhesive composition comprising a polymer having a cycloolefin structure and a (meth)acrylate monomer compatible with the polymer. [Prior Art Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Application Laid-Open No. 2014-105316

[Problems to be solved by the invention]

In addition, in the manufacture of a semiconductor package, after bonding the substrate and the support with an adhesive, high-temperature treatment such as sealing, film formation, and firing is performed. Furthermore, when the substrate and the support are bonded 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 above-mentioned high temperature treatment. The present invention was made in view of the above-mentioned circumstances, and an object of the present invention is to provide an adhesive composition, a support with an adhesive layer using the same, an adhesive film, a laminate, a method for producing the same, and a method for producing an electronic component, and the adhesive composition It is an adhesive composition for bonding a support and a substrate, and can form an adhesive layer with higher heat resistance. [Means to solve the problem]

In order to solve the above-mentioned problems, the present invention adopts the following configuration. That is, the first aspect of the present invention is an adhesive composition, which is an adhesive composition for bonding a support and a substrate, characterized by containing the following as the resin component (P), the hydrocarbon resin (P1) and the A resin (P2) having a glass transition temperature of 180°C or higher (however, the aforementioned hydrocarbon resin (P1) is not included). A second aspect of the present invention is an adhesive composition for laminating a support and a substrate, wherein the adhesive composition contains at least a hydrocarbon resin (P1) as the resin component (P), and the above A test piece with a thickness of 20 mm×5 mm and a thickness of 0.5 mm was prepared from the adhesive composition. Under the condition of stretching at a frequency of 1 Hz, from room temperature to 215 ° C, the above-mentioned test piece was transferred to the dynamic state under the condition of heating at a rate of 5 ° C/min. When viscoelasticity is measured, the following two requirements are met: the complex elastic modulus E* ₅₀ at 50°C is less than 1.0´10 ⁹ Pa, and the complex elastic modulus E* ₁₅₀ at 150°C exceeds 3.0´10 ⁶ Pa.

A third aspect of the present invention is a support with an adhesive layer, which is characterized by comprising: a support to which a substrate is bonded, and on the support, the adhesive as described in the first or second aspect is used The adhesive layer formed of the composition.

A fourth aspect of the present invention is an adhesive film characterized by comprising: a film and an adhesive layer formed on the film using the adhesive composition of the first or second aspect.

A fifth aspect of the present invention is a laminate in which a support and a substrate are bonded via an adhesive layer, wherein the adhesive layer uses the adhesive of the first or second aspect. layer formed from the composition.

A sixth aspect of the present invention is a method for producing a laminate, which is a method for producing a laminate in which a support and a substrate are bonded via an adhesive layer, characterized by comprising: a laminate on the support or the substrate. At least one, the adhesive layer forming step of forming the adhesive layer using the adhesive composition as described in the first or second aspect, and the adhesive layer formed through the adhesive layer forming step, and the support body and the above-mentioned adhesive layer are bonded together. The bonding step of the substrate.

A seventh aspect of the present invention is a method for producing an electronic component, characterized in that after the laminate is obtained by the method for producing a laminate as described in the sixth aspect, the method includes: A separation step of irradiating the separation layer with light to degrade the separation layer and separating the support substrate from the substrate included in the laminate; and, after the separation step, the adhesive layer attached to the substrate is Removal step of removal. [Effect of invention]

According to the present invention, there can be provided an adhesive composition, a support with an adhesive layer using the same, an adhesive film, a laminate, a method for producing the same, and a method for producing an electronic component, the adhesive composition for bonding the support and the substrate. The adhesive composition used can form an adhesive layer with higher heat resistance.

[The form of carrying out the invention]

In the present specification and the scope of the present invention, the term "aliphatic" is a relative concept to aromatic, and is defined to mean a group, a compound, or the like that does not have aromaticity. Unless otherwise specified, the "alkyl group" is regarded as including 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" is regarded as including a linear, branched, and cyclic divalent saturated hydrocarbon group. The "halogenated alkyl group" is a group in which a part or all of the hydrogen atoms of the alkyl group are substituted with a halogen atom, and the halogen atom includes a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. "Fluorinated alkyl group" or "fluorinated alkylene group" refers to a group in which part or all of the hydrogen atoms of an alkyl group or alkylene group are substituted with fluorine atoms. The "constituent unit" means a monomer unit constituting a polymer compound (resin, polymer, copolymer). When it is described as "may have a substituent" or "may have a substituent", both the case of substituting a hydrogen atom (-H) with a monovalent group and the case of substituting a methylene group (-CH ₂ -) with a divalent group are included. By. "Exposure" is regarded as a concept including the irradiation of the entirety of radiation.

The "constructive unit derived from hydroxystyrene" means a structural unit formed by cleavage of the ethylenic double bond of hydroxystyrene. The "constituent unit derived from a hydroxystyrene derivative" means a structural unit constituted by cleavage of the ethylenic double bond of the hydroxystyrene derivative. The so-called "hydroxystyrene derivatives" refers to the concept that the hydrogen atom at the a-position of hydroxystyrene is substituted with other substituents such as alkyl groups, halogenated alkyl groups, and their derivatives. As their derivatives, there may be mentioned hydroxystyrene in which the hydrogen atom of the a-position may be substituted by a substituent and the hydrogen atom of the hydroxyl group of hydroxystyrene substituted by an organic group; hydroxybenzene in which the hydrogen atom at the a-position may be substituted by a substituent On the benzene ring of vinyl, a substituent other than a hydroxyl group is bonded, etc. In addition, the so-called a-position (carbon atom at the a-position) refers to the carbon atom to which the benzene ring is bonded, unless otherwise specified. As the substituent which replaces the hydrogen atom at the a-position of hydroxystyrene, the same as those listed as the substituent at the a-position in the aforementioned α-substituted acrylate.

The alkyl group of the substituent at the a-position is preferably a straight-chain or branched-chain alkyl group, and specifically, an alkyl group having 1 to 5 carbon atoms (methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, isopentyl, neopentyl) and the like. In addition, the halogenated alkyl group as the substituent at the a-position specifically includes a group in which a part or all of the hydrogen atoms of the above-mentioned "alkyl group as the substituent at the α-position" are substituted with halogen atoms. As this halogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. are mentioned, A fluorine atom is especially preferable. In addition, the hydroxyalkyl group as the substituent at the a-position specifically includes a group in which a part or all of the hydrogen atoms of the above-mentioned "alkyl group as the substituent at the α-position" are substituted with a hydroxyl group. The number of hydroxyl groups in the hydroxyalkyl group is preferably 1 to 5, and most preferably 1.

(Adhesive composition (first aspect)) The adhesive composition of the first aspect of the present invention is used for bonding a support and a substrate. The adhesive composition of this embodiment contains a resin component (P). This resin component (P) contains at least a hydrocarbon resin (P1) and a resin (P2) having a glass transition temperature of 180° C. or higher (however, the aforementioned hydrocarbon resin (P1) is not included).

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

<Resin component (P)> In this embodiment, the resin component (P) (hereinafter also referred to as "(P) component") is in the adhesive composition, has a function as an adhesive imparting component, and contains at least The hydrocarbon resin (P1) and the resin (P2) having a glass transition temperature of 180° C. or higher (however, the aforementioned hydrocarbon resin (P1) is not included). The (P) component may contain resins other than these in addition to the aforementioned hydrocarbon resin (P1) and resin (P2). In addition, the resin component (P) in this embodiment contains, in addition to the resin, a monomer that can serve as a matrix constituting an adhesive layer, such as a curable monomer described later.

<<Hydrocarbon resin (P1)>> In the present embodiment, the hydrocarbon resin (P1) (hereinafter also referred to as "component (P1)") may be an aliphatic hydrocarbon resin or an aromatic hydrocarbon resin. As the component (P1), from the viewpoint of imparting heat resistance or flexibility, for example, elastomers and cycloolefin polymers can be mentioned.

・Elastomer The elastomer in the component (P1) can be suitably mentioned, for example, as a structural unit of the main chain, a structural unit derived from styrene or a structural unit derived from a styrene derivative (these are collectively referred to as "Styrene units").

The term "styrene derivative" as used herein refers to a concept that includes a hydrogen atom at the a-position of styrene substituted with other substituents such as an alkyl group and a halogenated alkyl group, and derivatives thereof. As such derivatives, there may be exemplified the benzene ring of styrene in which the hydrogen atom at the a-position may be substituted by a substituent, a substituent bonded thereto, and the like. The alkyl group of the substituent at the a-position is preferably a straight-chain or branched-chain alkyl group, and specifically, an alkyl group having 1 to 5 carbon atoms (methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, isopentyl, neopentyl) and the like. The halogenated alkyl group as the substituent at the a-position specifically includes a group in which a part or all of the hydrogen atoms of the "alkyl group as the substituent at the a-position" are substituted with halogen atoms. As this halogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. are mentioned, A fluorine atom is especially preferable. Examples of the substituent which can 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, and an ethyl group. Aryloxy, carboxyl, etc. In addition, the so-called a-position (carbon atom at the a-position) refers to the carbon atom to which the benzene ring is bonded unless otherwise specified. The so-called "structural units derived from styrene" and "structural units derived from styrene derivatives" refer to the structural units formed by cleavage of the ethylenic double bond of styrene or styrene derivatives.

Examples of the elastomer in the component (P1) include polystyrene-poly(ethylene/propylene) block copolymer (SEP) and styrene-isoprene-styrene block copolymer (SIS) , styrene-butadiene-styrene block copolymer (SBS), styrene-butadiene-butylene-styrene block copolymer (SBBS) or hydrogenated products of these; styrene-ethylene-butylene Styrene-styrene block copolymer (SEBS), styrene-ethylene-propylene-styrene block copolymer (styrene-isoprene-styrene block copolymer) (SEPS), styrene-ethylene- Ethylene-propylene-styrene block copolymer (SEEPS), styrene-ethylene-ethylene-propylene-styrene block copolymer whose styrene block is a reactive cross-linking type (Septon V9461 (manufactured by KURARAY Co., Ltd.), Septon V9475 (manufactured by KURARAY Co., Ltd.), styrene-ethylene-butylene-styrene block copolymer with reactive cross-linking type styrene block (reactive polystyrene-based hard block, Septon V9827 (Co., Ltd.) Company KURARAY system) and so on.

In the elastomer of the component (P1), the content of the styrene unit is preferably 10 to 70% by mass, more preferably 20 to 60% by mass, with respect to all the constituent units (100% by mass) constituting the elastomer, 25-50 mass % is especially preferable, and 30-45 mass % is especially preferable. When the content ratio of the styrene unit is not less than the lower limit of the above-mentioned preferred range, the adhesion or grindability between the support and the substrate is not lowered, and the procedures such as thinning and mounting are easy. If it is below the upper limit of the said preferable range, the chemical resistance of the adhesive layer formed of the adhesive composition can be suitably maintained.

The weight average molecular weight of the elastomer in the component (P1) is preferably in the range of 20,000 to 200,000, and more preferably in the range of 50,000 to 150,000. When the weight-average molecular weight of the elastomer is within the above-mentioned preferred range, an adhesive composition can be easily obtained which can form an adhesive layer that is easily dissolved in a hydrocarbon-based solvent and can be removed. In addition, since the weight average molecular weight of the elastomer is within the aforementioned preferable range, the chemical resistance of the adhesive layer formed of the adhesive composition increases.

The elastic system in the aforementioned (P1) component may be one type or two or more types.

Among the elastomers of the elastomeric system in the component (P1), hydrides are more preferable. When it is a hydride, the thermal stability is further improved, and deterioration such as decomposition and polymerization is less likely to occur. In addition, it is also more suitable from the viewpoint of solubility in hydrocarbon solvents and resistance to inhibitor solvents. In addition, among the elastomers, it is more preferable to use an end-capped polymer having styrene at both ends. Higher heat resistance is easily obtained by blocking both ends with styrene having high thermal stability. More specifically, the elastomer is preferably a hydrogenated product of a block copolymer of styrene and a conjugated diene. Thereby, the thermal stability is further improved, and deterioration such as decomposition or polymerization is less likely to occur. In addition, since both ends are blocked by styrene with high thermal stability, higher heat resistance is exhibited. Furthermore, it is also more preferable from the viewpoints of solubility in hydrocarbon solvents and resistance to inhibitor solvents.

Examples of commercially available elastomers that can be used as the component (P1) include “Septon (trade name)” manufactured by KURARAY Co., Ltd., “Hybrar (trade name)” manufactured by KURARAY Co., Ltd., and Asahi Kasei Co., Ltd. "Tuftec (trade name)" manufactured by a limited company, "Dynaron (trade name)" manufactured by JSR Co., Ltd., etc.

・Cycloolefin polymer Examples of the cycloolefin polymer include a ring-opening polymer containing a monomer component of a cycloolefin monomer, and an addition polymer obtained by addition-polymerizing a monomer component containing a cycloolefin monomer. .

Examples of the cycloolefin monomers include bicyclic bodies such as norbornene and norbornadiene, tricyclic bodies such as dicyclopentadiene and hydroxydicyclopentadiene, and tetracyclododecene. Pentacyclic bodies such as tetracyclic bodies and cyclopentadiene trimers, heptacyclic bodies such as tetracyclopentadiene, or alkyl groups (methyl, ethyl, propyl, butyl, etc.) of these polycyclic bodies ) substituents, alkenyl (vinyl, etc.) substituents, alkylene (ethylene, etc.) substituents, or aryl (phenyl, tolyl, naphthyl, etc.) substituents and other monomers.

Among the above, a polymer having a structural unit derived from a monomer having a norbornene structure selected from the group consisting of norbornene, tetracyclododecene, and alkyl substituents thereof is particularly preferred. By using the cycloolefin polymer having such a norbornene structure, for example, an adhesive composition can be easily obtained, which can be easily dissolved in a hydrocarbon solvent and can be removed while having high chemical resistance to the inhibitor solvent. the next layer.

The cycloolefin polymer may have a monomer copolymerizable with the aforementioned cycloolefin monomer as a monomer unit. As the copolymerizable monomer, for example, an alkene monomer can be suitably used. The alkene monomer system may be linear or branched, and examples thereof include alkene monomers having 2 to 10 carbon atoms, for example, ethylene, propylene, 1-butene, isobutylene, 1-butene are preferred. Among α-olefins such as hexene, it is more preferable to use ethylene as a monomer unit.

In the cycloolefin polymer of the component (P1), the content ratio of the cycloolefin monomer unit is preferably 10 to 100 mol% with respect to the total constituent units (100 mol%) constituting the cycloolefin polymer, More preferably, it is 20 to 100 mol %.

The weight average molecular weight of the cycloolefin polymer in the component (P1) is preferably in the range of 10,000 to 2,000,000, and more preferably in the range of 30,000 to 1,500,000. When the weight-average molecular weight of the cycloolefin polymer is equal to or greater than the lower limit of the above-mentioned preferred range, it is easy to control the softening temperature of the polymer to a temperature suitable for bonding the support to the substrate. If it is below the upper limit of the said preferable range, the adhesive agent composition which can form the adhesive layer which can be easily melt|dissolved in a hydrocarbon type solvent and can be removed can be obtained easily.

As for the cycloolefin polymer system in the said (P1) component, 1 type may be sufficient as it, and 2 or more types may be sufficient as it.

In addition, the cycloolefin polymer is, for example, a resin obtained by polymerizing a monomer component consisting of a cycloolefin monomer and an alkene monomer, and is a resin that does not have a polar group, and from the viewpoint of suppressing gas generation at high temperatures It looks better. There are no particular limitations on the polymerization method or polymerization conditions when the monomer components are polymerized, and they may be appropriately set according to conventional methods.

Examples of commercially available cycloolefin polymers that can be used as the component (P1) include "TOPAS (trade name)" manufactured by POLYPLASTICS Co., Ltd., "APEL (trade name)" manufactured by Mitsui Chemicals Co., Ltd., "ZEONOR (trade name)" manufactured by Japan ZEON Co., Ltd., "ZEONEX (trade name)" manufactured by Japan ZEON Co., Ltd., "ARTON (trade name)" manufactured by JSR Co., Ltd., etc.

In the adhesive composition of this embodiment, (P1) component may be used individually by 1 type, and may use 2 or more types together. The aforementioned (P1) component is preferably at least one selected from the group consisting of an elastomer and a cycloolefin polymer. Among these, an elastomer is more preferable in view of better heat resistance and die bondability.

The content ratio of the component (P1) occupied in the component (P) is preferably more than 50% by mass, more preferably more than 50% by mass and 90 mass % or less, especially 55 mass % or more and 80 mass % or less are preferable. By making it into the said preferable range, the removal performance of the cleaning liquid in the removal process mentioned later, especially a hydrocarbon-type solvent improves.

<<Resin (P2) with a Glass Transition Temperature of 180°C or More>> In this embodiment, the resin (P2) is a resin with a glass transition temperature (Tg) of 180°C or more (hereinafter also referred to as "(P2) component") ( However, the aforementioned hydrocarbon resin (P1)) is not included.

The glass transition temperature (Tg/°C) of the resin component can be determined by dynamic viscoelasticity measurement. For example, by using a dynamic viscoelasticity measuring device Rheologel-E4000 (manufactured by UBM Co., Ltd.), the temperature can be increased from 25°C to 300°C at a temperature increase rate of 5°C/min under the condition of a frequency of 1 Hz. The change in measured viscoelasticity was obtained.

The glass transition temperature (Tg) of the component (P2) is 180°C or higher, preferably 180 to 280°C, more preferably 200 to 280°C, particularly preferably 210 to 280°C, particularly preferably 220 to 280°C. If the Tg of the component (P2) is at least the lower limit value of the aforementioned range, an adhesive layer with higher heat resistance can be easily formed. If it is below the upper limit of the above-mentioned preferable range, it becomes easy to maintain the flexibility of the adhesive layer.

The (P2) component is not particularly limited as long as it is a resin having a Tg of 180° C. or higher, but it is preferably one having high compatibility with the above-mentioned (P1) component. For example, as the above-mentioned component (P2), a resin having a structural unit (u21) derived from a monomer containing a maleimide skeleton can be suitably used.

・Constitutional unit (u21) The constitutional unit (u21) is a constitutional unit derived from a monomer containing a maleimide skeleton. By using a resin having a maleimide skeleton, the glass transition temperature becomes higher, and the heat resistance of the adhesive layer becomes higher. As a preferable structural unit (u21), for example, the structural unit represented by the following general formula (p2-1) can be mentioned.

[式中，R^u10 表示碳數1～30的有機基]。

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

In the aforementioned formula (p2-1), R ^u10 represents an organic group having 1 to 30 carbon atoms. The organic group in R ^u10 may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group. The aliphatic hydrocarbon group means a hydrocarbon group having no aromaticity. In addition, the aliphatic hydrocarbon group may be saturated or unsaturated, but is usually preferably saturated. For example, as an organic group in R ^u10 , a cyclic group which may have a substituent, a chain alkyl group which may have a substituent, or a chain alkenyl group which may have a substituent is mentioned.

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

The aromatic hydrocarbon group in R ^u10 is a hydrocarbon group having an aromatic ring. The number of carbon atoms in the aromatic hydrocarbon group is preferably 3-30, more preferably 5-30, particularly preferably 5-20, particularly preferably 6-15, and most preferably 6-10. However, the carbon number in the substituent is not included in the carbon number. Specific examples of the aromatic ring contained in the aromatic hydrocarbon group in R ^u10 include benzene, fluoride, naphthalene, anthracene, phenanthrene, biphenyl, or those in which a part of carbon atoms constituting these aromatic rings is substituted with a heteroatom. Aromatic heterocycles, etc. As a hetero atom in an aromatic heterocyclic ring, an oxygen atom, a sulfur atom, a nitrogen atom, etc. are mentioned. Specific examples of the aromatic hydrocarbon group in R ^u10 include a group obtained by removing one hydrogen atom from the above-mentioned aromatic ring (aryl group: for example, a phenyl group, a naphthyl group, etc.), and one of the hydrogen atoms of the above-mentioned aromatic ring. Alkyl substituted groups (such as benzyl, phenethyl, 1-naphthylmethyl, 2-naphthylmethyl, 1-naphthylethyl, 2-naphthylethyl, etc. arylalkyl and many more. The number of carbon atoms in the alkylene group (the alkyl chain in the arylalkyl group) is preferably 1 to 4, more preferably 1 to 2, and particularly preferably 1.

The cyclic aliphatic hydrocarbon group in R ^u10 includes an aliphatic hydrocarbon group including a ring in the structure. Examples of the aliphatic hydrocarbon group including a ring in the structure include an alicyclic hydrocarbon group (a group obtained by removing one hydrogen atom from the aliphatic hydrocarbon ring), and one extended alkyl group of the hydrogen atom of the aliphatic hydrocarbon ring. Substituted base, etc. The number of carbon atoms in the alkylene group is preferably 1-4. The carbon number of the aliphatic hydrocarbon ring system is preferably 3-20, more preferably 3-12. The aforementioned aliphatic hydrocarbon ring system may be polycyclic or monocyclic. The monocyclic aliphatic hydrocarbon ring is preferably one having 3 to 8 carbon atoms, and specific examples thereof include cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, and cyclooctane. Preferred are cyclopentane and cyclohexane. The polycyclic aliphatic hydrocarbon ring is preferably one having 7 to 30 carbon atoms, more specifically, a bridge having a bridge such as adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane. Polycycloalkane of polycyclic skeleton of bicyclic system; polycycloalkane of polycyclic skeleton of polycyclic skeleton with condensed ring system, such as rings with steroid skeleton.

Among them, the cyclic aliphatic hydrocarbon group in R ^u10 is preferably a group obtained by removing one or more hydrogen atoms from a monocycloalkane or a polycycloalkane, more preferably one or more hydrogen atoms are removed from a monocycloalkane The group after the atom is preferably a group obtained by removing one hydrogen atom from a monocycloalkane, and particularly preferably a group obtained by removing one hydrogen atom from cyclopentane or cyclohexane.

As a substituent of the cyclic group of R ^u10 , an alkyl group, a halogen atom, a halogenated alkyl group, etc. are mentioned, for example. The alkyl group to be a substituent is preferably an alkyl group having 1 to 5 carbon atoms, and more preferably a methyl group, an ethyl group, a propyl group, an n-butyl group, and a tert-butyl group. As a halogen atom which becomes a substituent, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. are mentioned, Preferably it is a fluorine atom. Examples of the halogenated alkyl group to be a substituent include alkyl groups having 1 to 5 carbon atoms, for example, methyl, ethyl, propyl, n-butyl, tert-butyl, etc., where a part or all of the hydrogen atoms are substituted with the aforementioned halogens. The radical substituted by the atom.

Chain alkyl group which may have a substituent: As a chain alkyl group of R ^u10 , either straight chain or branched chain may be sufficient. As a linear alkyl group, 1-20 are preferable, 1-15 are more preferable, and 1-12 are especially preferable. Specifically, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, isodeca Three bases, fourteen bases, fifteen bases, sixteen bases, iso-sixteen bases, seventeen bases, eighteen bases, nineteen bases, twenty bases, twenty-one bases, twenty-two bases, etc. As a branched alkyl group, 3-20 are preferable, 3-15 are more preferable, and 3-10 are especially preferable. Specifically, 1-methylethyl, 1-methylpropyl, 2-methylpropyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1-methylbutyl, -Ethylbutyl, 2-ethylbutyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, etc.

Chain alkenyl group which may have a substituent: The chain alkenyl group of R ^u10 may be either linear or branched, preferably having 2 to 10 carbon atoms, more preferably having 2 to 5 carbon atoms , particularly preferably carbon number 2 to 4, particularly preferably carbon number 3. As a linear alkenyl group, a vinyl group, a propenyl group (allyl group), a butynyl group, etc. are mentioned, for example. As a branched alkenyl group, a 1-methylvinyl group, a 2-methylvinyl group, a 1-methacryl group, a 2-methacryl group, etc. are mentioned, for example. Among the above-mentioned chain alkenyl groups, linear alkenyl groups are preferred, vinyl groups and propenyl groups are more preferred, and vinyl groups are particularly preferred.

As a substituent of the chain-like alkyl group or alkenyl group of R ^u10 , for example, a halogen atom, a halogenated alkyl group, a cyclic group in the above-mentioned R ^u10 , etc. are mentioned.

Among the above, R ^u10 is preferably a cyclic group which may have a substituent, more preferably a cyclic hydrocarbon group which may have a substituent, and particularly preferably a cyclic aliphatic hydrocarbon group which may have a substituent.

Below, the specific example of a structural unit (u21) is shown.

The structural unit (u21) which the component (P2) has may be one type or two or more types. The ratio of the structural unit (u21) in the (P2) component is preferably 10 to 90 mol %, more preferably 20 to 80 mol %, relative to the total (100 mol %) of all the structural units constituting the (P2) component. Ear%, preferably 40 to 70 mole%. When the ratio of the structural unit (u21) is more than the lower limit value of the above-mentioned preferable range, the glass transition temperature becomes high, and the heat resistance of the adhesive layer becomes high. If it is below the upper limit of the said preferable range, it will be easy to achieve balance with other structural units.

・Constituent unit (u22) As the component (P2), it may have a structural unit other than the above-mentioned structural unit (u21). As a structural unit other than the above-mentioned structural unit (u21), for example, a structural unit (u22) derived from a cycloolefin can be mentioned. By using a cyclic olefin, that is, a resin having an unsaturated aliphatic hydrocarbon ring composed of carbon atoms, an adhesive composition can be easily obtained, which can form an adhesive layer that is easily dissolved in a hydrocarbon solvent and removed.

As a preferable structural unit (u22), the structural unit represented by the following general formula (p2-2) is mentioned, for example.

[式中，R^u11 ～R^u14 各自獨立地表示碳數1～30的有機基或氫原子；n為0～2之整數]。

[In the formula, R ^u11 to R ^u14 each independently represent an organic group or a hydrogen atom having 1 to 30 carbon atoms; n is an integer of 0 to 2].

In the aforementioned formula (p2-2), examples of the organic group in R ^u11 to R ^u14 include an alkyl group, an alkenyl group, an alkynyl group, an alkylene group, an aryl group, an aralkyl group, an alkaryl group, and a cycloalkane group. group, an organic group having a carboxyl group, and an organic group having a heterocyclic ring. The alkyl group in R ^u11 to R ^u14 is preferably an alkyl group having 1 to 10 carbon atoms, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, th Dibutyl, tert-butyl, pentyl, neopentyl, hexyl, heptyl, octyl, nonyl, decyl. Examples of the alkenyl group in R ^u11 to R ^u14 include an allyl group, a pentenyl group, and a vinyl group. As an alkynyl group in R ^u11 - R ^u14 , an ethynyl group is mentioned, for example. Examples of the alkylene group in R ^u11 to R ^u14 include a methylene group and an ethylene group. Examples of the aryl group in R ^u11 to R ^u14 include a phenyl group, a naphthyl group, and an anthracenyl group. Examples of the aralkyl group in R ^u11 to R ^u14 include a benzyl group and a phenethyl group. Examples of the alkaryl group in R ^u11 to R ^u14 include a tolyl group and a xylyl group. Examples of the cycloalkyl group in R ^u11 to R ^u14 include an adamantyl group, a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group. As an organic group which has a heterocyclic ring among R ^u11 - R ^u14 , the organic group which has an epoxy group, and the organic group which has an oxetanyl group is mentioned, for example.

The organic group in R ^u11 to R ^u14 is preferably an alkyl group from the viewpoints of further improving solubility in a hydrocarbon-based solvent and synthesis. Further, from the viewpoint of easily maintaining a high glass transition, an alkyl group having 1 to 8 carbon atoms is more preferred, and an alkyl group having 2 to 6 carbon atoms is particularly preferred. Moreover, from the viewpoint of improving the light transmittance of the adhesive layer formed using the adhesive composition, it is also preferable that any one or more of R ^u11 to R ^u14 is a hydrogen atom. Among the above, the organic group in R ^u11 to R ^u14 is preferably a combination of an alkyl group and a hydrogen atom, preferably any one of R ^u11 to R ^u14 is an alkyl group, and the remaining three are hydrogen atoms.

The organic groups in R ^u11 to R ^u14 may be substituted with one or more hydrogen atoms by halogen atoms. As this halogen atom, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned.

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

Below, the specific example of a structural unit (u22) is shown.

The structural unit (u22) which the component (P2) has may be one type or two or more types. The ratio of the structural unit (u22) in the (P2) component is preferably 10 to 90 mol %, more preferably 20 to 80 mol %, relative to the total (100 mol %) of all the structural units constituting the (P2) component. Ear%, preferably 30 to 60 mole%. When the ratio of the structural unit (u22) is equal to or more than the lower limit value of the above-mentioned preferable range, the solubility in the hydrocarbon-based solvent tends to be high. If it is below the upper limit of the said preferable range, it will be easy to achieve balance with other structural units.

In the adhesive composition of this embodiment, (P2) component may be used individually by 1 type, and may use 2 or more types together. The aforementioned (P2) component is preferably a resin having a structural unit (u21). Among them, resins having a structural unit (u21) and a structural unit (u22) are preferred in view of the ease of improvement in heat resistance and the ease of obtaining an adhesive composition capable of forming an adhesive layer that is easily dissolved in a hydrocarbon-based solvent and removed. .

Below, the specific example of (P2) component is shown.

The content ratio of the aforementioned (P2) component in the aforementioned (P) component is preferably 50 mass % or less, more preferably 5 mass % or more and 50 mass % or less, especially 10 mass % or more and 40 mass % or less are preferable.

Moreover, with respect to 100 parts by mass of the component (P1), the content of the component (P2) is preferably 5 to 75 parts by mass, more preferably 10 to 70 parts by mass, particularly preferably 10 to 65 parts by mass, particularly preferably It is 10-60 mass parts. When the content ratio of the said (P2) component is below the upper limit of the said preferable range, not only heat resistance but also adhesiveness will further improve. If it is more than the lower limit of the said preferable range, heat resistance, adhesiveness, and die bondability will all improve.

<<Other Resins (P3)>> The (P) component may contain resins other than the above (P1) and (P2) components (hereinafter also referred to as "(P3) components"). For example, as the component (P3), acrylic resins and the like can be mentioned.

・Acrylic resin In this embodiment, the (P) component may contain an acrylic resin as the (P3) component in addition to the aforementioned (P1) and (P2) components. Since (P) component contains an acrylic resin, the adhesiveness of a support body and a board|substrate can be improved more. Examples of acrylic resins include resins (homopolymers, copolymers) polymerized using (meth)acrylates as monomers. The so-called "(meth)acrylic acid" means at least one of acrylic acid or methacrylic acid.

Examples of (meth)acrylates include alkyl (meth)acrylates having a chain structure, (meth)acrylates having an aliphatic ring, and (meth)acrylates having an aromatic ring. . Among these, it is preferable to use the (meth)acrylate which has an aliphatic ring.

As an alkyl (meth)acrylate which consists of a chain structure, the acrylic alkyl ester which has a C1-C20 alkyl group is mentioned, for example. The alkyl group with 1 to 20 carbon atoms mentioned here can be linear or branched, such as methyl, ethyl, propyl, butyl, 2-ethylhexyl, isooctyl, isononyl, Isodecyl group, dodecyl group, lauryl group, tridecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group (stearyl group), n-nineteen group, n-twenty group, etc. , preferably an acrylic alkyl ester having an alkyl group having 15 to 20 carbon atoms.

Examples of (meth)acrylates having an aliphatic ring include cyclohexyl (meth)acrylate, cyclopentyl (meth)acrylate, 1-adamantyl (meth)acrylate, and (meth)acrylates. Norbornyl acrylate, isobornyl (meth)acrylate, tricyclodecyl (meth)acrylate, tetracyclododecyl (meth)acrylate, dicyclopentyl (meth)acrylate, etc. Among these, 1-adamantyl (meth)acrylate, isobornyl (meth)acrylate, and dicyclopentyl (meth)acrylate are preferred.

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

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

The acrylic resin is preferably selected from the group consisting of alkyl (meth)acrylates having a chain structure, (meth)acrylates having an aliphatic ring, and (meth)acrylates having an aromatic ring One or more of these resins are polymerized. Among them, preferred are resins obtained by polymerizing alkyl (meth)acrylate and (meth)acrylate having an aliphatic ring.

Acrylic resins can also be resins obtained by polymerizing (meth)acrylate monomers with other monomers that can be polymerized with them. Examples of the polymerizable monomers include styrene, styrene derivatives, and maleimide group-containing monomers. The styrene derivative here is the same as the above-mentioned "styrene derivative". The monomer system containing a maleimide group here is the same as the monomer from which the above-mentioned structural unit (u21) is derived.

Moreover, among the acrylic resins, those obtained by polymerizing a (meth)acrylate monomer and styrene are preferable. Since the acrylic resin has styrene units, the heat resistance of the acrylic resin increases. In addition, compatibility with other resins and solubility in hydrocarbon-based solvents increase. Among them, the acrylic resin is particularly preferably a resin obtained by polymerizing an alkyl (meth)acrylate having a chain structure, a (meth)acrylate having an aliphatic ring, and styrene.

The solubility parameter (SP value) of the acrylic resin is preferably 6 or more and 10 or less, more preferably 6.5 or more and 9.5 or less. Since the SP value is within the aforementioned preferable range, the compatibility of the acrylic resin with other resins can be improved, and a more stable adhesive composition can be easily obtained.

The weight average molecular weight of the acrylic resin is preferably 2,000 to 100,000, more preferably 5,000 to 50,000. Since the weight-average molecular weight of the acrylic resin is within the aforementioned preferred range, for example, an adhesive composition can be easily provided, which has thermal fluidity suitable for the bonding of the substrate and the support.

Acrylic resins may be used in combination of two or more. The content ratio of the aforementioned acrylic resin in the aforementioned (P) component is preferably 30 mass % or less, more preferably 25 mass % or less, particularly preferably 30 mass % or less with respect to the total amount (100 mass %) of the aforementioned (P) component It exceeds 0 mass % and is 20 mass % or less.

・Curable monomer In this embodiment, the (P) component includes the aforementioned (P1) component and (P2) component, and the adhesive composition may include a curable monomer as the (P3) component. Since the adhesive composition contains the curable monomer, the heat resistance of the adhesive layer can be further improved. The curable monomer is preferably a monomer that is polymerized by radical polymerization, typically a polyfunctional curable monomer, and particularly preferably a polyfunctional (meth)acrylate monomer.

Examples of polyfunctional (meth)acrylate monomers include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, and tetraethylene glycol di(meth)acrylate. Acrylates, propylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, butanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexane Diol di(meth)acrylate, 1,4-cyclohexanedimethanol di(meth)acrylate, tricyclodecanedimethanol di(meth)acrylate, 9,9-bis[4-( 2-(meth)acryloyloxyethoxy)phenyl] stilbene, propoxylated bisphenol A di(meth)acrylate, 1,3-adamantanediol di(meth)acrylate, 5-Hydroxy-1,3-adamantanediol di(meth)acrylate, 1,3,5-adamantanetriol tri(meth)acrylate, trimethylolpropane tri(meth)acrylate , glycerol di(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa (Meth)acrylate, 2-hydroxy-3-(meth)acryloyloxypropyl (meth)acrylate, ethylene glycol diglycidyl ether di(meth)acrylate, diethylene glycol Alcohol Diglycidyl Ether Di(meth)acrylate, Diglycidyl Phthalate Di(meth)acrylate, Glycerol Tri(meth)acrylate, Glycerin Polyglycidyl Ether Polyester (Meth)acrylates, urethane (meth)acrylates (ie, toluene diisocyanate), trimethylhexamethylene diisocyanate and hexamethylene diisocyanate and (meth)acrylic acid 2- The reactant of hydroxyethyl ester, etc.

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

Among the curable monomers, (meth)acrylate monomers having a cyclic group are particularly preferred, and more preferred are selected from tricyclodecane dimethanol di(meth)acrylate, 1,3-adamantine Alkanediol di(meth)acrylate, 5-hydroxy-1,3-adamantanediol di(meth)acrylate, 1,3,5-adamantanetriol tri(meth)acrylate, 1 ,4-Cyclohexanedimethanol di(meth)acrylate, 9,9-bis[4-(2-(meth)acrylooxyethoxy)phenyl]pyridine and propoxylated bisphenol At least one of the group consisting of A di(meth)acrylate, particularly preferably tricyclodecane dimethanol di(meth)acrylate.

The content ratio of the aforementioned curable monomer in the aforementioned (P) component is preferably 5 to 40 mass %, more preferably 5 to 30 mass % with respect to the total amount (100 mass %) of the aforementioned (P) component , particularly preferably 5 to 20 mass %. In addition, when further improvement of the adhesiveness is required for the adhesive composition, the content ratio of the curable monomer occupied in the component (P) with respect to the total amount (100% by mass) of the component (P) is also Numerical ranges of 1 to 30 mass %, 2 to 20 mass %, and 5 to 15 mass % can be set.

In addition, the content ratio of the aforementioned curable monomer is preferably 5 to 40 parts by mass, more preferably 5 to 30 parts by mass, particularly preferably 100 parts by mass of the total of the aforementioned (P1) component and the aforementioned (P2) component. It is 5-20 mass parts. Higher heat resistance can be imparted to the adhesive layer when the content ratio of the curable monomer is more than the lower limit value of the preferred range described above. If it is below the upper limit of the said preferable range, the solubility with respect to a hydrocarbon-type solvent can be improved more, and the cleaning removability of an adhesive layer can be made more favorable.

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

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

<<Polymerization inhibitor>> The adhesive composition of the present embodiment may further contain a polymerization inhibitor. A polymerization inhibitor refers to a component having a function of preventing radical polymerization caused by heat or light. Polymerization inhibitors show high reactivity towards free radicals. Therefore, for example, when a cycloolefin polymer is used as the component (P1), the reaction between the polymerization inhibitor and the radical proceeds more preferentially than the reaction between the cycloolefin polymer and the radical, and the polymerization of the cycloolefin polymers is suppressed. Thereby, the chemical resistance of the adhesive layer can be improved by heating the adhesive layer formed.

As a polymerization inhibitor, what has a phenol skeleton is preferable. For example, as the polymerization inhibitor, a hindered phenol-based antioxidant can be used, and examples thereof include pyrogallol, benzoquinone, hydroquinone, methylene blue, tert-butylcatechol, monobenzyl ether, methyl Hydroquinone, pentylquinone, pentyloxyhydroquinone, n-butylphenol, phenol, hydroquinone monopropyl ether, 4,4'-(1-methylethylene)bis(2-methylphenol), 4,4'-(1-Methylethylene)bis(2,6-dimethylphenol), 4,4'-[1-[4-(1-(4-hydroxyphenyl)-1- Methylethyl)phenyl]ethylene]bisphenol, 4,4',4"-ethylenetris(2-methylphenol), 4,4',4"-ethylenetriphenol, 1 ,1,3-Tris(2,5-dimethyl-4-hydroxyphenyl)-3-phenylpropane, 2,6-di-tert-butyl-4-methylphenol, 2,2'-diphenylene Methylbis(4-methyl-6-tert-butylphenol), 4,4'-butylenebis(3-methyl-6-tert-butylphenol), 4,4'-thiobis( 3-Methyl-6-tert-butylphenol), 3,9-bis[2-(3-(3-tert-butyl-4-hydroxy-5-methylphenyl)-propionyloxy) -1,1-Dimethylethyl]-2,4,8,10-tetraoxaspiro(5,5)undecane, triethylene glycol-bis-3-(3-tert-butyl- 4-Hydroxy-5-methylphenyl) propionate, n-octyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate, pentaerythritol tetrakis[3-(3, 5-di-tert-butyl-4-hydroxyphenyl) propionate] (trade name IRGANOX1010, manufactured by BASF), tris(3,5-di-tert-butylhydroxybenzyl) isocyanurate, Thiodieneethylbis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] and the like.

A polymerization inhibitor system may be used individually by 1 type, and may be used in combination of 2 or more types. The content of the polymerization inhibitor can be appropriately determined according to the type of resin component, the application of the adhesive composition and the use environment, for example, it is preferably 0.1 to 10 parts by mass relative to 100 parts by mass of the (P) component. If the content of the polymerization inhibitor is within the above-mentioned preferred range, the effect of inhibiting the polymerization can be well exerted, and the chemical resistance of the adhesive layer can be further improved after the high temperature process.

<<Polymerization Initiator>> The adhesive composition of the present embodiment may further contain a polymerization initiator. The polymerization initiator refers to a component having the function of promoting the polymerization reaction of the above-mentioned curable monomer. As the polymerization initiator, a thermal polymerization initiator, a photopolymerization initiator, and the like can be mentioned. As the thermal polymerization initiator, for example, peroxides, azo-based polymerization initiators, and the like can be mentioned.

As a peroxide in a thermal polymerization initiator, a ketone peroxide, a peroxyketal, a hydroperoxide, a dialkyl peroxide, a peroxyester etc. are mentioned, for example. Specific examples of such peroxides include acetyl peroxide, dicumyl peroxide, tert-butyl peroxide, tert-butyl cumyl peroxide, and propyl peroxide. , Benzyl peroxide (BPO), 2-chlorobenzyl peroxide, 3-chlorobenzyl peroxide, 4-chlorobenzyl peroxide, 2,4-dichlorobenzene peroxide Carboxylic, 4-bromomethylbenzyl peroxide, lauryl peroxide, potassium persulfate, diisopropyl peroxycarbonate, tetrahydronaphthalene hydroperoxide, 1-phenyl-2-methyl propylpropyl-1-hydroperoxide, 3-butyl pertriphenylacetate, 3-butyl hydroperoxide, 3-butyl performate, 3-butyl peracetate, 3-butyl perbenzoate ester, 3-butyl perphenylacetate, 3-butyl per-4-methoxyacetate, 3-butyl per-N-(3-tolyl)carbamate, etc.

Among the aforementioned peroxides, for example, trade names "Percumyl (registered trademark)", trade names "Perbutyl (registered trademark)", trade names "Peroyl (registered trademark)" and trade names manufactured by NOF Corporation can be used. Commercially available such as "Perocta (registered trademark)".

As the azo-based polymerization initiator among the thermal polymerization initiators, for example, 2,2'-azobispropane, 2,2'-dichloro-2,2'-azobispropane, 1,2'-azobispropane, 1'-Azo(methylethyl)diacetate, 2,2'-azobis(2-carboxamidinopropane) hydrochloride, 2,2'-azobis(2-aminopropane) ) nitrate, 2,2'-azobisisobutane, 2,2'-azobisisobutylamide, 2,2'-azobisisobutyronitrile, 2,2'-azobisisobutyronitrile -Methyl 2-methylpropionate, 2,2'-dichloro-2,2'-azobisbutane, 2,2'-azobis-2-methylbutyronitrile, 2,2'- Dimethyl azobisisobutyrate, 1,1'-azobis(1-methylbutyronitrile-3-sodium sulfonate), 2-(4-methylphenylazo)-2-methyl Malononitrile 4,4'-azobis-4-cyanovaleric acid, 3,5-dihydroxymethylphenylazo-2-allylmalononitrile, 2,2'-azobis- 2-Methylvaleronitrile, Dimethyl 4,4'-azobis-4-cyanovalerate, 2,2'-azobis-2,4-dimethylvaleronitrile, 1,1'- Azobiscyclohexanenitrile, 2,2'-azobis-2-propylbutyronitrile, 1,1'-azobiscyclohexanenitrile, 2,2'-azobis-2-propylbutyronitrile , 1,1'-azobis-1-chlorophenylethane, 1,1'-azobis-1-cyclohexanecarbonitrile, 1,1'-azobis-1-cycloheptanecarbonitrile , 1,1'-azobis-1-phenylethane, 1,1'-azobismethane, ethyl 4-nitrophenylazobenzylcyanoacetate, phenylazodiphenyl Methane, phenylazotriphenylmethane, 4-nitrophenylazotriphenylmethane, 1,1'-azobis-1,2-diphenylethane, poly(bisphenol A-4 , 4'-azobis-4-cyanovalerate), poly(tetraethylene glycol-2,2'-azobisisobutyrate), etc.

唑、2-巰基苯并噻唑、2-(鄰氯苯基)-4,5-二苯基咪唑二聚物、2-(鄰氯苯基)-4,5-二(甲氧基苯基)咪唑二聚物、2-(鄰氟苯基)-4,5-二苯基咪唑二聚物、2-(鄰甲氧基苯基)-4,5-二苯基咪唑二聚物、2-(對甲氧基苯基)-4,5-二苯基咪唑二聚物、2,4,5-三芳基咪唑二聚物、二苯基酮、2-氯二苯基酮、4,4’-雙二甲基胺基二苯基酮(即，米其勒酮)、4,4’-雙二乙基胺基二苯基酮(即，乙基米其勒酮)、4,4’-二氯二苯基酮、3,3-二甲基-4-甲氧基二苯基酮、二苯乙二酮、苯偶姻、苯偶姻甲基醚、苯偶姻乙基醚、苯偶姻異丙基醚、苯偶姻正丁基醚、苯偶姻異丁基醚、苯偶姻第三丁基醚、苯乙酮、2,2-二乙氧基苯乙酮、對二甲基苯乙酮、對二甲基胺基苯丙酮、二氯苯乙酮、三氯苯乙酮、對第三丁基苯乙酮、對二甲基胺基苯乙酮、對第三丁基三氯苯乙酮、對第三丁基二氯苯乙酮、a,a-二氯-4-苯氧基苯乙酮、噻噸酮、2-甲基噻噸酮、2-異丙基噻噸酮、二苯并環庚酮、戊基-4-二甲基胺基苯甲酸酯、9-苯基吖啶、1,7-雙-(9-吖啶基)庚烷、1,5-雙-(9-吖啶基)戊烷、1,3-雙-(9-吖啶基)丙烷、對甲氧基三

、2,4,6-三(三氯甲基)-s-三

、2-甲基-4,6-雙(三氯甲基)-s-三

、2-[2-(5-甲基呋喃-2-基)乙烯基]-4,6-雙(三氯甲基)-s-三

、2-[2-(呋喃-2-基)乙烯基]-4,6-雙(三氯甲基)-s-三

、2-[2-(4-二乙基胺基-2-甲基苯基)乙烯基]-4,6-雙(三氯甲基)-s-三

、2-[2-(3,4-二甲氧基苯基)乙烯基]-4,6-雙(三氯甲基)-s-三

、2-(4-甲氧基苯基)-4,6-雙(三氯甲基)-s-三

、2-(4-乙氧基苯乙烯基)-4,6-雙(三氯甲基)-s-三

、2-(4-正丁氧基苯基)-4,6-雙(三氯甲基)-s-三

、2,4-雙-三氯甲基-6-(3-溴-4-甲氧基)苯基-s-三

、2,4-雙-三氯甲基-6-(2-溴-4-甲氧基)苯基-s-三

、2,4-雙-三氯甲基-6-(3-溴-4-甲氧基)苯乙烯基苯基-s-三

、2,4-雙-三氯甲基-6-(2-溴-4-甲氧基)苯乙烯基苯基-s-三

等。Examples of the photopolymerization initiator include 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-[4-(2-hydroxyethoxy base)phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 1 -(4-Dodecylphenyl)-2-hydroxy-2-methylpropan-1-one, 2,2-dimethoxy-1,2-diphenylethan-1-one, bis( 4-Dimethylaminophenyl) ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-di Methylamino-1-(4-morpholinylphenyl)-butan-1-one, ethanone 1-[9-ethyl-6-(2-methylbenzyl)-9H-carbo Azol-3-yl]-1-(o-acetyloxime), 2,4,6-trimethylbenzyldiphenylphosphine oxide, 4-benzyl-4'-methyldiphenyl Methyl sulfide, 4-dimethylaminobenzoic acid, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, butyl 4-dimethylaminobenzoate , 4-dimethylamino-2-ethylhexyl benzoic acid, 4-dimethylamino-2-isoamyl benzoic acid, benzyl-β-methoxyethyl acetal, benzyl dimethyl acetal ketal, 1-phenyl-1,2-propanedione-2-(o-ethoxycarbonyl) oxime, methyl o-benzylbenzoate, 2,4-diethylthioxanthone, 2 -Chlorthioxanthene, 2,4-Dimethylthioxanthene, 1-Chloro-4-propoxythioxanthene, thioxanthene, 2-chlorothioxanthene, 2,4-diethylthioxanthene, 2 -Methylthioxanthene, 2-isopropylthioxanthene, 2-ethylanthraquinone, octamethylanthraquinone, 1,2-benzoanthraquinone, 2,3-diphenylanthraquinone, azobisisoquinone Nitrile, benzyl peroxide, cumene peroxide, 2-mercaptobenzimidazole, 2-mercaptobenzo

azole, 2-mercaptobenzothiazole, 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer, 2-(o-chlorophenyl)-4,5-bis(methoxyphenyl) ) imidazole dimer, 2-(o-fluorophenyl)-4,5-diphenylimidazole dimer, 2-(o-methoxyphenyl)-4,5-diphenylimidazole dimer, 2-(p-methoxyphenyl)-4,5-diphenylimidazole dimer, 2,4,5-triarylimidazole dimer, diphenyl ketone, 2-chlorodiphenyl ketone, 4 ,4'-bisdimethylamino diphenyl ketone (ie, Michler's ketone), 4,4'-bis-diethylamino diphenyl ketone (ie, ethyl Michler's ketone), 4 ,4'-Dichlorodiphenyl ketone, 3,3-dimethyl-4-methoxydiphenyl ketone, benzoin, benzoin, benzoin methyl ether, benzoin ethyl Base ether, benzoin isopropyl ether, benzoin n-butyl ether, benzoin isobutyl ether, benzoin tert-butyl ether, acetophenone, 2,2-diethoxyphenethyl Ketone, p-dimethylacetophenone, p-dimethylaminoacetophenone, dichloroacetophenone, trichloroacetophenone, p-tert-butylacetophenone, p-dimethylaminoacetophenone, p-tert-butyltrichloroacetophenone, p-tert-butyldichloroacetophenone, a,a-dichloro-4-phenoxyacetophenone, thioxanthone, 2-methylthioxanthone, 2-Isopropylthioxanthone, dibenzocycloheptanone, pentyl-4-dimethylaminobenzoate, 9-phenylacridine, 1,7-bis-(9-acridinyl ) heptane, 1,5-bis-(9-acridinyl)pentane, 1,3-bis-(9-acridinyl)propane, p-methoxytri

, 2,4,6-tris(trichloromethyl)-s-tris

, 2-methyl-4,6-bis(trichloromethyl)-s-tri

, 2-[2-(5-methylfuran-2-yl)vinyl]-4,6-bis(trichloromethyl)-s-tri

, 2-[2-(furan-2-yl)ethenyl]-4,6-bis(trichloromethyl)-s-tri

, 2-[2-(4-diethylamino-2-methylphenyl)vinyl]-4,6-bis(trichloromethyl)-s-tri

, 2-[2-(3,4-dimethoxyphenyl)vinyl]-4,6-bis(trichloromethyl)-s-tri

, 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-s-tri

, 2-(4-ethoxystyryl)-4,6-bis(trichloromethyl)-s-tri

, 2-(4-n-butoxyphenyl)-4,6-bis(trichloromethyl)-s-tri

, 2,4-bis-trichloromethyl-6-(3-bromo-4-methoxy)phenyl-s-tri

, 2,4-bis-trichloromethyl-6-(2-bromo-4-methoxy)phenyl-s-tri

, 2,4-bis-trichloromethyl-6-(3-bromo-4-methoxy)styrylphenyl-s-tri

, 2,4-bis-trichloromethyl-6-(2-bromo-4-methoxy)styrylphenyl-s-tri

Wait.

Among the aforementioned photopolymerization initiators, for example, "IRGACURE OXE02", "IRGACURE OXE01", "IRGACURE 369", "IRGACURE 651", "IRGACURE 907" (all trade names, manufactured by BASF Corporation) and "NCI- 831" (trade name, manufactured by ADEKA Co., Ltd.), etc.

A polymerization initiator system may be used individually by 1 type, and may be used in combination of 2 or more types. As the polymerization initiator, a thermal polymerization initiator is preferable, and a peroxide is more preferable. The polymerization initiator should be used in combination with the sclerosing monomer. The usage amount of the polymerization initiator should be adjusted according to the usage amount of the curable monomer. For example, in the adhesive composition of the present embodiment, the content ratio of the polymerization initiator is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 5 parts by mass, relative to 100 parts by mass of the curable monomer.

<<Solvent Component>> The adhesive composition of the present embodiment can be prepared by dissolving the (P) component and optional components in a solvent component. Among the solvent components, for example, one that can dissolve each component for the adhesive composition to form a uniform solution can be used alone or in combination of two or more.

As a solvent component, a hydrocarbon solvent and a petroleum-based solvent are mentioned, for example. In addition, hydrocarbon solvents and petroleum-based solvents are collectively referred to as "(S1) components" below. The solvent components other than the component (S1) are also referred to as "component (S2)".

Examples of the hydrocarbon solvent include linear, branched, or cyclic hydrocarbons, and examples thereof include hexane, heptane, octane, nonane, methyloctane, decane, undecane, and dodecane. , straight chain hydrocarbons such as tridecane; branched chain hydrocarbons such as isooctane, isononane, isododecane; 4-terpine, 1,8-terpine, campane, norbornane, pinane, thujyl, carane, longifene, a-terpinene, beta-terpinene, g-terpinene , α-pinene, β-pinene, α-thujone, β-thujone, cyclohexane, cycloheptane, cyclooctane, indene, pentylene, indane, tetrahydroindene, naphthalene, Cyclic hydrocarbons such as tetralin and decalin.

The so-called petroleum-based solvent is a solvent purified from heavy oil, and examples thereof include kerosene, paraffin-based solvent, and isoparaffin-based solvent.

Moreover, as (S2) component, the terpene solvent which has polar groups, such as oxygen atom, carbonyl group, acetyloxy group, etc., is mentioned, for example, geraniol, nerol, linalool, citral, citronella are mentioned, for example alcohol, menthol, isomenthol, neomenthol, a-terpineol, beta-terpineol, g-terpineol, terpinen-1-ol, terpinen-4-ol, dihydroacetate Terpineol, 1,4-cineole, 1,8-cineole, borneol, carvone, ionone, thujone, camphor, etc.

烷的環式醚類；乳酸甲酯、乳酸乙酯、醋酸甲酯、醋酸乙酯、醋酸丁酯、丙酮酸甲酯、丙酮酸乙酯、甲氧基丙酸甲酯、乙氧基丙酸乙酯等之酯類；苯甲醚、乙基苄基醚、甲苯酚基甲基醚、二苯基醚、二苄基醚、苯乙醚、丁基苯基醚等之芳香族系有機溶劑。In addition, as the component (S2), lactones such as g-butyrolactone; acetone, methyl ethyl ketone, cyclohexanone (CH), methyl n-amyl ketone, methyl isoamyl ketone can also be mentioned Ketones, 2-heptanone, etc.; ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, etc. polyols; ethylene glycol monoacetate, diethylene glycol monoacetate, propylene glycol monoethyl Compounds having ester bonds such as acid esters or dipropylene glycol monoacetate, monomethyl ethers, monoethyl ethers, monopropyl ethers, monobutyl ethers, etc. of the above polyols or the above compounds having ester bonds Derivatives of polyols such as compounds having ether bonds such as monoalkyl ethers or monophenyl ethers (among these, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ethers are preferred ether (PGME)); such as two

Cyclic ethers of alkanes; methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, ethoxypropionic acid Esters such as ethyl esters; aromatic organic solvents such as anisole, ethylbenzyl ether, cresyl methyl ether, diphenyl ether, dibenzyl ether, phenethyl ether, butyl phenyl ether, etc.

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. ~90% by mass. That is, the concentration of the solid content (the total amount of the compounded components other than the solvent component) in the adhesive composition of the present embodiment is preferably in the range of 10 to 80% by mass. When the content of the solvent component is within the aforementioned preferable range, the viscosity adjustment becomes easy.

As the adhesive composition of the present embodiment, the following compositions (I) to (III) can be preferably mentioned specifically. Composition (I): a composition containing (P1) components, (P2) components, a polymerization inhibitor and a solvent component Composition (II): (P1) components, (P2) components, curable monomers, polymerization initiator Composition of starter and solvent component Composition (III): a composition containing (P1) component, (P2) component, (P3) component, polymerization inhibitor and solvent component

The adhesive composition of the present embodiment can be prepared by mixing other components in a solvent component, and dissolving or dispersing it. Among the solvent components, from the viewpoint of the solubility of the (P) component, those containing a hydrocarbon solvent are preferably used, and those containing a branched chain hydrocarbon or a cyclic hydrocarbon solvent are more preferably used. Since the solvent component contains a branched or cyclic hydrocarbon solvent, it is easy to prevent white turbidity that may occur when the adhesive composition is stored in a liquid state (especially at low temperature), and the storage stability can be further improved.

Moreover, as a solvent component, it is preferable to use what contains a condensed polycyclic hydrocarbon or a branched-chain hydrocarbon as a hydrocarbon solvent. In this case, the solvent component may be selected only from the group consisting of condensed polycyclic hydrocarbons and branched chain hydrocarbons, and may also contain other components such as saturated aliphatic hydrocarbons. The content of the solvent component selected from the group consisting of condensed polycyclic hydrocarbons and branched chain hydrocarbons is preferably 40 parts by mass or more, more preferably 60 parts by mass or more with respect to 100 parts by mass of the entire hydrocarbon solvent , particularly preferably 80 parts by mass or more. When it is 40 mass parts or more of the whole hydrocarbon solvent, the solubility of (P)component will become favorable.

In the case of the aforementioned composition (II), the polymerization initiator can be blended by a well-known method immediately before using the adhesive composition. In addition, the polymerization initiator or polymerization inhibitor can also be blended in the form of a solution previously dissolved in the above-mentioned component (S2). The usage amount of the component (S2) may be appropriately adjusted according to the type of the polymerization initiator or the polymerization inhibitor. For example, it is preferably 1 to 50 parts by mass, and more preferably 5 parts by mass relative to 100 parts by mass of the component (S1). ~30 parts by mass. When the usage-amount of (S2) component is in the said preferable range, a polymerization initiator or a polymerization inhibitor can be fully melt|dissolved.

In addition, the adhesive composition of the present embodiment preferably satisfies at least one of the following requirements. (Requirement 1): A test piece of 20mm×5mm′ thickness 0.5mm is made from the above-mentioned adhesive composition, and the temperature is raised at a rate of 5°C/min from room temperature to 215°C under the tensile condition of the frequency of 1Hz. , the complex elastic modulus E* ₅₀ at 50°C did not reach 1.0´10 ⁹ Pa when the aforementioned test piece was submitted to the dynamic viscoelasticity measurement. (Requirement 2): Under the same conditions as (Requirement 1), when the test piece is subjected to dynamic viscoelasticity measurement, the complex elastic modulus E* ₁₅₀ at 150°C exceeds 3.0´10 ⁶ Pa. (Requirement 3): When the complex elastic modulus E* ₅₀ at 50°C and the complex elastic modulus E* ₁₅₀ at 150°C are obtained under the same conditions as (Requirement 1) and (Requirement 2), E* The ratio of ₅₀ /E* ₁₅₀ is 2000 or less. In addition, the dynamic viscoelasticity measurement system in each requirement can be performed according to the following procedure using a dynamic viscoelasticity measuring apparatus (Rheogel-E4000, UBM Co., Ltd. make) (the same applies to the following requirements). (Procedure) First, the adhesive composition was coated on a release agent-attached PET film, and heated in an oven under atmospheric pressure at 50° C. and 150° C. for 60 minutes each to form an adhesive layer (thickness 0.5 mm). Next, the complex elastic modulus E* at each temperature of the adhesive layer peeled from the PET film was measured using the aforementioned dynamic viscoelasticity measuring apparatus. The measurement conditions are that the shape of the sample is 20mm × 5mm × thickness 0.5mm, under the stretching condition of the frequency 1Hz, from room temperature to 215°C, under the condition of heating at a rate of 5°C/min, the measurement is performed at 50°C, 150°C The complex elastic modulus of .

Since the adhesive composition of the present embodiment satisfies (requirement 1), the adhesive composition system can exhibit higher adhesive ability in a temperature range relatively close to room temperature. The complex elastic modulus E* ₅₀ at 50°C is more preferably less than 0.9´10 ⁹ Pa, still more preferably less than 0.6´10 ⁹ Pa. The lower limit of the complex elastic modulus E* ₅₀ at 50°C is not particularly limited, but is, for example, 1.0´10 ⁷ Pa or more.

Since the adhesive composition of the present embodiment satisfies (requirement 2), the adhesive composition can precisely suppress the flow and the like occurring in the high temperature region. As a result, the positional displacement of the substrate is less likely to occur during high temperature processing. The complex elastic modulus E* ₁₅₀ at 150°C is more preferably over 3.5´10 ⁶ Pa, particularly preferably over 5.0´10 ⁶ Pa. The upper limit of the complex elastic modulus E* ₁₅₀ at 150°C is not particularly limited, but is, for example, 1.0´10 ⁸ Pa or less.

Since the adhesive composition of the present embodiment satisfies (requirement 3), the adhesive composition tends to exhibit a stable adhesive function both at normal temperature and during heating. The ratio of E* ₅₀ /E* ₁₅₀ is preferably 1000 or less, more preferably 500 or less, and still more preferably 100 or less. The lower limit of the ratio of E* ₅₀ /E* ₁₅₀ is not particularly limited, but is, for example, 5 or more, preferably 1.5 or more.

In the adhesive composition of the present embodiment described above, by combining the hydrocarbon resin (P1) and the resin (P2) having a glass transition temperature of 180° C. or higher, an adhesive layer with higher heat resistance can be formed. Thereby, the adhesive layer formed of the adhesive composition of the present embodiment is less likely to cause positional displacement of the substrate, eg, before and after the sealing operation, due to the influence of high-temperature treatment at the time of semiconductor package manufacturing.

In addition, according to the adhesive composition of the present embodiment, the substrate (bare wafer) is fixed to the formed adhesive layer with sufficient strength (good die bondability). Furthermore, according to the adhesive composition of the present embodiment, the adhesive layer formed has a high solubility in a hydrocarbon-based solvent. Thereby, the adhesive layer can be easily cleaned and removed from the substrate during the manufacture of the semiconductor package.

(Adhesive composition (2nd aspect)) Next, the adhesive composition of the 2nd aspect of this invention is demonstrated. The adhesive composition of the second aspect of the present invention is used for bonding a support and a substrate. The adhesive composition of this embodiment contains a resin component (P). The resin component (P) contains at least the hydrocarbon resin (P1) and satisfies the following requirements. (Requirement 1): Prepare a test piece of 20mm´5mm´ thickness 0.5mm from the above-mentioned adhesive composition, and under the condition of stretching at a frequency of 1Hz, from room temperature to 215°C, under the condition of heating at a rate of 5°C/min , the complex elastic modulus E* ₅₀ at 50°C did not reach 1.0´10 ⁹ Pa when the aforementioned test piece was submitted to the dynamic viscoelasticity measurement. (Requirement 2): Under the same conditions as (Requirement 1), when the test piece is subjected to dynamic viscoelasticity measurement, the complex elastic modulus E* ₁₅₀ at 150°C exceeds 3.0´10 ⁶ Pa.

The components (P1), (P2), and (P3) that can constitute the resin component (P) of this aspect, and their blending ratios, are as described in the adhesive composition of the first aspect. However, the adhesive composition of the present embodiment does not necessarily need to contain the component (P2), and a component corresponding to the component (P2) may be blended, and the glass transition temperature (Tg) of the component may not be within the aforementioned range.

It is preferable that the adhesive composition of this aspect contains the component which has a structural unit (u21) derived from the monomer containing a maleimide skeleton. This structural unit (u21) is typically included in any one of the resins that constitute the resin component (P).

[式中，R^u10 表示碳數1～30的有機基]。Here, the structural unit (u21) is typically a structural unit represented by the following general formula (p2-1). Incidentally, as for the organic group having 1 to 30 carbon atoms shown here, those that can be used are as described above.

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

In addition, the adhesive composition of this aspect may contain any components or solvent components that may be contained in the adhesive composition of the first aspect, and the blending ratio thereof is also as described above.

As an adhesive agent composition of this aspect, the following compositions (IV)-(VI) are mentioned suitably. These compositions can be obtained by dissolving or dispersing necessary components in solvent components. Composition (IV): a composition containing the component (P1), a polymerization inhibitor and a solvent component Composition (V): a composition containing the (P1) component, a curable monomer, a polymerization initiator and a solvent component (VI): A composition containing the component (P1), the component (P3), a polymerization inhibitor and a solvent component

The adhesive composition of the present embodiment must satisfy the above (requirement 1). Thereby, the adhesive composition system can exhibit higher adhesiveness in a temperature region relatively close to room temperature. The complex elastic modulus E* ₅₀ at 50°C is more preferably less than 0.9´10 ⁹ Pa, still more preferably less than 0.6´10 ⁹ Pa. The lower limit value of the complex elastic modulus E* ₅₀ at 50°C is not particularly limited, but is, for example, 1.0´10 ⁷ Pa or more.

In addition, the adhesive composition of the present embodiment must satisfy the above-mentioned (requirement 2) in addition to the above-mentioned (requirement 1). The adhesive composition system can precisely suppress the flow or the like that occurs in a high temperature region. As a result, the positional displacement of the substrate is less likely to occur during high temperature processing. The complex elastic modulus E* ₁₅₀ at 150°C is more preferably over 3.5´10 ⁶ Pa, particularly preferably over 5.0´10 ⁶ Pa. The upper limit of the complex elastic modulus E* ₁₅₀ at 150°C is not particularly limited, but is, for example, 1.0´10 ⁸ Pa or less.

In addition, the adhesive composition of the present embodiment preferably satisfies the following requirements (requirement 3). (Requirement 3): When the complex elastic modulus E* ₅₀ at 50°C and the complex elastic modulus E* ₁₅₀ at 150°C are obtained under the same conditions as (Requirement 1) and (Requirement 2), E* The ratio of ₅₀ /E* ₁₅₀ is 2000 or less. Since the adhesive composition of the present embodiment satisfies (requirement 3), the adhesive composition tends to exhibit a stable adhesive function both at normal temperature and during heating. The ratio of E* ₅₀ /E* ₁₅₀ is preferably 1000 or less, more preferably 500 or less, and still more preferably 100 or less. The lower limit of the ratio of E* ₅₀ /E* ₁₅₀ is not particularly limited, but is, for example, 5 or more, preferably 1.5 or more.

In the adhesive composition of the present embodiment described above, by satisfying specific requirements while including the hydrocarbon resin (P1), an adhesive layer with higher heat resistance can be formed. Thereby, the adhesive layer formed of the adhesive composition of the present embodiment is less likely to cause positional displacement of the substrate, eg, before and after the sealing operation, due to the influence of high-temperature treatment at the time of semiconductor package manufacturing.

In addition, according to the adhesive composition of the present embodiment, the substrate (bare wafer) is fixed to the formed adhesive layer with sufficient strength (good die bondability). Furthermore, according to the adhesive composition of the present embodiment, the adhesive layer formed has a high solubility in a hydrocarbon-based solvent. Thereby, the adhesive layer can be easily cleaned and removed from the substrate during the manufacture of the semiconductor package.

(Adhesive layer-attached support) The adhesive layer-attached support of the third aspect of the present invention includes: a substrate to which a substrate is attached; and, on the support, the first or second aspect is used The adhesive layer formed by the adhesive composition of the sample. Therefore, in the support with the adhesive layer, heat resistance can be improved. The laminate 10 shown in FIG. 1 is the one in which the support 12 and the substrate 4 are laminated with the adhesive layer 3 interposed therebetween, that is, the substrate 4 is fixed on the support 123 with the adhesive layer. The adhesive layer-attached support 123 of this embodiment includes the support 12 provided with the separation layer 2 on the support base 1 , and the adhesive layer 3 formed on the support 12 .

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

"Supporting Substrate" The supporting substrate has the property of penetrating light. The support base is a member that supports the substrate, and is attached to the substrate via the adhesive layer. Therefore, it is preferable that the support base has the necessary strength to prevent breakage or deformation of the substrate during thinning of the sealing body, transportation of the substrate, and mounting to the substrate. In addition, it is preferable that the support substrate transmits light of a wavelength which can degenerate the separation layer. As the material of the support matrix, for example, glass, silicon, acrylic resin, etc. can be used. Examples of the shape of the support substrate include, but are not limited to, a rectangle, a circle, and the like. Moreover, as a support base, the size of a circular support base may be enlarged for the purpose of higher density integration or improvement of production efficiency, and the shape of a plan view is a square large panel.

"Separation layer" The separation layer is adjacent to the adhesive layer and is degraded by light irradiation, and the layer of the support base can be separated from the substrate attached to the support. This separation layer can be formed using the composition for forming a separation layer described later, for example, by firing the components contained in the composition for forming a separation layer, or by chemical vapor deposition (CVD) method. This separation layer is appropriately degraded by absorbing light irradiated through the support substrate. In addition, the separation layer is preferably formed of only a material that absorbs light, but may be a layer in which a material that does not have a structure that absorbs light is blended within a range that does not impair the essential characteristics of the present invention.

The so-called "deterioration" of the separation layer refers to a phenomenon in which the separation layer is in a state where it can be destroyed by external force, or the adhesion force between the separation layer and the adjoining layer is reduced. The separation layer becomes weak by absorbing light, and loses strength or adhesiveness before being irradiated with light. The deterioration of the separation layer is caused by the occurrence of decomposition due to the energy of absorbed light, changes in steric configuration, or dissociation of functional groups.

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

Preferably, the surface of the separation layer on the side contacting the adhesive layer is flat (no concavities and convexities are formed), whereby the formation of the adhesive layer can be easily performed, and the support base and the substrate can be easily and uniformly attached.

(Composition for forming a separation layer) The composition for forming a separation layer, which is a material for forming a separation layer, includes, for example, fluorocarbons, polymers having repeating units having a structure having light absorbing properties, inorganic substances, and infrared absorbing properties. The structural compounds, infrared absorbing substances, reactive polysilsesquioxanes, or resin components with a phenolic skeleton. In addition, the composition for forming a separation layer may contain a filler, a plasticizer, a thermal acid generator component, a photoacid generator component, an organic solvent component, a surfactant, a sensitizer, a component capable of improving the separability of the support substrate, and the like as an optional ingredient.

・Fluorocarbon The separation layer system may contain fluorocarbon. The separation layer made of fluorocarbon deteriorates by absorbing light, and as a result loses strength or adhesiveness before being irradiated with light. Therefore, by applying a slight external force (for example, lifting the support, etc.) to break the separation layer, the support and the substrate can be easily separated. The fluorocarbon constituting the separation layer can be suitably formed into a film by the plasma CVD method. Fluorocarbons absorb light with a specific range of wavelengths depending on their species. By irradiating the separation layer with light of a wavelength in the absorption range of the fluorocarbon used for the separation layer, the fluorocarbon can be appropriately modified. The light absorptivity of the separation layer is preferably 80% or more.

As the light irradiated to the separation layer, solid-state lasers such as YAG lasers, ruby lasers, glass lasers, YVO ₄ lasers, LD lasers, fiber lasers, etc. Liquid lasers such as pigment lasers, CO ₂ lasers, excimer lasers, Ar lasers, He-Ne lasers and other gas lasers, semiconductor lasers, free electron lasers and other laser light or non-laser light That's it. As a wavelength which can change a fluorocarbon, the wavelength in the range of 600 nm or less can be used, for example.

・A polymer having a repeating unit having a light-absorbing structure The separation layer also contains a polymer having a repeating unit having a light-absorbing structure. The polymer is degraded by exposure to light. The light-absorbing structure includes, for example, an atomic group containing a conjugated π electron system composed of a substituted or unsubstituted benzene ring, a condensed ring, or a heterocyclic ring. A structure having light absorption properties, more specifically, a cardo structure, or a diphenyl ketone structure, a diphenyl arylene structure, and a diphenyl arsenic structure existing in the side chain of the polymer. (bisphenyl sulfone structure), diphenyl structure or diphenylamine structure. The above-mentioned light-absorbing structure can absorb light having a desired range of wavelengths according to its type. For example, the wavelength of light that can be absorbed by the above-mentioned light-absorbing structure is preferably in the range of 100 to 2000 nm, 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 above 254 nm and below 436 nm), KrF excimer laser (wavelength 248 nm), ArF excimer laser (wavelength 193 nm), F ₂ Light emitted by molecular laser (wavelength 157nm), XeCl laser (wavelength 308nm), XeF laser (wavelength 351nm) or solid UV laser (wavelength 355nm), or g-line (wavelength 436nm), h-line (wavelength 405nm) ) or i-line (wavelength 365nm), etc.

・The inorganic substance separation layer may be composed of inorganic substances. This inorganic substance should just be what changes quality by absorbing light, for example, one or more types selected from the group which consists of a metal, a metal compound, and carbon are mentioned suitably. A metal compound is a compound containing a metal atom, for example, a metal oxide and a metal nitride are mentioned. As such an inorganic substance, one or more kinds selected from the group consisting of gold, silver, copper, iron, nickel, aluminum, titanium, chromium, SiO ₂ , SiN, Si ₃ N ₄ , TiN, and carbon can be mentioned. Also, the so-called carbon is a concept that can contain allotropes of carbon, including, for example, diamonds, fullerenes, diamond-like carbons, carbon nanotubes, and the like. The above-mentioned inorganic substances absorb light of wavelengths having a specific range, depending on the kind.

As the light irradiating the separation layer made of inorganic substances, as long as the wavelengths that the inorganic substances can absorb, for example, YAG lasers, ruby lasers, glass lasers, YVO ₄ lasers, LD lasers, fiber lasers, etc. are suitably used. solid-state lasers, liquid lasers such as pigment lasers, CO ₂ lasers, excimer lasers, Ar lasers, He-Ne lasers and other gas lasers, semiconductor lasers, free electron lasers, etc. Light or non-laser light can be used. The separation layer composed of inorganic substances can be formed on the support substrate by well-known techniques such as sputtering, chemical vapor deposition (CVD), plating, plasma CVD, spin coating, and the like.

・The compound separation layer having an infrared absorbing structure may contain a compound having an infrared absorbing structure. The compound having this infrared absorbing structure is degraded by absorbing infrared rays. Examples of structures having infrared absorption properties or compounds having such structures include alkanes, alkenes (vinyl, trans, cis, vinylidene, trisubstituted, tetrasubstituted, conjugated, alkenes, cyclics) ), alkynes (monosubstituted, disubstituted), monocyclic aromatics (benzene, monosubstituted, disubstituted, trisubstituted), alcohols or phenols (free OH, intramolecular hydrogen bonds, intermolecular hydrogen bonds, saturated secondary , saturated tertiary, unsaturated secondary, unsaturated tertiary), acetal, ketal, aliphatic ether, aromatic ether, vinyl ether, ethylene oxide cyclic ether, peroxide ether, ketone, dialkyl Carbonyl, aromatic carbonyl, enols of 1,3-diketones, o-hydroxyaryl ketones, dialkyl aldehydes, aromatic aldehydes, carboxylic acids (dimers, carboxylate anions), formates, acetates , conjugated esters, non-conjugated esters, aromatic esters, lactones (β-, g-, d-), aliphatic acid chlorides, aromatic acid chlorides, acid anhydrides (conjugated, non-conjugated, cyclic , acyclic), primary amide, secondary amide, lactamide, primary amine (aliphatic, aromatic), secondary amine (aliphatic, aromatic), tertiary amine (aliphatic, aromatic) , primary amine salt, secondary amine salt, tertiary amine salt, ammonium ion, aliphatic nitrile, aromatic nitrile, carbodiimide, aliphatic isonitrile, aromatic isonitrile, isocyanate, thiocyanate, aliphatic Isothiocyanates, aromatic isothiocyanates, aliphatic nitro compounds, aromatic nitro compounds, nitroamines, nitrosoamines, nitrates, nitrites, nitroso bonds (aliphatic, Aromatic, monomer, dimer), thiol or thiophenol or thiol acid and other sulfur compounds, thiocarbonyl, sulfite, sulfite, sulfonyl chloride, primary sulfonamides, secondary sulfonamides, sulfate esters , carbon-halogen bond, Si-A ¹ bond (A ¹ is H, C, O or halogen), PA ² bond (A ² is H, C or O) or Ti-O bond.

Examples of the structure including the carbon-halogen bond include -CH ₂ Cl, -CH ₂ Br, -CH ₂ I, -CF ₂ -, -CF ₃ , -CH=CF ₂ , -CF=CF ₂ , Fluorinated aryl or aryl chloride, etc.

Examples of the structure including the Si-A ¹ bond include SiH, SiH ₂ , SiH ₃ , Si-CH ₃ , Si-CH ₂ -, Si-C ₆ H ₅ , SiO-aliphatic, and 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 a structure containing a Si- ^Al bond, one in which a siloxane skeleton or a silsesquioxane skeleton is formed is particularly preferable.

Examples of the structure including the PA ² bond include PH, PH ₂ , P-CH ₃ , P-CH ₂ -, PC ₆ H ₅ , A ³ ₃ -PO (A ³ is an aliphatic group or an 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 , POP, P-OH or O=P-OH, etc.

As the compound containing the above-mentioned Ti—O bond, for example, (i) tetraisopropoxytitanium, tetra-n-butoxytitanium, tetra(2-ethylhexyloxy)titanium, or titanium isopropoxyoctene can be mentioned. Titanium alkoxides such as glycolate; (ii) chelated titanium such as diisopropoxy, bis(acetylacetonate) titanium or propanedioxytitanium bis(ethylacetate); (iii) iC ₃ H ₇ O-[-Ti(OiC ₃ H ₇ ) ₂ -O-] _n -iC ₃ H ₇ or nC ₄ H ₉ O-[-Ti(OnC ₄ H ₉ ) ₂ -O-] Titanium polymers such as nnC ₄ H ₉ ; (iv) tri-n-butoxytitanium monostearate, titanium stearate, diisopropoxytitanium diisostearate or (2-n-butoxytitanium) (v) Water-soluble titanium compounds such as di-n-butoxy and bis(triethanolamido) titanium, etc. Among them, as the compound containing a Ti-O bond, di-n-butoxy·bis(triethanolamido)titanium (Ti(OC ₄ H ₉ ) ₂ [OC ₂ H ₄ N(C ₂ H ₄ OH) ₂ ] ₂ ).

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

In addition, the wavelength of infrared rays that can be absorbed by the above-mentioned structures can be easily understood by those in the industry. For example, for the absorption band of each structure, refer to the non-patent literature: SILVERSTEIN・BASSLER・MORRILL, "Method of Identification by Spectroscopy of Organic Compounds (5th Edition)-Combination of MS, IR, NMR, and UV-" (1992) Published in 2008) on pages 146 to 151.

As a compound having an infrared absorbing structure used for the formation of the separation layer, among the compounds having the above-mentioned structure, as long as it can be dissolved in a solvent and cured to form a cured layer for coating, there is no particular limited. However, in order to effectively degenerate the compound in the separation layer and facilitate the separation of the support substrate and the substrate, it is preferable that the absorption of infrared rays in the separation layer be large, that is, the transmittance of infrared rays when irradiating the separation layer with infrared rays. Low. Specifically, the transmittance of infrared rays in the separation layer is preferably less than 90%, and the transmittance of infrared rays is more preferably less than 80%.

・Infrared absorbing substance The separation layer may also contain an infrared absorbing substance. This infrared absorbing material may be changed by absorbing light. For example, carbon black, iron particles, or aluminum particles can be suitably used. Depending on the type of infrared absorbing substance, it absorbs light with a wavelength of its own. By irradiating the separation layer with light having a wavelength in the absorption range of the infrared absorbing material used in the separation layer, the infrared absorbing material can be appropriately degenerated.

・Reactive polysilsesquioxane The separation layer can be formed by polymerizing reactive polysilsesquioxane. Thereby, the formed separation layer has high chemical resistance and high heat resistance.

The so-called "reactive polysilsesquioxane" refers to a polysilsesquioxane having a silanol group or a functional group that can form a silanol group due to hydrolysis at the end of the polysilsesquioxane skeleton. By condensing the silanol group or the functional group capable of forming a silanol group, they can be polymerized with each other. Also, as long as the reactive polysilsesquioxane has a silanol group or a functional group capable of forming a silanol group, the reactivity of a silsesquioxane skeleton having a random structure, a cage structure, a trapezoid structure, etc. can be used. Polysilsesquioxane.

The siloxane content of the reactive polysilsesquioxane is preferably 70-99 mol %, more preferably 80-99 mol %. If the siloxane content of the reactive polysilsesquioxane is within the above-mentioned preferred range, it is possible to form a material that can be suitably deteriorated by irradiation with infrared rays (preferably far infrared rays, more preferably light with a wavelength of 9-11 μm). separate layers.

The weight average molecular weight (Mw) of the reactive polysilsesquioxane is preferably 500-50,000, more preferably 1,000-10,000. If the weight-average molecular weight (Mw) of the reactive polysilsesquioxane is within the aforementioned preferred range, it can be appropriately dissolved in a solvent and can be appropriately coated on a support plate.

As a commercial item which can be used as a reactive polysilsesquioxane, SR-13, SR-21, SR-23, or SR-33 (trade name) by Konishi Chemical Industry Co., Ltd., etc. are mentioned, for example.

・A resin component having a phenol skeleton The separation layer may contain a resin component having a phenol skeleton. Since it has a phenol skeleton, it is easy to change in quality (oxidation, etc.) by heating or the like, and has high photoreactivity. "Having a phenol skeleton" here means that it contains a hydroxybenzene structure. The resin component having a phenol skeleton has film-forming ability, and the molecular weight is preferably 1,000 or more. Since the molecular weight of the resin component is 1,000 or more, the film-forming ability increases. The molecular weight of the resin component is more preferably 1,000 to 30,000, particularly preferably 1,500 to 20,000, and particularly preferably 2,000 to 15,000. Since the molecular weight of the resin component is equal to or less than the upper limit of the above-mentioned preferred range, the solubility of the composition for forming a separation layer in a solvent can be improved. In addition, as the molecular weight of the resin component, the weight average molecular weight (Mw) in terms of polystyrene measured by GPC (gel permeation chromatography) was used.

Examples of the resin component having a phenol skeleton include novolak-type phenol resins, resol-type phenol resins, hydroxystyrene resins, hydroxyphenyl silsesquioxane resins, hydroxybenzyl silsesquioxane resins, Acrylic resins having a phenol skeleton, resins having repeating units represented by the general formula (P2) described later, and the like. Among these, a novolac-type phenol resin and a resol-type phenol resin are used.

<Adhesive layer> The adhesive layer 3 is a layer for bonding the support base 1 and the substrate 4, and can be formed using the composition for forming an adhesive layer of the above-described embodiment.

The thickness of the next layer 3 is, for example, preferably within a range of 0.1 μm or more and 50 μm or less, and more preferably within a range of 1 μm or more and 10 μm or less. If the thickness of the adhesive layer is in the range of not less than 0.1 μm and not more than 50 μm, the support base 1 and the substrate 4 can be adhered more favorably. In addition, since the thickness of the adhesive layer is 1 μm or more, the substrate can be sufficiently fixed on the support base, and since the thickness of the adhesive layer is 10 μm or less, the adhesive layer can be easily removed in the subsequent removal step.

The adhesive layer-attached support system of the present embodiment can be produced by similarly performing the operation of the later-described [adhesive layer forming step].

The adhesive layer-attached support of the above-described embodiment is provided with an adhesive layer to which the adhesive layer-forming composition of the above-described embodiment is applied, so that heat resistance is improved, and more preferably die bondability and cleaning removability are also improved.

(Adhesive Film) The adhesive film of the fourth aspect of the present invention includes: a film; and an adhesive layer formed on the film using the adhesive composition of the first or second aspect. By using this adhesive film, an adhesive layer can be appropriately formed on the support. Compared with the case where the adhesive composition is directly applied on the support to form the adhesive layer, the adhesive layer with favorable film thickness uniformity and surface smoothness can be easily formed.

As the film, for example, the adhesive layer formed on the film can be easily peeled off from the film, and a mold release film that can transfer the adhesive layer to the surface to be treated such as a support is preferably used. Specific examples of the film include synthetic resin films such as polyethylene terephthalate, polyethylene, polypropylene, polycarbonate, and polyvinyl chloride, and are preferably flexible films. As for the above-mentioned film, it is preferable to give a mold release treatment as necessary to facilitate transfer. The thickness of the film can be set appropriately, for example, 15 to 125 μm.

The adhesive film is produced by forming an adhesive layer on the film. For example, a method of coating the adhesive composition on a thin film so that the dry film thickness of the adhesive layer becomes 10 to 1000 μm can be used. In this case, a well-known method can be suitably used according to the desired film thickness and uniformity of the adhesive layer.

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

The method of using the adhesive film, for example, when a protective film is used, after peeling off, the exposed adhesive layer is superimposed on the support surface, and the adhesive layer is exposed from the film (the back side of the surface on which the adhesive layer is formed). The method of moving the heating roller to thermally press the adhesive layer to the surface of the support. In addition, the protective film peeled from the adhesive film can be reused if it is successively wound into a roll shape on a roll such as a winding roll.

(Laminate) The laminate system of the fifth aspect of the present invention is a laminate system in which a support and a substrate are bonded via an adhesive layer. As shown in FIG. 1 , the laminate 10 of the present embodiment is one in which a support 12 and a substrate 4 are bonded with an adhesive layer 3 interposed therebetween, that is, a support 123 with an adhesive layer and a support with an adhesive layer are provided. The substrate 4 arranged on the surface 3 s of the adhesive layer 3 provided in the 123 is on the opposite side to the support 12 side.

The support 12 is the one in which the support base 1 and the separation layer 2 are laminated, and the description of this is the same as that described in the above-mentioned <Support>. The description of the adhesive layer 3 is the same as that described in the above-mentioned <Adhesive Layer>.

<Substrate> The substrate 4 is in a state supported by the supporting base 1, and is used for processes such as thinning and mounting. On the substrate 4, structures such as integrated circuits and metal bumps are mounted, for example. As the substrate 4, a silicon wafer substrate is typically used, but it is not limited to this, and a ceramic substrate, a thin film substrate, a flexible substrate, or the like may also be used.

In this embodiment, the element is a semiconductor element or other element, and may have a structure of a single layer or a plurality of layers. In addition, when the element is a semiconductor element, the electronic component obtained by dicing the sealing substrate becomes a semiconductor device.

The laminate of the above-described embodiment is provided with an adhesive layer to which the composition for forming an adhesive layer of the above-described embodiment is applied, and thus has higher heat resistance. Thereby, in the laminated body of this embodiment, the positional shift of the board|substrate before and after the sealing operation by the influence of a high temperature process is hard to generate|occur|produce at the time of a semiconductor package manufacture.

In addition, in the laminate of the present embodiment, the substrate (bare wafer) is adhered to the formed adhesive layer with sufficient strength (good die bondability). Furthermore, in the laminate of the present embodiment, the subsequent layer system has high solubility in a hydrocarbon-based solvent. Thereby, the adhesive layer can be easily cleaned and removed from the substrate during the manufacture of the semiconductor package.

In the laminate of the above-described embodiment, the support base 1 and the separation layer 2 are adjacent to each other, but the present invention is not limited to this, and other layers may be further formed between the support base 1 and the separation layer 2 . In this case, the other layers may be made of a material that transmits light. Therefore, it is possible to appropriately add a layer that imparts preferable properties and the like to the laminate 10 without hindering the incidence of light to the separation layer 2 . Depending on the kind of material constituting the separation layer 2, the wavelengths of available light are different. Therefore, it is not necessary for the materials constituting the other layers to transmit light of all wavelengths, and may be appropriately selected from materials that transmit light of wavelengths capable of deteriorating the materials constituting the separation layer 2 .

(Manufacturing method of laminate) The sixth aspect of the present invention is a method of manufacturing a laminate in which a support and a substrate are bonded via an adhesive layer, and includes an adhesive layer forming step and a bonding step.

<1st Embodiment> The manufacturing method of the laminated body of 1st Embodiment includes the step of preparing a support, the step of forming an adhesive layer, and a step of laminating. Fig. 2 is a schematic sequence diagram illustrating an embodiment of a method for producing a laminate. Fig. 2(a) is a diagram illustrating the step of making the support, Fig. 2(b) is a diagram illustrating the step of forming the adhesive layer, and Fig. 2(c) is a diagram illustrating the step of laminating. In the method for producing the laminate of the present embodiment, as the composition for forming the separation layer, one containing fluorocarbon is used. In addition, as the composition for forming an adhesive layer, those containing the (P1) component and the (P2) component of the above-described embodiment were used.

[Procedure for producing a support] The step for producing a support in the embodiment is a step for obtaining a support by forming a separation layer using the composition for forming a separation layer on one side of the support base. In Fig. 2(a), on the support base 1, the separation layer 2 is formed by using the separation layer forming composition (containing fluorocarbon) (that is, the support base with the separation layer is produced).

The method of forming the separation layer 2 on the support substrate 1 is not particularly limited, and examples thereof include spin coating, dipping, roll knife, spray coating, slit coating, chemical vapor deposition (CVD), and the like. For example, in the step of preparing the support, in a heating environment or a reduced pressure environment, the solvent component is removed from the coating layer of the separation layer-forming composition coated on the support substrate 1 to form a film, or a film is formed on the support substrate 1, a support was obtained by forming a film by a vapor deposition method.

[Adhesive layer forming step] The adhesive layer forming step in the embodiment is a step of forming an adhesive layer using the adhesive layer forming composition of the above-mentioned embodiment on one side of the support. In Fig. 2(b), on the surface of the support 12 on the side of the separation layer 2, the adhesive layer 3 is formed using the composition for forming an adhesive layer of the above-mentioned embodiment (that is, the support 123 with the adhesive layer is produced).

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

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

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

[Lamination step] The lamination step in the embodiment is a step of laminating the support and the substrate through the adhesive layer formed in the adhesive layer forming step. As described above, when the separation layer 2 is provided on the support base 1, the bonding system bonds the support 12 and the substrate 4 while making the separation layer 2 and the adhesive layer 3 face each other. In FIG. 2( c ), the support base 1 (support 12 ) on which the separation layer 2 is formed and the substrate 4 without the separation layer 2 are laminated via the adhesive layer 3 to obtain the support base 1 and the separation layer 2 . , followed by the layer 3 and the substrate 4 stacked in the order of the laminate 10 .

The method of laminating the support 12 and the substrate 4 via the adhesive layer 3 is to arrange the substrate 4 at a specified position on the adhesive layer 3 and heat it under vacuum (for example, about 100° C.), while bonding by die The support body 12 and the substrate 4 are press-bonded by a machine or the like.

According to the method for producing the laminate of the first embodiment, since the adhesive layer forming composition of the above-described embodiment is applied to provide the adhesive layer, the heat resistance is higher, and the positional displacement of the substrate is less likely to occur, for example, before and after the sealing operation. In addition, the substrate (bare wafer) is fixed to the formed adhesive layer with sufficient strength (good die bondability).

In the manufacturing method of the laminate of the present embodiment described above, the separation layer 2 is formed on the support base 1 , but it is not limited to this, and the separation layer 2 may be formed on the substrate 4 . In the above-described method for producing the laminate of the present embodiment, the adhesive layer 3 is formed on the separation layer 2 , but it is not limited to this, and the adhesive layer 3 may be formed on the substrate 4 . In addition, the separation layer 2 may be formed on both the support base 1 and the substrate 4. In this case, the support base 1 and the substrate 4 are bonded via the separation layer 2, the adhesive layer 3 and the separation layer 2.

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

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

In the sealing step, for example, the sealing material heated to 130 to 170° C. is supplied to the adhesive layer 3 so as to cover the substrate 4 while maintaining a high viscosity state, and is formed on the adhesive layer 3 by compression molding. The sealing body 20 (laminated body) provided with the sealing material layer 5 is provided. At this time, the temperature conditions are, for example, 130 to 170°C. The pressure applied to the substrate 4 is, for example, 50 to 500 N/cm ² .

For the sealing material, for example, a composition containing an epoxy-based resin or a polysiloxane-based resin can be used. The sealing material layer 5 is preferably not provided on each of the substrates 4 , but is provided so as to cover all the substrates 4 on the adhesive layer 3 .

According to the method for producing the laminate of the second embodiment, since the adhesive layer forming composition of the above-described embodiment is applied to provide the adhesive layer, the heat resistance is higher, and the positional displacement of the substrate is less likely to occur, for example, before and after the sealing operation.

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

[grinding step] The grinding step in the embodiment is a grinding step of grinding the sealing material portion (sealing material layer 5) in the sealing body 20 so that a part of the substrate 4 is exposed after the sealing step. The grinding of the sealing material portion is carried out by grinding the sealing material layer 5 to a thickness almost equal to that of the substrate 4, as shown in FIG. 4(b), for example.

[Rewiring Forming Step] The rewiring forming step in the embodiment is a step of forming the rewiring layer 6 on the exposed substrate 4 after the above-mentioned grinding step. The redistribution layer is also called RDL (Redistribution Layer), is a thin film wiring body that constitutes wiring for connecting elements, and may have a single-layer or plural-layer structure. For example, the rewiring layer can be formed on a dielectric (silicon oxide (SiO _x ), photosensitive resin such as photosensitive epoxy resin, etc.), by a conductor (aluminum, copper, titanium, nickel, gold, silver, etc.) such as metals and silver-tin alloys) with wiring formed, but not limited to this.

As a method of forming the rewiring layer 6 , first, a dielectric layer such as silicon oxide (SiO _x ) or a photosensitive resin is formed on the sealing material layer 5 . The dielectric layer made of silicon oxide can be formed by, for example, a sputtering method, a vacuum evaporation method, or the like. The dielectric layer made of photosensitive resin can be formed by coating the photosensitive resin on the sealing material layer 5 by, for example, spin coating, dipping, roll knife, spray coating, slit coating, or the like.

Next, on the dielectric layer, wiring is formed by a conductor such as metal. As a method of forming the wiring, for example, well-known semiconductor processing methods such as photolithography (resist lithography) and the like, and etching processes can be used. As such a lithography process, the lithography process using a positive resist material, and the lithography process using a negative resist material are mentioned, for example.

In this way, the sealing body 20 (laminated body) is exposed to an acid such as hydrofluoric acid, an alkali such as tetramethylammonium hydroxide (TMAH), or a resist for dissolving the resist material during lithography, etching, and the like. solvent, while being treated at high temperature. However, the adhesive layer is formed by using the composition for forming an adhesive layer of the above-described embodiment, and the adhesive layer has high heat resistance. Therefore, the rewiring layer 6 can be appropriately formed on the sealing material layer 5 .

According to the manufacturing method of the laminate of the third embodiment, a layer formed by laminating the support substrate 1, the separation layer 2, the adhesive layer 3, the sealing material layer 5 covering the substrate 4, and the rewiring layer 6 in this order can be stably manufactured. Combine 30. The laminate 30 is a laminate produced in a process based on a fan-out technology in which terminals provided on the substrate 4 are mounted on the rewiring layer 6 extending beyond the wafer area.

In the manufacturing method of the laminated body of this embodiment, the formation of bumps or the mounting of components can be further performed on the rewiring layer 6 . Mounting of components on the rewiring layer 6 can be performed using, for example, a wafer mounter or the like.

(Manufacturing method of electronic component) The manufacturing method of the electronic component of the 6th aspect of this invention has a separation step and a removal step after obtaining a laminated body by the manufacturing method of the laminated body of the said 5th aspect.

FIG. 5 is a schematic flow chart illustrating an embodiment of a method of manufacturing a semiconductor package (electronic component). Fig.5 (a) is a figure which shows the laminated body manufactured by the manufacturing method of 3rd Embodiment, FIG.5(b) is a figure explaining a separation step, and FIG.5(c) is a figure explaining a removal step.

[Separation step] The separation step in the embodiment is to separate the support base from the substrate 4 included in the laminate 30 by irradiating the separation layer 2 with light (arrow) through the support base 1 to degenerate the separation layer 2 1 steps.

As shown in FIG. 5( a ), in the separation step, the separation layer 2 is degraded by irradiating light (arrow) to the separation layer 2 through the support substrate 1 . As a wavelength which can degenerate the separation layer 2, the range of 600 nm or less is mentioned, for example. The type and wavelength of the irradiated light can be appropriately selected according to the penetrability 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, and an LD laser can be used. solid-state lasers such as lasers, fiber lasers, liquid lasers such as pigment lasers, CO ₂ lasers, excimer lasers, Ar lasers, He-Ne lasers, etc., gas lasers, semiconductor lasers, free Laser light, non-laser light such as electronic laser. As a result, the quality of the separation layer 2 is changed, and the support base 1 and the substrate 4 can be easily separated from each other.

When irradiating laser light, the following conditions are mentioned as an example of the laser light irradiation conditions. The average output value of the laser light is preferably 1.0W or more and 5.0W or less, more preferably 3.0W or more and 4.0W or less. The repetition frequency of the laser light is preferably 20 kHz or more and 60 kHz or less, more preferably 30 kHz or more and 50 kHz or less. The scanning speed of the laser light is preferably not less than 100 mm/s and not more than 10000 mm/s.

After light (arrow) is irradiated to the separation layer 2 to change the quality of the separation layer 2 , as shown in FIG. 5( b ), the support base 1 is separated from the substrate 4 . For example, the support base 1 and the base plate 4 are separated by applying a force in a direction in which the support base 1 and the base plate 4 are separated from each other. Specifically, in a state where one of the support base 1 or the substrate 4 side (rewiring layer 6 ) is fixed to the stage, the other side is adsorbed and held by a separation plate having an adsorption pad such as a bellows pad. By lifting, the support base 1 and the substrate 4 can be separated. The force applied to the laminate 30 is not limited as long as it is appropriately adjusted according to the size of the laminate 30. For example, in the case of a laminate with a diameter of about 300 mm, a force of about 0.1 to 5 kgf (0.98 to 49 N) is applied. , the support base 1 and the substrate 4 can be appropriately separated.

[Removal step] The removal step in the embodiment is a step of removing the adhesive layer 3 attached to the substrate 4 after the aforementioned separation step. In Figure 5(b), after the separation step, the adhesive layer 3 and the separation layer 2 are attached to the substrate 4. In the present embodiment, in the removal step, the electronic component 40 is obtained by removing the adhesive layer 3 and the separation layer 2 attached to the substrate 4 .

As a method of removing the adhesive layer 3 etc. adhering to the board|substrate 4, the method of removing the residue of the adhesive layer 3 and the separation layer 2 using a cleaning liquid is mentioned, for example. As the cleaning solution, a cleaning solution containing an organic solvent is preferably used. As the organic solvent in this cleaning solution, it is preferable to use the organic solvent blended with the composition for forming a separation layer and the solvent component blended with the composition for forming an adhesive layer. The adhesive layer formed using the composition for forming an adhesive layer of the above-described embodiment has improved solubility in hydrocarbon solvents. Therefore, in the embodiment, the cleaning removability of the adhesive layer is favorable.

In the manufacturing method of the electronic component of the present embodiment, after the above-mentioned removal step, the electronic component 40 may be further subjected to processes such as solder ball formation, dicing, or oxide film formation. [Example]

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

<Preparation of Adhesive Compositions> (Examples 1 to 10, Comparative Examples 1 to 6) The components shown in Tables 1 to 3 were mixed and dissolved to prepare the adhesive compositions of each example (resin component concentration: 20 mass %) ).

In Tables 1 to 3, the respective abbreviations have the following meanings, respectively. The numerical value in [ ] is the compounding amount (mass part). In addition, the glass transition temperature (°C) of the resin component shown below is based on the use of a dynamic viscoelasticity measuring apparatus Rheogel-E4000 (manufactured by UBM Co., Ltd.), at a frequency of 1 Hz, and a temperature rise of 5°C/min. The speed was obtained from the change in viscoelasticity measured by increasing the temperature from 25°C to 300°C.

(P1)-1: Septon 8004 (trade name), manufactured by KURARAY Co., Ltd. A styrene content of 31% by mass, a weight average molecular weight of 98,000; a hydrocarbon resin having plural constituent units represented by the following chemical formula (P1)-1.

(P1)-2: Tuftec H1051 (trade name), manufactured by Asahi Kasei Co., Ltd. The styrene content is 42% by mass, the ethylene/butene content is 58% by mass, and the weight average molecular weight is 78,000; hydrogenated styrene thermoplastic elastomer.

(P1)-3: Septon 2002 (trade name), manufactured by KURARAY Co., Ltd. A styrene content of 30% by mass, a weight average molecular weight of 54,000, and a hydrocarbon resin having plural constituent units represented by the following chemical formula (P1)-3.

(P1)-4: APL8008T (trade name), manufactured by Mitsui Chemicals Co., Ltd. Glass transition temperature of 70°C, weight average molecular weight of 100,000; hydrocarbon resin (m:n=80:20 (mol ratio)) represented by the following chemical formula (P1)-4.

(P1)-5: TOPAS8007 (trade name), manufactured by POLYPLASTICS Co., Ltd. The glass transition temperature is 65°C, the weight average molecular weight is 95000; the hydrocarbon resin (m:n=35:65 (mol ratio)) represented by the following chemical formula (P1)-5.

(P2)-1: PRZ-10014 (trade name), manufactured by SUMITOMO BAKELITE Co., Ltd. The glass transition temperature was 224° C., and the weight average molecular weight was 8700; the resin represented by the following chemical formula (P2)-1 (m:n=65:35 (molar ratio)).

(P3)-1: glass transition temperature 84°C, weight average molecular weight 9800; adamantyl methacrylate (AdMA) unit/stearyl methacrylate (STMA) unit/styrene (Sty) unit=60/20/ 20 (mass ratio) of the copolymer.

A-DCP: tricyclodecane dimethanol diacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.; a polyfunctional curable monomer represented by the following chemical formula.

(lb)-1: A polymerization inhibitor, IRGANOX1010 (trade name), manufactured by BASF Corporation. Pentaerythritol tetra[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]; a compound represented by the following chemical formula.

(Ia)-1: Thermal polymerization initiator, Percumyl D (trade name), manufactured by NOF Corporation. Bis(1-methyl-1-phenylethyl) peroxide; a compound represented by the following chemical formula.

<Adhesive layer forming step> On a glass support substrate (size 10cm×10cm, thickness 700μm), under the conditions of flow rate 400sccm, pressure 700mTorr, high frequency power 2500W and film forming temperature 240°C, by using C ₄ F ₈ as By the CVD method of the reactive gas, a fluorocarbon film (thickness 1 μm) was formed as a separation layer, and a support was produced.

Next, the adhesive composition of each example was coated on the separation layer formed on the glass support substrate by spin coating at 1500 rpm while rotating. Subsequently, by preliminarily heating the support coated with the adhesive composition of each example at 160°C for 4 minutes, an adhesive layer with a thickness of 5 μm was formed.

<Evaluation> With respect to the adhesive layer formed in the above-mentioned <Adhesive layer forming step>, the compression molding test shown below was performed to evaluate the heat resistance. In addition, the measurement of the complex elastic modulus at the time of heating, the die bonding test, and the evaluation of the cleaning removability were performed, respectively. These results are shown in Tables 4, 5 and 6.

[Compression Molding Test] A substrate (bare wafer) was arranged at a designated position of the adhesive layer formed in the above-mentioned <adhesive layer forming step>, and the support and the substrate were bonded (bonding step). Then, the substrate bonded to the support via the adhesive layer is sealed with a sealing material to produce a sealing body (sealing step). For the sealing body produced here, the positional displacement (displacement amount) of the bare wafer before sealing and after sealing was measured, and the heat resistance was evaluated. Specifically, it is performed as follows.

Using a die bonder (manufactured by Tresky Corporation), the positional displacement (displacement amount) of the bare wafer was measured. First, heat the stage of the die bonder to 50°C and the head to 100°C, and press the substrate (bare wafer) (5mm×5mm×0.7mm) to the adhesive layer with a pressure of 35N for 1 second. superior.

FIG. 6 shows the laminate 10 in which the support 12 and the substrate 4 (bare wafer) are bonded with the adhesive layer 3 interposed therebetween. In FIG. 6 , the laminate 10 is substantially rectangular in plan view, and the substrates 4 ( bare wafer). In addition, regarding the laminated body 10 in plan view, the lateral direction is the X direction, and the vertical direction is the Y direction.

Next, the laminate 10 was heated at 200° C. in a nitrogen atmosphere for 1 hour. After heating, the laminate 10 was placed on a stage heated to 50°C. Next, 12 g of a sealing material containing epoxy resin was applied on the substrate 4 (bare wafer) in the center of the laminate 10 placed on the stage. Next, a force of 10 tons was applied to the laminate 10 while pressing the laminate 10 with a pressing plate (300 mmf) heated to 130° C. under a reduced pressure condition of less than 10 Pa using a sticking device. , while expanding the sealing material so as to cover the entire substrate 4 (bare wafer) at the four corner end portions and the central portion, and compressing for 5 minutes (sealing step). In this way, a sealed body in which the bare wafer is sealed via the sealing material is obtained.

The obtained sealing body was observed from the support body 1 (glass support substrate surface) side using an optical microscope, and the positional shift (displacement amount) of the bare wafer before sealing and after sealing was measured. As shown in FIG. 6 , the sum of the movement distance in the X direction and the movement distance in the Y direction of each substrate 4 (bare wafer) disposed on the next layer 3 from the position before sealing is obtained as each substrate as shown in FIG. 6 . 4 (bare wafer) moving distance. Next, the average value of the moving distance of the substrate 4 (bare wafer) was obtained, and this was used as an evaluation value of the moving distance. Then, the heat resistance was evaluated according to the evaluation criteria shown below. The lower the evaluation value of this moving distance, the higher the heat resistance. Evaluation criteria ○: When the evaluation value of the moving distance of the substrate 4 (bare wafer) is 10 μm or less ×: When the evaluation value of the moving distance of the substrate 4 (bare wafer) exceeds 10 μm

[Measurement of Complex Elastic Modulus] For the adhesive composition of each example, the complex elastic modulus E at 50°C and at 150°C was measured using a dynamic viscoelasticity measuring apparatus (Rheogel-E4000, manufactured by UBM Co., Ltd.). *. First, the adhesive composition was coated on the PET film with the release agent, and heated in an oven under atmospheric pressure at 50° C. and 150° C. for 60 minutes each to form an adhesive layer (thickness 0.5 mm). Next, using the aforementioned dynamic viscoelasticity measuring apparatus, the complex elastic modulus E* of the adhesive layer peeled from the PET film was measured. The measurement conditions are that the shape of the sample is 20mm × 5mm and the thickness is 0.5mm. Under the stretching conditions of the frequency of 1 Hz, the temperature is set to be from room temperature to 215 ° C, and the temperature is increased at a rate of 5 ° C / min. The measurement is performed at 50 ° C and 150 ° C. The complex elastic modulus of . If the complex elastic modulus E* ₅₀ at 50° C. is less than 1.0× ^{10 9} Pa, it can be said that the adhesiveness of the substrate to the support is good. When the complex elastic modulus E* ₁₅₀ at 150°C exceeds 3.0´10 ⁶ Pa, it can be said that the heat resistance of the adhesive layer is high. In addition, in Tables 4-6, the measurement result of the complex elastic modulus E* ₅₀ and the complex elastic modulus E* ₁₅₀ , and the ratio of E* ₅₀ /E* ₁₅₀ are described.

[Die Bonding Test] A substrate (bare wafer) was placed at a specified position of the adhesive layer formed in the above <adhesive layer forming step>, and the support and the substrate were bonded (bonding step). Specifically, the stage of the die bonder (manufactured by Tresky Corporation) was heated to 23°C and the head was heated to 100°C, and the substrate (bare wafer) (5mm x 5mm x 0.7 mm) is crimped on the adhesive layer. Then, according to the evaluation criteria shown below, the bonding state of the substrate (bare wafer) to the bonding layer was evaluated. Evaluation Criteria ○: The substrate (bare wafer) is fixed to the adhesive layer with sufficient strength. ×: When a force is applied, the substrate (bare wafer) is easily peeled off from the adhesive layer.

[Evaluation of Removability by Cleaning] The sealing body obtained in the above sealing step was irradiated with laser light having a wavelength of 532 nm from the glass support substrate side toward the separation layer (fluorocarbon film). Thereby, the separation layer is degenerated, the glass support base is separated from the substrate (bare wafer) included in the sealing body, and the sealing substrate with the adhesive layer exposed is obtained (separation step). Next, the obtained sealing substrate was spray-cleaned for 5 minutes using p-menthane as a cleaning solution to remove the adhesive layer adhering to the substrate (bare wafer) (removal step). Then, the cleaning and removability was evaluated according to the evaluation criteria shown below. Evaluation Criteria ○: No residue of the adhesive layer was seen on the sealing substrate after spray cleaning ×: Residue of the adhesive layer was observed on the sealing substrate after spray cleaning

From the results shown in Tables 4 to 6, it was confirmed that, compared with the adhesive compositions of Comparative Examples 1 to 6, the adhesive compositions of Examples 1 to 10 performed better in the compression molding test, that is, the heat resistance was higher. taller.

1‧‧‧Support base 2‧‧‧Separation layer 3‧‧‧Adhesion layer 4‧‧‧Substrate 5‧‧‧Sealing material layer 6‧‧‧Rewiring layer 10‧‧‧Laminated body 12‧‧‧Support body 20 ‧‧‧Sealing body 30‧‧‧Laminate body 40‧‧‧Electronic component 123‧‧‧Support body with adhesive layer

Fig. 1 is a schematic view showing an embodiment of a laminate to which the present invention is applied. Fig. 2 is a schematic flow chart illustrating an embodiment of a method for producing a laminate. FIG. 2( a ) is a diagram illustrating a step of producing a support, FIG. 2( b ) is a diagram illustrating a step of forming an adhesive layer, and FIG. 2( c ) is a diagram illustrating a bonding step. Fig. 3 is a schematic flow chart illustrating another embodiment of the method for producing the laminate. FIG.3(a) is a figure which shows the laminated body manufactured by the manufacturing method of 1st Embodiment, and FIG.3(b) is a figure explaining a sealing process. Fig. 4 is a schematic flow chart illustrating another embodiment of the method for producing the laminate. FIG. 4( a ) is a diagram showing a sealing body manufactured by the manufacturing method of the second embodiment, FIG. 4( b ) is a diagram illustrating a grinding step, and FIG. 4( c ) is a diagram illustrating a rewiring formation step. Fig. 5 is a schematic sequence diagram illustrating an embodiment of a method of manufacturing a semiconductor package (electronic component). Fig.5 (a) is a figure which shows the laminated body manufactured by the manufacturing method of 3rd Embodiment, FIG.5(b) is a figure which demonstrates a separation process, and FIG.5(c) is a figure which demonstrates a removal process. 6 is a plan view showing a laminate 10 in which the support 1 and the substrate 4 (bare wafer) are bonded with the adhesive layer 3 interposed therebetween.

1‧‧‧Support matrix

2‧‧‧Separation layer

3‧‧‧Additional layer

3s‧‧‧Opposite side

4‧‧‧Substrate

10‧‧‧Laminate

12‧‧‧Support

123‧‧‧Support with adhesive layer

Claims (21)

An adhesive composition, which is an adhesive composition for bonding a support body and a substrate, which contains a hydrocarbon resin (P1) as a resin component (P) and a resin (P2) with a glass transition temperature of 180 ° C or more (but , excluding the aforementioned hydrocarbon resin (P1)), the aforementioned resin (P2) further having a constitution represented by the following general formula (p2-1) of a constituent unit (u21) derived from a monomer comprising a maleimide skeleton unit;

[wherein, R ^u10 represents an organic group having 1 to 30 carbon atoms] and a structural unit (u22) derived from a cycloolefin, the content of the aforementioned resin (P2) is 5 parts by mass relative to 100 parts by mass of the aforementioned hydrocarbon resin (P1) ~75 parts by mass. The adhesive composition of claim 1, wherein the aforementioned constituent unit (u22) is a constituent unit represented by the following general formula (p2-2);

[In the formula, R ^u11 to R ^u14 each independently represent an organic group or a hydrogen atom having 1 to 30 carbon atoms; n is an integer of 0 to 2]. The adhesive composition according to claim 1, which is an adhesive composition for bonding a support and a substrate, wherein the adhesive composition contains at least a hydrocarbon resin (P1) as the resin component (P), and the adhesive composition is obtained from the adhesive composition. Make a test piece of 20mm×5mm×thickness 0.5mm, and under the condition of stretching at a frequency of 1Hz, from room temperature to 215°C, at a rate of 5°C/min, the temperature rises at a rate of 5°C/min. , satisfies both of the following requirements: the complex elastic modulus E* ₅₀ at 50°C is less than 1.0×10 ⁹ Pa, and the complex elastic modulus E* ₁₅₀ at 150°C exceeds 3.0×10 ⁶ Pa. The adhesive composition of claim 3 further satisfies the requirement that the ratio of E* ₅₀ /E* ₁₅₀ is 2000 or less. The adhesive composition according to any one of claims 1 to 4, wherein the hydrocarbon resin (P1) is at least one selected from the group consisting of elastomers and cycloolefin polymers. The adhesive composition according to any one of claims 1 to 4, further comprising a polyfunctional curable monomer. The adhesive composition according to claim 6, wherein the polyfunctional curable monomer contains a polycyclic aliphatic structure. The adhesive composition according to claim 6, wherein relative to the aforementioned resin component (P) Content of the said polyfunctional curable monomer is 5-40 mass % based on a total amount of 100 mass %. The adhesive composition according to any one of claims 1 to 4, which further contains a polymerization inhibitor. The adhesive composition according to claim 6, which further contains a thermal polymerization initiator. The adhesive composition according to any one of claims 1 to 4, which further contains a hydrocarbon solvent. An adhesive layer-attached support, comprising: a support to which a substrate is attached, and an adhesive layer formed on the support using the adhesive composition according to any one of claims 1 to 11. The support with an adhesive layer according to claim 12, wherein the support is provided with a light-transmitting support substrate and a separation layer provided on the support substrate, the separation layer is adjacent to the adhesive layer, and is irradiated by light. Deterioration, the layer of the support base can be separated from the substrate attached to the support body. An adhesive film comprising: a film, and an adhesive layer formed on the film using the adhesive composition according to any one of claims 1 to 11. A laminate comprising a support and a substrate via an adhesive layer, wherein the adhesive layer is a layer formed using the adhesive composition according to any one of claims 1 to 11. A kind of laminate, it has: as the support of claim 12 or 13 with the adhering layer, and the adhering layer that is equipped with the aforementioned support that is attached with the adhering layer is configured with the face on the opposite side of the aforementioned support side substrate. A kind of manufacture method of laminated body, it is the manufacture method of the laminated body that is bonded with support body and substrate through adhering layer, it has: on aforementioned support body or at least one on aforementioned base plate, use as claim 1～11 In any one of the adhesive compositions, the adhesive layer forming step of forming the adhesive layer, and the adhesive layer formed via the adhesive layer forming step, laminating the support and the substrate. The method for producing a laminate according to claim 17, further comprising, after the bonding step, sealing the substrate bonded to the support via the adhesive layer via a sealing material to form a seal for the sealing body step. The method for manufacturing a laminate of claim 18, further comprising: after the sealing step, grinding a portion of the sealing material in the sealing body so that a part of the substrate is exposed, and after the grinding step, the Rewiring is formed on the exposed substrate Wiring forming step. The method for producing a laminate according to any one of claims 17 to 19, further comprising the step of forming a separation layer degraded by light irradiation on at least one side of the support substrate that transmits light, and the steps of producing the aforementioned support body, in In the bonding step, the support and the substrate are bonded while making the separation layer and the adhesive layer face each other. A method of manufacturing an electronic component, comprising: after obtaining a laminate according to the method for manufacturing a laminate of claim 20, the method comprising: irradiating the separating layer with light through the supporting substrate to degenerate the separating layer and a separation step of separating the support substrate from the substrate included in the laminate, and a removal step of removing the adhesive layer attached to the substrate after the separation step.

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