TWI643922B - Adhesive composition and adhesive film - Google Patents

Abstract

An object of the present invention is to provide an adhesive composition and an adhesive film capable of reducing swelling and peeling from a support due to a resist solvent.

The solution of the present invention is an adhesive composition containing an elastomer, a hydrocarbon resin, and an acrylic resin. The elastic system contains a styrene unit as a structural unit of the main chain, and the content of the styrene unit is 14 weight. % Or more and 50% by weight or less.

Description

Adhesive composition and adhesive film

The present invention relates to an adhesive composition and an adhesive film.

As mobile phones, digital audio and video devices, and chip cards have become more functional, and the semiconductor silicon wafers (hereinafter referred to as wafers) have been miniaturized and thinned, there is a demand for high silicon integration in packages. improve. For example, in integrated circuits in which a plurality of chips such as a chip size package (CSP) or a multi-chip package (MCP) are integrated and packaged, thinning is required. In order to achieve higher integration of the wafers in the package, the thickness of the wafers must be reduced to a range of 25 to 150 μm.

However, a semiconductor wafer (hereinafter referred to as a wafer), which is the basis of the wafer, is thinned by grinding, so that its strength becomes weaker, and cracks or warpage on the wafer easily occur. In addition, since it is difficult to automatically transfer a wafer system whose strength is weakened due to the thinning of the plate, it must be manually transferred, and the processing is complicated.

Therefore, a wafer handling system (wafer handling system), which adheres a plate made of glass, rigid plastic, etc. called a support plate to a wafer to be ground, and maintains the strength of the wafer to prevent cracks and wafers Warping. Since wafer strength can be maintained by the wafer handling system (WHS), the transportation of thinned semiconductor wafers can be automated.

In the wafer transfer system, the wafer and the support plate are bonded using an adhesive tape, a thermoplastic resin, an adhesive, or the like. Next, after the wafer to which the support plate is attached is thinned, the support plate is peeled from the substrate before the wafer is diced. When the adhesive is used for bonding the wafer to the support plate, the adhesive is dissolved and the wafer is peeled from the support plate.

Here, in recent years, a hydrocarbon-based adhesive has been developed as the above-mentioned adhesive (Patent Document 1).

[Prior technical literature] [Patent Literature]

[Patent Document 1] Japanese Special Publication No. 2009-529065 (publication on August 13, 2009)

However, when the hydrocarbon-based adhesive described in Patent Document 1 is used in WHS, the wafer with the support plate dipped in the resist solvent is swelled in the resist peeling step in the resist peeling step, and A problem of peeling of the support plate occurred.

The adhesive composition and the adhesive film of the present invention have been completed in view of the above-mentioned problems, and a main object thereof is to provide an adhesive composition and an adhesive film capable of reducing swelling due to a resist solvent and peeling from a support.

The adhesive composition of the present invention is to solve the above-mentioned problems, and is characterized by containing an elastomer, a hydrocarbon resin, and an acrylic resin. The elastic system contains a styrene unit as a structural unit of the main chain, and the content of the styrene unit It is 14% by weight or more and 50% by weight or less.

According to the above-mentioned structure, it is possible to achieve an effect of providing an adhesive composition capable of reducing swelling and peeling from a support due to a resist solvent.

Hereinafter, embodiments of the present invention will be described in detail. The adhesive composition according to an embodiment of the present invention contains an elastomer, a hydrocarbon resin, and an acrylic resin. The elastic system includes a styrene unit as a structural unit of a main chain, and the content of the styrene unit is 14% by weight. Above 50% by weight.

Since the adhesive composition of the present invention contains an elastomer and a hydrocarbon resin, it can reduce the swelling of the composition caused by the solvent of the inhibitor. The elastic system contains a styrene unit as a structural unit of the main chain, and the content of the styrene unit is 14% by weight or more and 50% by weight or less. Furthermore, since the adhesive composition of the present invention contains an acrylic resin, the wafer (substrate) and the support can be appropriately bonded while maintaining heat resistance.

The content of the elastomer is preferably in a range of 50% by weight or more and 98% by weight or less based on the total amount of the elastomer, the hydrocarbon resin, and the acrylic resin contained in the adhesive composition of the present invention. The content rate is in the range of 1% by weight to 49% by weight, and the content rate of the acrylic resin is in the range of 1% by weight to 49% by weight. Furthermore, it is more preferable that the content of the elastomer is in a range of 50% by weight or more and 90% by weight or less with respect to the total amount of the elastomer, the hydrocarbon resin, and the acrylic resin. The range of the weight% or less is the range of the content of the acrylic resin of 5 weight% or more and 45% by weight or less. By making the elastomer the main component of the adhesive composition of the present invention, it is possible to more appropriately reduce the swelling of the composition and the peeling of the support due to the inhibitor solvent.

[Elastomer]

The elastomer contained in the adhesive composition of the present invention contains a styrene unit as a structural unit of the main chain, and the content of the styrene unit is 14% by weight or more and 50% by weight or less.

In the present specification, "construction unit" means a structure derived from a main chain of a monomer of one molecule in a structure constituting a polymer.

In the present specification, "styrene unit" refers to a structural unit derived from the styrene when the styrene or a styrene derivative is polymerized, and the "styrene unit" may have a substituent. Examples of the substituent group include an alkyl group having 1 to 5 carbons, an alkoxy group having 1 to 5 carbons, an alkoxyalkyl group having 1 to 5 carbons, ethoxyl, carboxyl, and the like.

When the content of the styrene unit is 14% by weight or more, it can be used for processes such as thinning and mounting without reducing the adhesion or grinding properties of the substrate. When the content of the styrene unit is 50% by weight or less, the chemical resistance of the adhesive composition of the present invention can be appropriately maintained.

The elastomer contained in the adhesive composition of the present invention preferably has a weight average molecular weight in a range of 20,000 or more and 200,000 or less, and more preferably in a range of 50,000 or more and 150,000 or less.

When the content of the styrene unit is in the range of 14% by weight or more and 50% by weight or less, and the weight average molecular weight of the elastomer is in the range of 20,000 or more and 200,000 or less, the styrene unit can be easily dissolved in a hydrocarbon-based solvent described later. The adhesive composition is easily and quickly removed. In addition, by setting the weight-average molecular weight to the above range, the resist solvents (for example, PGMEA, PGME, NMP, etc.) and acids (hydrofluoric acid, etc.) exposed when the wafer is supplied to the resist lithography step are used. And alkali (TMAH, etc.) show excellent resistance.

The content of the styrene unit is more preferably within a range of 17% by weight to 40% by weight.

As for the elastomer, if the content of the styrene unit is in the range of 14% by weight to 50% by weight, various elastomers can be used. For example: polystyrene-poly (ethylene / propylene) fluorene copolymer (SEP), styrene-isoprene-styrene fluorene copolymer (SIS), styrene-butadiene-styrene fluorene copolymer (SBS), styrene-butadiene-butene-styrene fluorene copolymer (SBBS), and hydrides thereof, styrene-ethylene-butene-styrene fluorene copolymer (SEBS), Styrene-ethylene-propylene-styrene fluorene copolymer (styrene-isoprene-styrene fluorene copolymer) (SEPS), styrene-ethylene-ethylene-propylene-styrene fluorene copolymer (SEEPS) ), Styrene block is a styrene-ethylene-ethylene-propylene-styrene fluorene copolymer (SeptonV9461 (KURARAY Co., Ltd.), SeptonV9475 (KURARAY Co., Ltd.)), a styrene block copolymer The block is a reactive cross-linked styrene-ethylene-butene-styrene fluorene block copolymer (Septon V9827 (made by Kuraray Co., Ltd.) having a reactive polystyrene hard block), etc., and a styrene unit can be used. The content is within the above range.

The elastomer contained in the adhesive composition of the present invention is preferably a styrene-based elastomer having two or more types of styrene units contained in the structural unit as a main chain, which are different from each other. For example, two types of elastomers such as Septon8007L and Septon2004, SeptonV9827, and Septon2002 produced by Sepura (trade name) manufactured by KURARAY Co., Ltd. may be included.

That is, the adhesive composition of the present invention may contain plural kinds of elastomers. As long as at least one of plural kinds of elastomers contains a styrene unit as a structural unit of the main chain, and the content of the styrene unit is in a range of 14% by weight to 50% by weight, The scope of the invention. In addition, when a plurality of types of elastomers are contained in the adhesive composition of the present invention, the results of mixing may be adjusted so that the content of the styrene unit falls within the above-mentioned range. For example, if the content of the styrene unit is 30% by weight of Septon4033 produced by Kuraray Co., Ltd. and the content of the styrene unit is 13% by weight of Septon2063, the weight ratio is When mixing 1: 1, the styrene content is 21 to 22% by weight and 14% by weight or more based on the entire elastomer contained in the adhesive composition. In addition, for example, when 10% by weight of styrene units and 60% by weight of styrene are mixed in a ratio of 1: 1, the ratio becomes 35% by weight, which is within the above range. The present invention can also take such a form. Moreover, it is more preferable that the plurality of types of elastomers contained in the adhesive composition of the present invention all contain a styrene unit within the above range.

When the content of the two types of styrene units is an elastomer different from each other, the styrene-based elastomer having a large content of styrene units is preferably 20% by weight or more and 80% by weight or less. Range. In addition, for a styrene-based elastomer having a small content of styrene units, the content of styrene units is preferably in a range of 1% by weight to 30% by weight. By using a styrene-based elastomer having a large content of styrene units, it is possible to provide processes for thinning and mounting without reducing the adhesion or grinding properties of the substrate. By using a styrene-based elastomer having a small amount of styrene units, the chemical resistance of the adhesive composition of the present invention can be appropriately maintained.

Furthermore, the content of two types of styrene units is In the case of such a different elastomer, the styrene-based elastomer having a larger content of styrene units relative to the total amount of the styrene-based elastomer is preferably in a range of 20% by weight or more and 80% by weight or less.

Next, even in elastomers, hydrides are preferred. If it is a hydride, it will further improve the stability to heat, and it is not easy to cause degradation such as decomposition or polymerization. In addition, it is more preferable from the viewpoint of solubility in a hydrocarbon-based solvent and resistance to a resist solvent.

In addition, even in an elastomer, a block polymer having styrene at both ends is preferable. This is because styrene having high thermal stability is blocked at both ends to exhibit higher heat resistance.

More specifically, the elastic system is more preferably a hydride of a block copolymer of styrene and a conjugated diene. This will further improve the stability to heat and will not easily cause deterioration such as decomposition or polymerization. In addition, by blocking styrene having high thermal stability at both ends, higher heat resistance is exhibited. Furthermore, it is more preferable from a viewpoint of the solubility with respect to a hydrocarbon type solvent, and the resistance to a resist solvent.

Commercially available products that can be used as the elastomer contained in the adhesive composition of the present invention include, for example, "Septon (trade name)" manufactured by KURARAY Co., Ltd. and "HYBRAR (trade name)" manufactured by KURARAY Co., Ltd. "," Tuftec (trade name) "manufactured by Asahi Kasei Corporation," DYNARON (trade name) "manufactured by JSR Corporation, and so on.

[Acrylic resin]

The adhesive composition of the present invention contains an acrylic resin. By adding an acrylic resin, the Young's modulus of the adhesive composition can be increased, and the adhesiveness of the adhesive composition can be improved.

In addition, since an acrylic resin as a low-molecular plastic component is contained in the adhesive composition, it has high thermal fluidity and can be bonded to, for example, a wafer and a support plate without applying high temperature or high pressure. Therefore, for example, the adhesive composition can appropriately adhere the wafer to the support even at a bonding temperature of 220 ° C. or lower.

The acrylic resin preferably has a 5% thermal weight reduction temperature of 280 ° C or higher. Thereby, heat resistance required in a wafer processing process can be obtained. The acrylic resin can be said to have, for example, a heat resistance of 220 ° C. or higher required in a wafer processing process. The 5% thermal weight reduction temperature of the acrylic resin is more preferably 300 ° C or more.

Here, the 5% thermal weight reduction temperature of acrylic resin is that for acrylic resin, heating starts at 25 ° C in a nitrogen environment and increases the heating temperature by 10 ° C every 1 minute. Only 5 weights of the initial weight are reduced. Temperature at% weight. The weight of the acrylic resin can be measured by a thermogravimetric measuring device.

Examples of the acrylic resin include resins obtained by polymerizing a (meth) acrylate as a monomer.

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

Examples of the (meth) acrylic acid alkyl esters having a chain structure include acrylic long-chain alkyl esters having an alkyl group having 15 to 20 carbon atoms, and acrylic alkanes having an alkyl group having 1 to 14 carbon atoms. Esters and the like. Examples of acrylic long-chain alkyl esters having an alkyl group having 15 to 20 carbon atoms include alkyl groups of n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, and n- Nondecyl, n-icosyl, etc. alkyl esters of acrylic acid or methacrylic acid. The alkyl group may be branched.

Examples of the acrylic alkyl esters having an alkyl group having 1 to 14 carbon atoms include well-known acrylic alkyl esters used in conventional acrylic adhesives. For example: the alkyl group is composed of methyl, ethyl, propyl, butyl, 2-ethylhexyl, isooctyl, isononyl, isodecyl, dodecyl, lauryl, tridecyl, etc. Alkyl esters of acrylic or methacrylic acid.

Examples of the (meth) acrylate having an aliphatic ring include cyclohexyl (meth) acrylate, cyclopentyl (meth) acrylate, 1-adamantyl (meth) acrylate, norbornyl ( (Meth) acrylate, isofluorenyl (meth) acrylate, tricyclodecyl (meth) acrylate, tetracyclododecyl (meth) acrylate, dicyclopentanediyl (meth) Acrylates and the like, but more preferably isoamyl methacrylate and dicyclopentadiyl (meth) acrylate.

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

The acrylic resin contained in the adhesive composition of the present invention may be obtained by polymerizing one of the monomers using the (meth) acrylic acid ester monomer described above, or may be obtained by polymerizing using a plurality of monomers. By.

The acrylic resin contained in the adhesive composition of the present invention may be a resin obtained by polymerizing a monomer using the above (meth) acrylic acid ester and another monomer capable of polymerizing the same. Examples of the single system capable of polymerizing with a monomer such as (meth) acrylate include styrene or a derivative of styrene, a monomer containing a maleimide group, and the like.

Examples of single systems containing maleimide imine include: N-methylmaleimide, N-ethylmaleimide, Nn-propylmaleimide, N-isopropylimine Lyme, Nn-butylmaleimide, N-isobutylmaleimide, N-sec-butylmaleimide, N-tert-butylmaleimide, Nn-pentylmaleimide, Nn-hexylmaleimide, Nn-heptylmaleimide, Nn-octylmaleimide, N-laurylmaleimide, N -Stelyl maleimide, alkyl-containing maleimide, N-cyclopropylmaleimide, N-cyclobutylmaleimide, N-cyclopentylmaleimide Imine, N-cyclohexylmaleimide, N-cycloheptylmaleimide, N-cyclooctylmaleimide, maleimide having aliphatic hydrocarbon groups, N-phenyl Aromatic maleates with aryl groups such as maleimide, Nm-methylphenylmaleimide, No-methylphenylmaleimide, Np-methylphenylmaleimide醯 imine and so on.

The acrylic resin preferably contains a styrene unit as a structural unit. The acrylic resin contains styrene units, which not only improves the heat resistance of the acrylic resin, but also its solubility and resistance to solvents. It is also preferable from the viewpoint of the resistance of the solvent.

The acrylic resin is preferably soluble in a hydrocarbon solvent. Examples of the hydrocarbon-based solvent capable of dissolving the acrylic resin include decalin, but details of other hydrocarbon-based solvents are described later.

The solubility parameter (SP value) of the acrylic resin is preferably 6 or more and 10 or less. When the SP value is 6 or more and 10 or less, the acrylic resin is compatible with the elastomer, and a more stable adhesive composition can be obtained. The SP value of the acrylic resin is more preferably 6.5 or more and 9.5 or less.

The weight average molecular weight of the acrylic resin is preferably from 2,000 to 70,000. When the weight average molecular weight of the acrylic resin is 2,000 or more and 70,000 or less, an adhesive composition having thermal fluidity suitable for bonding of a wafer and a support, for example, can be provided. The weight average molecular weight of the acrylic resin is preferably 5,000 or more and 50,000 or less.

Acrylic resins may be mixed in plural types. That is, the adhesive composition of the present invention may contain plural kinds of acrylic resins. In addition, the acrylic resin of the plurality of types contained in the adhesive composition of the present invention preferably has a thermal weight reduction temperature of 280 ° C or higher for all 5%.

The acrylic resin contained in the adhesive composition of the present invention is a resin that synthesizes each monomer by well-known radical polymerization.

Examples of the acrylic resin are: A resin obtained by random polymerization of (meth) acrylates of a family ring, alkyl (meth) acrylates composed of a chain structure, and styrene as monomers. In this case, examples of the (meth) acrylic acid ester having an aliphatic ring include tricyclodecyl (meth) acrylate, 1-adamantyl (meth) acrylate, and the like, which are composed of a chain structure Examples of the (meth) acrylic acid alkyl ester include acrylic acid having an alkyl group of n-icosyl, or alkyl ester of methacrylic acid. These acrylic resins can also be used in appropriate combination.

[Hydrocarbon resin]

The hydrocarbon resin is a resin having a hydrocarbon skeleton and polymerizing a monomer component. Examples of the hydrocarbon resin contained in the adhesive composition of this embodiment include cycloolefin polymers (hereinafter, also referred to as "resin A"), and terpene-based resins, rosin-based resins, and petroleum-based resins. At least one resin selected from the constituent group (hereinafter, also referred to as "resin B").

The cycloolefin polymer is a resin obtained by polymerizing a cycloolefin monomer as a monomer component. Examples of cycloolefin monosystems include bicyclics such as norbornene, norbornene, tricyclics such as dicyclopentadiene, hydroxydicyclopentadiene, and tetracyclics such as tetracyclododecene. , Pentacyclics such as cyclopentadiene trimers, heptads such as tetracyclopentadiene, or alkyl (methyl, ethyl, propyl, butyl, etc.) substituents of these polycyclics , An alkenyl (e.g. vinyl) substitute, an alkylidene (e.g. ethylene) substitute, an aryl (phenyl, tolyl, naphthyl, etc.) substitute, and the like. The resin (A) may be one obtained by polymerizing only one of these cycloolefin monomers, or may be one obtained by copolymerizing two or more kinds thereof.

The monomer component contained in the resin (A) is not limited. The cycloolefin monomer may contain other monomers which can be copolymerized with the cycloolefin monomer. Examples of other monomers include linear or branched olefinic monomers. Examples of such olefinic single systems include ethylene, propylene, 1-butene, isobutylene, and 1-hexene. Α-olefin. The olefinic single system may be used alone or in combination of two or more.

Although the molecular weight of the resin (A) is not particularly limited, for example, the weight average molecular weight (Mw) measured as a polystyrene conversion value by gel permeation chromatography (GPC) is 50,000 to 200,000, and more preferably 50,000 ~ 150,000. When the weight average molecular weight of the resin (A) is within the above range, cracking is unlikely to occur after film formation, and solubility in a specific solvent can be obtained.

In addition, the monomer component constituting the resin (A) in which 5 mol% or more is a cyclic olefin monomer is preferable from the viewpoint of high heat resistance (low thermal decomposition property, thermal weight reduction property), and 10 mol % Or more is a cyclic olefin monomer, and more preferably 20% or more. Although the upper limit is not particularly limited, a value of 80 mol% or less is preferable from the viewpoints of solubility and stability over time of the solution, and a value of 70 mol% or less is more preferable. When other monomers are linear or branched olefinic monomers, 10 to 90 mol% of the monomer component constituting the resin (A) is soluble and flexible. From a viewpoint point of view, 20 to 85 mole% is more preferable, and 30 to 80 mole% is particularly preferable.

The polymerization method and polymerization conditions of the monomer component are not particularly limited, and may be performed using a conventionally known method.

Examples of commercially available products that can be used as resin (A) For example: "APEL (trade name)" by Mitsui Chemicals Co., Ltd., "TOPAS (trade name)" by Polyplastics Co., Ltd., "ZEONOR (trade name)" and "ZEONEX (commodity)" by Japan Zeon Corporation Name) "and" ARTON (trade name) "made by JSR Corporation.

The resin (B) is at least one resin selected from the group consisting of the above-mentioned terpene-based resin, rosin-based resin, and petroleum-based resin. Examples of terpene-based resins include terpene resins, terpene phenol resins, modified terpene resins, hydrogenated terpene resins, and hydrogenated terpene phenol resins. Examples of the rosin-based resins include rosin, rosin ester, hydrogenated rosin, hydrogenated rosin ester, polymerized rosin, polymerized rosin ester, and modified rosin. Examples of petroleum-based resins include aliphatic or aromatic petroleum resins, hydrogenated petroleum resins, modified petroleum resins, alicyclic petroleum resins, and coumarone-indene petroleum resins. Among these, hydrogenated terpene resins and hydrogenated terpene phenol resins are particularly preferred.

Although the molecular weight of the resin (B) is not particularly limited, for example, the weight average molecular weight (Mw) measured as a polystyrene conversion value by GPC is 300 to 10,000, and preferably 500 to 5,000. When the weight average molecular weight of the resin (B) is within the above range, cracking is unlikely to occur after film formation, and high heat resistance (resistance to thermal decomposition and sublimation) can be obtained.

Alternatively, the resin (A) and the resin (B) may be mixed and used. The content of the resin (A) is preferably 40 parts by weight or more of the entire hydrocarbon resin, and more preferably 60 parts by weight or more. When the content of the resin (A) is 40 parts by weight or more of the entire hydrocarbon resin, the system exhibits flexibility and high heat resistance (low Thermal decomposition).

[Solvent]

The solvent contained in the adhesive composition of the present invention is only required to have the function of dissolving an elastomer, a hydrocarbon resin, and an acrylic resin. For example, non-polar hydrocarbon solvents, polar and non-polar petroleum solvents can be used. Solvents, etc.

Preferably, the solvent system can contain a condensed polycyclic hydrocarbon. By making the solvent contain condensed polycyclic hydrocarbons, it is possible to avoid white turbidity that may occur when the adhesive composition is stored in a liquid form (especially at low temperature), and to improve product stability.

Examples of the hydrocarbon-based solvent include straight-chain, branched-chain, or cyclic hydrocarbons. Examples include linear hydrocarbons such as hexane, heptane, octane, nonane, methyloctane, decane, undecane, dodecane, and tridecane, and branches having 4 to 15 carbon atoms. Chained hydrocarbons; p-menthane, o-menthane, m-menthane, diphenylmenthane, 1,4-terpenediol, 1,8-terpenediol, pinane, norbornane, fluorene Saturated aliphatic hydrocarbons such as alkane, thujane, pinane, longifolene, α-terpinene, β-terpinene, γ-terpinene, α-pinene, β-pinene, α-side Ketone, β-Thujone and so on.

Examples of the petroleum-based solvent include cyclohexane, cycloheptane, cyclooctane, naphthalene, decahydronaphthalene, and tetrahydronaphthalene.

In addition, a condensed polycyclic hydrocarbon refers to a hydrocarbon in which two or more monocyclic rings are condensed rings formed by supplying only one edge of each ring to each other, and it is preferable to use a hydrocarbon obtained by condensing two monocyclic rings .

Such a hydrocarbon system may be a combination of a 5-membered ring and a 6-membered ring, or a combination of 2 6-membered rings. Examples of the hydrocarbon system combining a 5-membered ring and a 6-membered ring include: indene, pentalene, dihydroindene, and tetrahydroindene. Examples of the hydrocarbon system combining two 6-membered rings include: Naphthalene, tetrahydronaphthalene and decahydronaphthalene.

When the solvent contains the above-mentioned condensed polycyclic hydrocarbon, the component system contained in the solvent may be only the above-mentioned condensed polycyclic hydrocarbon, or may contain other components such as a saturated aliphatic hydrocarbon. In this case, the content of the condensed polycyclic hydrocarbon is preferably 40 parts by weight or more of the entire hydrocarbon-based solvent, and more preferably 60 parts by weight or more. When the content of the condensed polycyclic hydrocarbon is 40 parts by weight or more of the entire hydrocarbon-based solvent, the system can exhibit high solubility to the resin. If the mixing ratio of the condensed polycyclic hydrocarbon and the saturated aliphatic hydrocarbon is within the above range, the odor of the condensed polycyclic hydrocarbon can be reduced.

In addition, although the content of the solvent in the adhesive composition of the present invention may be appropriately adjusted in accordance with the thickness of the adhesive layer to be formed using the adhesive composition, for example, the total amount of the adhesive composition is set to 100. In the case of parts by weight, a range of 20 parts by weight to 90 parts by weight is preferred. When the content of the solvent is within the above range, viscosity adjustment becomes easy.

(Thermal polymerization inhibitor)

In the present invention, the adhesive composition may contain a thermal polymerization inhibitor. Thermal polymerization inhibitors have the function of preventing free radical polymerization caused by heat. can. Specifically, since a thermal polymerization inhibitor exhibits high reactivity to radicals, it reacts more preferentially than a monomer and inhibits polymerization of the monomer. The adhesive composition containing such a thermal polymerization inhibitor is subjected to a high temperature environment (especially 250 ° C to 350 ° C), and the polymerization reaction is suppressed.

For example, in a semiconductor manufacturing step, there is a high-temperature process in which a wafer to which a support plate (support) is adhered is heated at 250 ° C. for one hour. At this time, if the adhesive composition is polymerized due to the high temperature, the solubility of the release liquid used to peel the support plate from the wafer after the high temperature process is reduced, and the support plate cannot be well peeled off from the wafer. . However, the adhesive composition of the present invention containing a thermal polymerization inhibitor can inhibit oxidation due to heat and the subsequent polymerization reaction. Therefore, the support plate can be easily peeled off even after a high-temperature process, and Suppresses the occurrence of residue.

The thermal polymerization inhibitor is not particularly limited as long as it is effective in preventing free radical polymerization caused by heat, but a thermal polymerization inhibitor having a phenol is preferred. This ensures good solubility even after high-temperature treatment in the atmosphere. As such a thermal polymerization inhibitor, a hindered phenol-based antioxidant can be used. Examples include gallophenol, 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 "-ethylene ginseng (2-methylphenol), 4,4', 4 "-Ethylene ginsengol, 1,1,3-ginseng (2,5-dimethyl-4-hydroxyphenyl) -3-phenylpropane, 2,6-di-tert-butyl-4- Methylphenol, 2,2'-methylenebis (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) -propanyloxy) -1,1-dimethyl Ethyl] -2,4,8,10-tetraoxaspiro (5,5) undecane, triethylene glycol-bis-3- (3-tert-butyl-4-hydroxy-5-methyl Phenyl) propionate, n-octyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, pentaerythritol [3- (3,5-di-tert -Butyl-4-hydroxyphenyl) propionate] (trade name IRGANOX1010, manufactured by BASF), ginseng (3,5-di-tert-butylhydroxybenzyl) isocyanurate, thiodioxane Ethylbis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate]. The thermal polymerization inhibitors may be used alone or in combination of two or more.

The content of the thermal polymerization inhibitor may be appropriately determined according to the type of the elastomer, the type of the hydrocarbon resin, the type of the acrylic resin, and the use and use environment of the adhesive composition. When the total amount of the resin and the acrylic resin is 100 parts by weight, it is preferably 0.1 part by weight or more and 10 parts by weight or less. When the content of the thermal polymerization inhibitor is within the above range, the effect of inhibiting polymerization due to heat can be exerted well, and after the high-temperature process, the decrease in the solubility of the adhesive composition to the peeling liquid can be further suppressed.

(Add solvent)

In addition, the adhesive composition of the present invention may contain an additive solvent composed of a composition that dissolves a thermal polymerization inhibitor and is different from a solvent that dissolves an elastomer, a hydrocarbon resin, and an acrylic resin. structure. Although the solvent to be added is not particularly limited, an adhesive composition may be used. An organic solvent in which the contained ingredients are dissolved.

The organic solvent may be any one that can dissolve each component of the adhesive composition to form a homogeneous solution, and can be used arbitrarily or in combination of two or more.

Specific examples of the organic solvent include, for example, terpene solvents having an oxygen atom, a carbonyl group, or an acetoxy group as a polar group, and examples thereof include geraniol, nerol, agarol, lemon olein, and fragrance. Mannitol, menthol, isomenthol, neomenthol, α-terpineol, β-terpineol, γ-terpineol, terpinen-1-ol, terpinen-4-ol, dihydro Rosinol acetate, 1,4-Eucalyptol, 1,8-Eucalyptol, Borneol, Carrageenone, Ionone, Thujone, Camphor. In addition, lactones such as γ-butyrolactone; acetone, methyl ethyl ketone, cyclohexanone (CH), methyl-n-pentyl ketone, methyl isoamyl ketone, 2-heptanone, etc. Ketones; Polyols of ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, etc .; ethylene glycol monoacetate, diethylene glycol monoacetate, propylene glycol monoacetate, or dipropylene glycol monoethyl Monomethyl ethers, monoethyl ethers, monopropyl ethers, monobutyl ethers, and monobenzenes of compounds having an ester bond such as an acid ester, the above-mentioned polyols, or compounds having the above-mentioned ester bond Derivatives of polyhydric alcohols such as compounds with ether linkages such as alkyl ethers (among these, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME) is preferred); such as two Dioxane cyclic ethers, or methyl lactate, ethyl lactate (EL), methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, Ester of ethyl ethoxypropionate; aromatics of anisole, ethyl benzyl ether, cresyl methyl ether, diphenyl ether, dibenzyl ether, phenyl ether, butyl phenyl ether, etc. Family Tied Organic solvents and so on.

Although the content of the added solvent may be appropriately determined depending on the type of the thermal polymerization inhibitor, etc., for example, a solvent (a main solvent) in which the elastomer, a hydrocarbon resin and an acrylic resin are dissolved, and a solvent (a solvent in which the thermal polymerization inhibitor is dissolved ( When the total of the added solvents) is 100 parts by weight, it is preferably 1 part by weight or more and 50 parts by weight or less, and more preferably 1 part by weight or more and 30 parts by weight or less. When the content of the added solvent is within the above range, the thermal polymerization inhibitor can be sufficiently dissolved.

(Other ingredients)

The adhesive composition may further contain other substances having miscibility within a range that does not impair the essential characteristics of the present invention. For example, conventional additives such as addition resins, plasticizers, auxiliary adhesives, stabilizers, colorants, and surfactants can be used to improve the performance of the adhesive.

(Method for preparing adhesive composition)

The method for preparing the adhesive composition of the present embodiment is not particularly limited, and a known method may be used. For example, an elastomer, a hydrocarbon resin, and an acrylic resin are dissolved in a solvent, and an existing stirring device is used. By stirring each composition, the adhesive composition of this embodiment is obtained.

In addition, when a thermal polymerization inhibitor is added to the adhesive composition of this embodiment, the thermal polymerization inhibitor is dissolved in It is preferable to add a solvent to dissolve the thermal polymerization inhibitor in advance.

(Use of the adhesive composition of this embodiment)

The adhesive composition of this embodiment is used to adhere a wafer (substrate) and a support for the wafer.

The support is a member that exerts the effect of supporting the wafer in the step of thinning the wafer, and is adhered to the wafer by the adhesive composition of this embodiment. In one embodiment, the support system is formed of, for example, glass or silicon having a film thickness of 500 to 1,000 μm.

Moreover, in one embodiment, the support system is provided with a hole penetrating the support in the thickness direction. Through the hole, a solvent for dissolving the adhesive composition is allowed to flow between the support and the wafer, whereby the support and the wafer can be easily separated.

Adhesion of the wafer to the support by the adhesive composition, for example, as long as the adhesive composition is coated on the wafer, a bonding layer is formed by heating, and the support is attached to the crystal through the bonding layer. Just round it. Although the film thickness of an adhesive agent is not specifically limited, For example, it can be the range of 5 micrometers or more and 200 micrometers or less. In addition, the heating conditions are not particularly limited as long as they are appropriately set according to the adhesive composition to be used, but they can be carried out by increasing the temperature, for example, in a range of 50 ° C or higher and 250 ° C or lower. The baking is performed in stages, and the adhesive layer is efficiently formed into a film.

In addition, for attaching a support for a wafer, for example, the support can be superposed on the side where the film is formed with an adhesive layer and pressurized in a vacuum at a high temperature (for example, 215 ° C), thereby And attach the support On wafer. However, the method of attaching is to appropriately select a suitable one from various conventionally known methods according to the state of the substrate (concave and convex on the surface, strength, etc.), the composition of the adhesive composition, and the material of the support. .

In addition, in other embodiments, in addition to the bonding layer, another reaction layer may be interposed between the support and the wafer. The reaction layer is deteriorated by absorbing the light irradiated through the support, and the reaction layer is irradiated with light or the like by irradiating light on the reflection layer, whereby the support can be easily separated from the wafer. In this case, it is preferable to use a support body without a hole provided in the thickness direction.

As long as the light irradiated to the reaction layer is appropriate for the wavelength that the reaction layer can absorb, for example, YAG laser, Libbey laser, glass laser, YVO ₄ laser, LD laser, fiber laser, etc. are used as appropriate. Liquid lasers such as solid lasers, pigment lasers, CO ₂ lasers, excimer lasers, Ar lasers, He-Ne lasers, gas lasers, semiconductor lasers, free electron lasers, etc. , Or non-laser light. The wavelength of light to be absorbed by the reaction layer is not limited to this, but may be, for example, light having a wavelength of 600 nm or less.

The reaction layer may contain, for example, a light absorber which is decomposed by light or the like. As the light absorbing agent, for example, graphite powder, iron, aluminum, copper, nickel, cobalt, manganese, chromium, zinc, tellurium and other fine metal powders, black titanium oxide and other metal oxide powders, carbon black, or aromatic Diamine-based metal complexes, aliphatic diamine-based metal complexes, aromatic dithiol-based metal complexes, mercaptophenol-based metal complexes, squaraine-based compounds, cyanine-based pigments, methine Dyes such as basic pigments, naphthoquinone pigments, anthraquinone pigments, or pigment. Such a reaction layer can be formed, for example, by mixing with a binder resin and coating the reaction layer on a support. In addition, a resin having a light absorbing group can also be used.

In addition, as the reaction layer, an inorganic film or an organic film formed by a plasma CVD method may be used. As the inorganic film system, for example, a metal film can be used. As the organic film system, for example, a fluorocarbon film can be used. Such a reaction film can be formed on a support by a plasma CVD method, for example.

In addition, the adhesive composition of this embodiment is suitably used for bonding a wafer for a thinning step to the support after bonding to the support. As mentioned above, this support system maintains the strength of the wafer when the wafer is thinned. The adhesive composition of this embodiment is suitable for use in bonding such a wafer and a support.

That is, the adhesive composition of this embodiment is a substrate processing method that can be used for a step including attaching a support to a substrate through an adhesive layer composed of the adhesive composition. The method for processing the substrate may further include a step of heat-treating the substrate to which the support is attached at a temperature of 100 ° C or higher and 400 ° C or lower.

In particular, the adhesive composition according to this embodiment has excellent heat resistance, and therefore can be suitably used for bonding a wafer to the support after being bonded to the support and exposed to an environment of 150 ° C. or higher. Specifically, it can be suitably used in an environment of 180 ° C or higher and furthermore 220 ° C or higher.

In addition, using the adhesive composition of this embodiment, a method of manufacturing a laminated body in which a wafer and a support are bonded at a temperature of 220 ° C. or lower is used. The method of thinning the wafer of the laminated body, the method of thinning the wafer of the laminated body, and the method of heating the laminated body at a temperature of 220 ° C. or higher are also within the scope of this embodiment.

(Removal of the adhesive layer formed by the adhesive composition)

After the wafer and the support adhered by the adhesive composition according to this embodiment are separated from the reaction layer by modification or the like, the adhesive layer can be easily dissolved and removed when the adhesive layer is removed when the adhesive layer is removed. In addition, without using the above-mentioned reaction layer or the like, the solvent is directly supplied to the adhesive layer in a state where the wafer and the support are adhered, and the adhesive layer can be easily dissolved to remove the adhesive layer, and the wafer and the support can be easily removed. Body separation. In this case, in order to improve the supply efficiency of the solvent to the adhesive layer, it is more preferable to provide a through hole in the support.

In this way, the substrate processing method of this embodiment may further include a step of separating the substrate and the support by dissolving the adhesive layer in a solvent.

[Adhesive film]

The adhesive composition of the present invention can be used in various forms depending on the application. For example, it is possible to use a method of forming an adhesive layer by directly applying liquid to a processed object such as a semiconductor wafer, or to use the adhesive film of the present invention, that is, a film in advance on a flexible film or the like. A method of forming an adhesive layer containing an adhesive composition of any of the above, drying the film, and then applying the film (adhesive film) to the object to be processed. (Following the thin film method).

As described above, the adhesive film of the present invention is provided on the film with an adhesive layer containing the adhesive composition of any of the above.

Next, the protective film may be further used by coating the protective film on the film. In this case, the protective film on the adhesive layer is peeled off, and the exposed adhesive layer is overlapped on the object to be processed, and then the film is peeled off from the adhesive layer, so that the adhesive layer can be easily removed. The agent layer is provided on the object to be processed.

Therefore, when this adhesive film is used, compared with the case where an adhesive agent layer is directly apply | coated on a to-be-processed body, and an adhesive agent layer is formed, an adhesive agent layer with favorable film thickness uniformity and surface smoothness can be formed.

The above-mentioned thin film used in the production of the adhesive film is processed as long as the adhesive layer formed on the film can be peeled from the film, and the adhesive layer can be transferred to a protective substrate or a wafer. There is no particular limitation on the release film on the surface. Examples include flexible films made of synthetic resin films such as polyethylene terephthalate, polyethylene, polypropylene, polycarbonate, and polyvinyl chloride having a film thickness of 15 to 125 μm. It is preferable that the film is subjected to a release treatment as necessary to facilitate the transfer.

The method of forming an adhesive layer on the above-mentioned thin film can be exemplified by using a known method appropriately in accordance with the desired film thickness or uniformity of the adhesive layer, so that the dry film thickness of the adhesive layer becomes 10 to 1,000 μm. A method for applying the adhesive composition of the present invention to a film.

In addition, when using a protective film, Although it does not specifically limit peeling from an adhesive layer, For example, a polyethylene terephthalate film, a polypropylene film, and a polyethylene film are preferable. In addition, each protective film is preferably one in which silicon is coated or sintered. This is because peeling from the adhesive layer becomes easy. Although the thickness of the protective film is not particularly limited, it is preferably 15 to 125 μm. This is because the flexibility of the adhesive film with the protective film can be ensured.

Although the method of using the subsequent film is not particularly limited, for example, when a protective film is used, after this is peeled off, the exposed adhesive layer is superposed on the object to be heated, and a heating roller is formed on the film (forming A method of moving the adhesive layer on the surface of the object by moving the back surface of the adhesive layer). At this time, if the protective film peeled from the adhesive film can be sequentially wound into a roll shape by a roll such as a take-up roll, it can be stored and reused.

Examples are shown below, and embodiments of the present invention will be described in further detail. Of course, the present invention is not limited to the following embodiments, and there may be various aspects of the details, and it is needless to say here. In addition, the present invention is not limited to the above-mentioned embodiments, and various changes can be made within the scope shown in the claims. Embodiments obtained by appropriately combining the technical means disclosed separately are also included in the present invention. Technical scope.

[Example] [Preparation of Adhesive Composition]

First, the adhesive composition was prepared as Examples 1-20. Compositions of the elastomer, hydrocarbon resin, acrylic resin, polymerization inhibitor, main solvent, and additive solvent used in Examples 1 to 20 are shown in Tables 1 and 2 below. The "parts" in Tables 1 and 2 are all parts by weight. In Tables 1 and 2, the elastomers, hydrocarbon resins, and acrylic resins represent the ratios of the individual resins to these totals. The polymerization inhibitor refers to the amount when the total amount of the elastomer, the hydrocarbon-based resin, and the acrylic resin is 100 parts, and the added solvent is an amount based on 100 parts of the main solvent.

For example, in Example 1, 70 parts of hydrogenated styrene-based elastomer Septon8007L (manufactured by KURARAY Co., Ltd.), 10 parts of Septon2004 (manufactured by KURARAY Co., Ltd.), 10 parts of TOPAS TM (manufactured by Polyplastics Co., Ltd.), 10 parts of A1 as an acrylic resin (details are described later) were dissolved in decalin at a concentration of 25%, and IRGANOX 1010 as a polymerization inhibitor and butyl acetate as an added solvent were added to prepare an adhesive composition.

Use of the elastic system in Examples 1 to 20: Septon 8007L (SEP: polystyrene-poly (ethylene / propylene) fluorene copolymer by Sepura (trade name) manufactured by KURARAY Co., Ltd .; styrene content 30%, Mw = 80,000), Septon (trade name) manufactured by KURARAY Co., Ltd. (SEP: polystyrene-poly (ethylene / propylene) fluorene copolymer; styrene content 18% by weight, Mw = 90,000), and KURARAY Co., Ltd. Septon (trade name) made by Septon V9827 (SEBS: styrene block is a styrene-ethylene-butene-styrene fluorene copolymer with a reactive cross-linking type; styrene content 30%, Mw = 90,000), Septon 2002 (trade name) manufactured by KURARAY Co., Ltd. (SEPS: styrene-isoprene-styrene triblock copolymer; styrene content 30%, Mw = 53,000), Asahi Kasei Co., Ltd. Tuftec (trade name) H1051 (SEBS; hydrogenated styrene thermoplastic elastomer; 42% styrene content, Mw = 78,000) manufactured by the company.

In addition, the hydrocarbon resins in Examples 1 to 20 used TOPAS (trade name) TM (cyclic olefin copolymer; ethylene-norbornene copolymer) manufactured by Polyplastics Co., Ltd., Mw = 10,000, Mw / Mn = 2.08 , Norbornene: ethylene = 50:50 (weight ratio)). Furthermore, A1 (Mw = 10,000) or A2 (Mw = 10,000) was used as the acrylic resin in Examples 1 to 20.

A1 is a random polymer having the following structure (wherein, l / m / n = 60/20/20).

Similarly, A2 is a random polymer having the following structure (wherein, 1 / m / n = 60/20/20).

As the thermal polymerization inhibitor, "IRGANOX (trade name) 1010" manufactured by BASF was used. In addition, as the main solvent, decalin represented by the following chemical formula (I) was used. The solvent used was butyl acetate.

The adhesive composition was prepared as Comparative Example 1 and Comparative Example 2. Compositions of the resin, polymerization inhibitor, main solvent, and added solvent used in Comparative Examples 1 and 2 are shown in Tables 1 and 2 below.

In Comparative Example 1, only the Septon (brand name) Septon8007L (SEP: polystyrene-poly (ethylene / propylene) block copolymer manufactured by KURARAY Co., Ltd. was used as the resin component; the styrene content was 30% and Mw = 80,000. ), In Comparative Example 2, only Asahi Kasei was used as the resin component Co., Ltd.'s Tuftec (trade name) H1051 (SEBS; hydrogenated styrene thermoplastic elastomer; styrene content 42%, Mw = 78,000).

[Next film formation]

The viscosity of the adhesive composition of Example 1 at 25 ° C. was adjusted to 10,000 cP using a main solvent or the like. Using a coating machine CAG-750 manufactured by LABO Co., Ltd., the adhesive composition after viscosity adjustment was applied to a PET film (trade name: LUMIRRORS10 (thickness 100um)) (base film) manufactured by Toray Co., Ltd. using a roller The roll-to-roll wet coating (slot die) method was applied at a coating speed of 1 m / min to a width of 500 mm. After that, the adhesive film 1 was dried by passing through a drying oven at 150 ° C. to obtain an adhesive film 1 having a thickness of 50 μm. Next, a polyethylene protective film (cover film) was laminated on the exposed surface of the adhesive layer and wound into a roll shape, and the adhesive film was formed into a roll shape for easy storage. For the adhesive compositions of Examples 2 to 20, adhesive films 2 to 20 having a thickness of 50 um in the adhesive layer were also obtained in the same manner, and formed into a roll shape.

[Next layer formation]

The adhesive compositions of Examples 1 to 20 were spin-coated on semiconductor wafer substrates (12 inches, silicon), and baked at 100 ° C, 160 ° C, and 220 ° C for 5 minutes each to form a film thickness of 50 μm. Next layer. That is, an adhesive layer is formed on a semiconductor wafer substrate by spin coating.

In addition, the peeled surface of the adhesive film 1 was superposed on another semiconductor wafer substrate (12 inches, silicon), and a laminator was used at 100 ° C, 0.2 MPa, and 0.5 m / min. The next layer will be stacked. Thereafter, the base film was peeled to form an adhesive layer having a film thickness of 50 μm on the semiconductor wafer substrate. That is, an adhesive film is used to form an adhesive layer on a semiconductor wafer substrate. In addition, for the adhesive films 2 to 20, the adhesive layer is formed on the semiconductor wafer substrate in the same manner.

[Attach]

Under vacuum, at 215 ° C and 4,000 kg for 5 minutes, a bare glass support (12 inches) having a fluorocarbon layer (thickness: 0.5 μm) and a reaction layer showing a laser absorption of 532 nm, and each of the above semiconductors The wafer substrate is bonded to form a laminated body. That is, a laminate in which an adhesive layer is formed on a semiconductor wafer substrate and a laminate in which an adhesive layer is formed on a semiconductor wafer substrate are produced by spin coating. At this time, in the subsequent thinning step and thermal step, it was confirmed that there were no defective attachments (parts that were not followed) that were related to the damage of the wafer or the reduction of the in-plane uniformity of the wafer. The reaction layer was formed by a CVD method using C ₄ F ₈ as a reaction gas under conditions of a flow rate of 400 sccm, a pressure of 700 mTorr, a high-frequency power of 2,800 W, and a film formation temperature of 240 ° C.

Next, the back surface of the wafer was thinned (50 μm) with a back grinding device made by DISCO, and then immersed in NMP (N-methyl-2-pyrrolidone) to confirm whether swelling or support of the adhesive composition occurred. body Of stripping.

[Stripping]

The wafer was irradiated with 532 nm of laser light from the glass surface, and was separated between the glass support and the adhesive layer. The wafer after the glass support is removed is rotated and cleaned by p-menthane to remove the adhesion layer without residue. The results of Examples 1 to 20 are shown in Tables 1 and 2, and the results of Comparative Example 1 and Comparative Example 2 are shown in Table 3. In Examples 1 to 20, the laminated body in which the adhesive layer was formed on the semiconductor wafer substrate by spin coating, and the laminated body in which the adhesive layer was formed on the semiconductor wafer substrate by using an adhesive film were obtained. result.

Whether the film-forming property is in the adhesive composition of the example or the comparative example is judged by whether or not the coating can be performed on the wafer substrate with a thickness of 15 μm or more. The case where coating was not possible was regarded as "×".

Whether the grindability can be determined is determined by the presence or absence of in-plane uniformity of the wafer after the wafer back surface is thinned by a back-side polishing device. The case where the thinned wafer surface is uniform is regarded as "○ ", The unevenness is regarded as" × ".

The heat resistance is determined by heating the laminate formed using the adhesive composition of the examples or comparative examples under a reduced pressure environment (10 Pa) at 220 ° C. for 1 hour. This evaluated the heat resistance of the adhesive composition. The heat resistance is evaluated if there is no foaming between the wafer and the support or The separation is regarded as "○", and if there is, it is regarded as "×".

The chemical resistance is determined by immersing the adhesive composition of the examples or comparative examples in NMP, and judging by the swelling or non-swelling. The case without swelling is regarded as "○", and the case with swelling is regarded as " × ".

In the adhesive composition of Examples 1 to 20, even when immersed in NMP, no swelling of the adhesive composition was generated, and as a result, no peeling from the adhesive composition of the glass support was generated. On the other hand, in the adhesive composition of Comparative Examples 1 and 2, the adhesive composition was swelled by immersion in NMP, and as a result, peeling from the adhesive composition of the glass support was generated. Therefore, it was shown that even if the laminate formed from the adhesive composition of Examples 1 to 20 was immersed in NMP, it did not cause swelling of the adhesive composition, and it did not produce the adhesive composition from the glass support. Peel off.

[Industrial availability]

The adhesive composition and the adhesive film of the present invention can be suitably used, for example, in the manufacturing steps of a miniaturized semiconductor device.

Claims (9)

An application of an adhesive composition, characterized in that an elastomer, a hydrocarbon resin, an acrylic resin, and an organic solvent are used. The elastic system contains a styrene unit as a structural unit of a main chain, and the content of the styrene unit is 14 This acrylic resin is an adhesive composition containing a (meth) acrylic acid ester having an aliphatic ring as a monomer, and is then bonded to a wafer and a support. For example, the application of the adhesive composition in the first scope of the patent application, wherein the (meth) acrylate having an aliphatic ring is selected from cyclohexyl (meth) acrylate, cyclopentyl (meth) acrylate Ester, 1-adamantyl (meth) acrylate, norbornyl (meth) acrylate, isofluorenyl (meth) acrylate, tricyclodecyl (meth) acrylate, tetracyclododecane (Meth) acrylate, dicyclopentyl (meth) acrylate. For example, the application of the adhesive composition in the second item of the patent application, wherein the (meth) acrylate having an aliphatic ring is 1-adamantyl (meth) acrylate or dicyclopentyl (methyl )Acrylate. For example, the application of the adhesive composition in the first scope of the patent application, wherein the content of the elastomer is 50% by weight or more and 98% by weight or less based on the total amount of the elastomer, the hydrocarbon resin, and the acrylic resin. In this range, the content ratio of the hydrocarbon resin is in the range of 1% by weight to 49% by weight, and the content ratio of the acrylic resin is in the range of 1% by weight to 49% by weight. For example, in the application of the adhesive composition of the first claim, the content of the styrene unit contained in the above-mentioned elastomer as a structural unit of the main chain is 17% by weight or more and 40% by weight or less. For example, the application of the adhesive composition of item 1 of the patent scope, wherein the above-mentioned elastomer is a styrene-based elastomer having two or more types of styrene units contained in a structural unit as a main chain, which are different from each other. . For example, the application of the adhesive composition of item 1 of the patent scope, wherein the weight average molecular weight of the above elastomer is 20,000 or more and 200,000 or less. For example, the application of the adhesive composition of item 1 of the patent scope, wherein the elastomer is a hydride. For example, the application of the adhesive composition of item 1 of the patent scope, wherein both ends of the above-mentioned elastomer are block polymers of styrene.