KR102148125B1 - Adhesive composition and adhesive film - Google Patents

Abstract

(Problem) An adhesive composition and an adhesive film capable of reducing swelling by a resist solvent and peeling from a support are provided.
(Solution means) The adhesive composition contains a styrene unit as a structural unit of the main chain, and contains an elastomer in which the content of the styrene unit is 14% by weight or more and 50% by weight or less, a hydrocarbon resin, and an acrylic resin.

Description

Adhesive composition and adhesive film TECHNICAL FIELD: ADHESIVE COMPOSITION AND ADHESIVE FILM

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

Along with the high functionality of mobile phones, digital AV devices, and IC cards, there is a growing demand for high integration of silicon in a package by reducing the size and thickness of semiconductor silicon chips (hereinafter, chips) to be mounted. For example, in an integrated circuit for converting a plurality of chips represented by a chip size package (CSP) or a multi-chip package (MCP) into a single package, a thinner is required. In order to achieve high integration of chips in a package, it is necessary to reduce the thickness of the chip to a range of 25 to 150 µm.

However, since the semiconductor wafer (hereinafter, referred to as the wafer) serving as the base of the chip becomes thinner by grinding, its strength is weakened, and cracks or warping are likely to occur in the wafer. In addition, since it is difficult to automatically transport a wafer whose strength is weakened by making it thinner, it must be transported by human hand, and handling thereof is complicated.

Therefore, a wafer handling system has been developed that maintains the strength of the wafer and prevents the occurrence of cracks and warping of the wafer by bonding a plate made of glass, hard plastic, etc., called a support plate, to a wafer to be ground. . Since the wafer handling system (WHS) can maintain the strength of the wafer, it is possible to automate the transportation of the thinned semiconductor wafer.

In a wafer handling system, a wafer and a support plate are bonded together using an adhesive tape, a thermoplastic resin, an adhesive, or the like. Then, after the wafer to which the support plate is affixed is thinned, the support plate is peeled from the substrate before dicing the wafer. When an adhesive is used for bonding the wafer and the support plate, the adhesive is dissolved and the wafer is peeled from the support plate.

Here, recently, a hydrocarbon-based adhesive has been developed as the adhesive (Patent Document 1).

Japanese Patent Publication No. 2009-529065 (published on August 13, 2009)

However, when the hydrocarbon-based adhesive described in Patent Document 1 is used for WHS, in the resist peeling step, when the wafer to which the support plate is attached is immersed in a resist solvent, swelling of the adhesive occurs, resulting in peeling of the support plate. there is a problem.

The adhesive composition and adhesive film according to the present invention have been made in view of the above problems, and their main object is to provide an adhesive composition and an adhesive film capable of reducing swelling by a resist solvent and peeling of a support.

In order to solve the above problems, the adhesive composition according to the present invention contains a styrene unit as a constituent unit of the main chain, an elastomer having a content of 14% by weight or more and 50% by weight or less, a hydrocarbon resin, and an acrylic resin. It is characterized by containing.

According to the above configuration, the effect of being able to provide an adhesive composition capable of reducing swelling by a resist solvent and peeling of the support is exhibited.

Hereinafter, an embodiment of the present invention will be described in detail. The adhesive composition according to an embodiment of the present invention contains a styrene unit as a structural unit of the main chain, and contains an elastomer having a content of 14% by weight or more and 50% by weight or less, a hydrocarbon resin, and an acrylic resin. .

Since the adhesive composition according to the present invention contains a styrene unit as a structural unit of the main chain, and contains an elastomer having a content of the styrene unit of 14% by weight or more and 50% by weight or less, and a hydrocarbon resin, the composition using a resist solvent Swelling and peeling of the support can be reduced. Further, since the adhesive composition according to the present invention contains an acrylic resin, the wafer (substrate) and the support can be preferably bonded while maintaining heat resistance.

In addition, with respect to the total amount of the elastomer, hydrocarbon resin and acrylic resin contained in the adhesive composition according to the present invention, the content rate of the elastomer is in the range of 50% by weight or more and 98% by weight or less, and the content rate of the hydrocarbon resin is 1% by weight or more and 49% by weight. % Or less, and the content rate of the acrylic resin is preferably 1% by weight or more and 49% by weight or less. In addition, with respect to the total amount of the elastomer, the hydrocarbon resin and the acrylic resin, the content rate of the elastomer is in the range of 50% by weight or more and 90% by weight or less, the content rate of the hydrocarbon-based resin is in the range of 5% by weight or more and 45% by weight or less, and the acrylic resin It is more preferable that the content rate of is in the range of 5% by weight or more and 45% by weight or less. By using the elastomer as a main component of the adhesive composition according to the present invention, swelling of the composition and peeling of the support by the resist solvent can be more preferably reduced.

[Elastomer]

The elastomer contained in the adhesive composition according to 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, the "constituent unit" refers to a structure of a main chain originating from one molecule of a monomer in a structure constituting a polymer.

In this specification, the "styrene unit" is a structural unit derived from the styrene contained in the polymer when styrene or a styrene derivative is polymerized, and the "styrene unit" may have a substituent. Examples of the substituent include an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an alkoxyalkyl group having 1 to 5 carbon atoms, an acetoxy group, and a carboxyl group.

When the content of the styrene unit is 14% by weight or more, it can be applied to processes such as thinning and mounting without lowering the sticking property or grinding property of the substrate. When the content of the styrene unit is 50% by weight or less, the chemical resistance of the adhesive composition according to the present invention can be preferably maintained.

The elastomer contained in the adhesive composition according to the present invention preferably has a weight average molecular weight of 20,000 or more and 200,000 or less, and more preferably 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, since it is easily dissolved in a hydrocarbon-based solvent described later, the adhesive composition is more easily and quickly Can be removed. In addition, since the weight average molecular weight is in the above range, the resist solvent (e.g., PGMEA, PGME, NMP, etc.), acid (hydrofluoric acid, etc.), alkali (TMAH, etc.) exposed when the wafer is applied to the resist lithography process It exhibits excellent resistance to

The content of the styrene unit is more preferably in the range of 17% by weight or more and 40% by weight or less.

As the elastomer, various elastomers can be used as long as the content of the styrene unit is in the range of 14% by weight or more and 50% by weight or less. For example, polystyrene-poly(ethylene/propylene) block copolymer (SEP), styrene-isoprene-styrene block copolymer (SIS), styrene-butadiene-styrene block copolymer (SBS), styrene-butadiene-butylene- Styrene block copolymer (SBBS), and hydrogenated products thereof, styrene-ethylene-butylene-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 (Septon V9461 (manufactured by Kuraray Co., Ltd.), Septon V9475 (Co., Ltd.) Kuraray)), a styrene-ethylene-butylene-styrene block copolymer having a reactive crosslinked styrene block (Septon V9827 having a reactive polystyrene-based hard block (manufactured by Kuraray Co., Ltd.)), etc., wherein the content of the styrene unit is described above. What is in the stated range can be used.

It is preferable that the elastomer contained in the adhesive composition according to the present invention contains two or more types of styrene-based elastomers in which the content of the styrene units contained as structural units of the main chain differ from each other. For example, you may contain two types of elastomers having different contents of styrene units, such as Septon8007L and Septon2004, SeptonV9827 and Septon2002 manufactured by Kuraray Co., Ltd. (trade name).

In short, the adhesive composition according to the present invention may contain a plurality of types of elastomers. If at least one of the plurality of elastomers contains a styrene unit as a structural unit of the main chain, and the content of the styrene unit is in the range of 14% by weight or more and 50% by weight or less, it is the scope of the present invention. In addition, in the adhesive composition according to the present invention, when a plurality of types of elastomers are contained, as a result of mixing, the content of the styrene unit may be adjusted so that the content of the styrene unit falls within the above range. For example, if Septon4033 of Cepton (brand name) manufactured by Kuraray Co., Ltd. having a styrene unit content of 30% by weight and Septon2063 of Septon (brand name) having a styrene unit content of 13% by weight are mixed at a weight ratio of 1 to 1, The styrene content with respect to the whole elastomer contained in the adhesive composition is 21 to 22% by weight, and is 14% by weight or more. Further, for example, when a styrene unit of 10% by weight and 60% by weight are mixed 1 to 1, it will be 35% by weight and fall within the above range. The present invention may have such a form. Moreover, it is more preferable that all of the plural types of elastomers contained in the adhesive composition according to the present invention contain styrene units within the above range.

When two types of elastomers having different styrene units content are contained, the styrene-based elastomer having a higher content of styrene units preferably has a styrene unit content of 20% by weight or more and 80% by weight or less. In addition, it is preferable that the content of the styrene unit is in the range of 1% by weight or more and 30% by weight or less in the styrene-based elastomer having a smaller content of the styrene unit. By using a styrene-based elastomer having a larger content of styrene units, it is possible to provide for processes such as thinning and mounting, without lowering the adhesion or grinding properties of the substrate. By using a styrene-based elastomer having a smaller content of styrene units, the chemical resistance of the adhesive composition according to the present invention can be preferably maintained.

In addition, in the case of containing two types of elastomers having different contents of styrene units, it is preferable that the styrene-based elastomer having a higher content of styrene units is in the range of 20% by weight or more and 80% by weight or less with respect to the total amount of the styrene-based elastomer. .

And among the elastomers, hydrogenated products are more preferable. If it is a hydrogenated product, the stability against heat is further improved, and deterioration such as decomposition or polymerization does not occur easily. Further, it is more preferable from the viewpoint of solubility in a hydrocarbon-based solvent and resistance to a resist solvent.

Moreover, it is more preferable that both ends are block polymers of styrene among elastomers. This is because it exhibits higher heat resistance by blocking styrene having high thermal stability at both ends.

More specifically, the elastomer is more preferably a hydrogenated product of a block copolymer of styrene and conjugated diene. As a result, the stability against heat is further improved, and deterioration, such as decomposition or polymerization, is less likely to occur. Further, by blocking styrene having high thermal stability at both ends, higher heat resistance is exhibited. Further, it is more preferable from the viewpoint of solubility to a hydrocarbon-based solvent and resistance to a resist solvent.

Commercially available products that can be used as an elastomer contained in the adhesive composition according to the present invention include, for example, "Cepton (brand name)" manufactured by Kuraray Co., Ltd. "Hybra (brand name)" manufactured by Kuraray Co., Ltd. Toughtech (brand name)", JSR Co., Ltd. "Dynaron (brand name)", etc. are mentioned.

[Acrylic resin]

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

Further, since the adhesive composition contains an acrylic resin which is a low molecular weight plasticizing component, it is possible to bond a wafer and a support plate, for example, without applying high thermal fluidity and high temperature or high pressure. Accordingly, the adhesive composition can preferably bond the wafer and the support even at a bonding temperature of 220° C. or lower, for example.

Further, it is preferable that the acrylic resin has a 5% thermal weight reduction temperature of 280°C or higher. Thereby, heat resistance required in the wafer processing process can be obtained. It can be said that the acrylic resin may 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 higher.

Here, the 5% thermal weight reduction temperature of the acrylic resin is only 5% by weight of the initial weight when heating is started at 25°C in a nitrogen atmosphere and the heating temperature is increased by 10°C in 1 minute intervals with respect to the acrylic resin. Is the temperature when it decreases. In addition, the weight of the acrylic resin can be measured with a thermogravimetric device.

As an acrylic resin, a resin which polymerized using (meth)acrylic acid ester as a monomer is mentioned, for example.

Examples of (meth)acrylic acid esters include alkyl (meth)acrylates 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)acrylic acid ester having.

Examples of the alkyl (meth)acrylate having a chain structure include an acrylic long-chain alkyl ester having an alkyl group having 15 to 20 carbon atoms, and an acrylic alkyl ester having an alkyl group having 1 to 14 carbon atoms. As an acrylic long-chain alkyl ester having an alkyl group having 15 to 20 carbon atoms, the alkyl group is n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-nonadecyl group, n- Alkyl esters of acrylic acid or methacrylic acid, such as an eicosyl group, are mentioned. Further, the alkyl group may be branched.

Examples of the acrylic alkyl ester having an alkyl group having 1 to 14 carbon atoms include known acrylic alkyl esters used in existing acrylic adhesives. For example, an alkyl group consisting of a methyl group, an ethyl group, a propyl group, a butyl group, a 2-ethylhexyl group, an isooctyl group, an isononyl group, isodecyl group, dodecyl group, lauryl group, tridecyl group, etc. Alkyl ester of an acid is mentioned.

Examples of the (meth)acrylic acid ester having an aliphatic ring include cyclohexyl (meth)acrylate, cyclopentyl (meth)acrylate, 1-adamantyl (meth)acrylate, norbornyl (meth)acrylate, and isobor Nyl (meth) acrylate, tricyclodecanyl (meth) acrylate, tetracyclododecanyl (meth) acrylate, dicyclopentanyl (meth) acrylate, etc. are mentioned, but isobornyl methacrylate, dicy Clofentanyl (meth)acrylate is more preferred.

The (meth)acrylic acid ester having an aromatic ring is not particularly limited, but examples of the aromatic ring include phenyl group, benzyl group, tolyl group, xylyl group, biphenyl group, naphthyl group, anthracenyl group, phenoxymethyl group And a phenoxyethyl group. Moreover, the aromatic ring may have a C1-C5 linear or branched alkyl group. Specifically, phenoxyethyl acrylate is preferable.

The acrylic resin contained in the adhesive composition according to the present invention may be polymerized using one type of monomer among the monomers of the (meth)acrylic acid ester described above, or may be polymerized using a plurality of types of monomers. .

The acrylic resin contained in the adhesive composition according to the present invention may be a resin polymerized using the above-described (meth)acrylic acid ester monomer and another monomer capable of being polymerized therewith. As a monomer polymerizable with a monomer such as (meth)acrylic acid ester, styrene or a styrene derivative, a monomer containing a maleimide group, and the like may be mentioned.

As a monomer containing a maleimide group, N-methylmaleimide, N-ethylmaleimide, Nn-propylmaleimide, N-isopropylmaleimide, Nn-butylmaleimide, N-isobutylmaleimide, N-sec- Butylmaleimide, N-tert-butylmaleimide, Nn-pentylmaleimide, Nn-hexylmaleimide, Nn-heptylmaleimide, Nn-octylmaleimide, N-laurylmaleimide, N-stearylmaleimide, etc. Maleimide, N-cyclopropylmaleimide, N-cyclobutylmaleimide, N-cyclopentylmaleimide, N-cyclohexylmaleimide, N-cycloheptylmaleimide, N-cyclooctylmaleimide, etc. And aromatic maleimide having an aryl group such as maleimide having an aliphatic hydrocarbon group, N-phenylmaleimide, Nm-methylphenylmaleimide, No-methylphenylmaleimide, and Np-methylphenylmaleimide.

It is preferable that the acrylic resin contains a styrene unit as a structural unit. By containing the styrene unit in the acrylic resin, the heat resistance of the acrylic resin is improved, and it is also preferable from the viewpoint of solubility in a solvent and resistance to a resist solvent.

It is preferable that the acrylic resin is soluble in a hydrocarbon-based solvent. Examples of the hydrocarbon solvent in which the acrylic resin can be dissolved include decahydronaphthalin, but the details of other hydrocarbon solvents will be described later.

It is preferable that the solubility parameter (SP value) of an acrylic resin is 6 or more and 10 or less. When the SP value is 6 or more and 10 or less, the acrylic resin and the elastomer are compatible, and a more stable adhesive composition is obtained. It is more preferable that the SP value of the acrylic resin is 6.5 or more and 9.5 or less.

It is preferable that the weight average molecular weight of an acrylic resin is 2,000 or more and 70,000 or less. When the weight average molecular weight of the acrylic resin is 2,000 or more and 70,000 or less, for example, an adhesive composition having heat fluidity suitable for bonding a wafer and a support can be provided. It is more preferable that the weight average molecular weight of an acrylic resin is 5,000 or more and 50,000 or less.

You may mix a plurality of types of acrylic resin. In short, the adhesive composition according to the present invention may contain a plurality of types of acrylic resins. In addition, it is most preferable that all of the plurality of types of acrylic resins contained in the adhesive composition according to the present invention have a 5% thermal weight reduction temperature of 280°C or higher.

The acrylic resin contained in the adhesive composition according to the present invention is a resin obtained by synthesizing each monomer by known radical polymerization.

Examples of the acrylic resin include a (meth)acrylic acid ester having an aliphatic ring, an alkyl (meth)acrylate having a chain structure, and a resin obtained by randomly polymerizing styrene using styrene as a monomer. At this time, as the (meth)acrylic acid ester having an aliphatic ring, for example, tricyclodecanyl (meth)acrylate or 1-adamantyl (meth)acrylate, etc. may be mentioned, and consisting of a chain structure As an alkyl (meth)acrylate, an alkyl ester of acrylic acid or methacrylic acid in which an alkyl group is an n-eicosyl group etc. is mentioned, for example. These acrylic resins may be appropriately combined and used.

[Hydrocarbon resin]

The hydrocarbon resin has a hydrocarbon skeleton and is a resin obtained by polymerizing a monomer component. As the hydrocarbon resin contained in the adhesive composition according to the present embodiment, for example, selected from the group consisting of a cycloolefin polymer (hereinafter, also referred to as ``resin A''), and a terpene resin, a rosin resin, and a petroleum resin. At least one type of resin (hereinafter, also referred to as "resin B") can be mentioned.

The cycloolefin polymer is a resin obtained by polymerizing a cycloolefin monomer as a monomer component. As a cycloolefin monomer, for example, a dicyclic substance such as norbornene and norbornadiene, a tricyclic substance such as dicyclopentadiene and a hydroxydicyclopentadiene, and a tetracyclic substance such as tetracyclododecene , 5 cyclic groups such as cyclopentadiene trimer, 7 cyclic groups such as tetracyclopentadiene, or alkyl (methyl, ethyl, propyl, butyl, etc.) substituents of these polycyclics, alkenyl (vinyl, etc.) substituents, alkylidene (Ethylidene, etc.) substituent, aryl (phenyl, tolyl, naphthyl, etc.) substituent, etc. are mentioned. 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 types.

Further, the monomer component contained in the resin (A) is not limited to the cycloolefin monomer, and may contain another monomer copolymerizable with the cycloolefin monomer. Other monomers include, for example, linear or branched alkene monomers, and such alkene monomers include, for example, ethylene, propylene, 1-butene, isobutene, and 1-hexene. And α-olefins of. Moreover, only 1 type may be used for the alkene monomer, and may be used in combination of 2 or more types.

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, more preferably It is 50,000 to 150,000. When the weight average molecular weight of the resin (A) is within the above range, cracks are less likely to occur after film formation, and solubility in a specific solvent can be obtained.

In addition, the monomer component constituting the resin (A) is preferably 5 mol% or more of the cycloolefin monomer from the viewpoint of high heat resistance (low thermal decomposition property and thermoweight reduction property), and 10 mol% or more is a cycloolefin monomer. It is more preferable, and 20 mol% or more is still more preferable. The upper limit is not particularly limited, but 80 mol% or less is preferable from the viewpoints of solubility and stability over time in a solution, and more preferably 70 mol% or less. In the case of containing a linear or branched alkene monomer as another monomer, it is preferable from the viewpoint of solubility and flexibility that it is 10 to 90 mol% with respect to the whole monomer component constituting the resin (A), and 20 to 85 mol It is more preferable that it is %, and it is especially preferable that it is 30 to 80 mol%.

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

Commercially available products that can be used as resin (A) include, for example, ``APEL (brand name)'' manufactured by Mitsui Chemicals Co., Ltd., ``TOPAS (brand name)'' manufactured by Polyplastics Corporation, and ``ZEONOR (brand name) manufactured by Nippon Xeon Corporation. And "ZEONEX (brand name)", and "ARTON (brand name)" manufactured by JSR Corporation.

Resin (B) is at least one resin selected from the group consisting of terpene resins, rosin resins, and petroleum resins as described above. As a terpene resin, a terpene resin, a terpene phenol resin, a modified terpene resin, a hydrogenated terpene resin, a hydrogenated terpene phenol resin, etc. are mentioned, for example. Examples of rosin-based resins include rosin, rosin ester, hydrogenated rosin, hydrogenated rosin ester, polymerized rosin, polymerized rosin ester, and modified rosin. Examples of petroleum resins include aliphatic or aromatic petroleum resins, hydrogenated petroleum resins, modified petroleum resins, alicyclic petroleum resins, and chromaon-indene petroleum resins. Among these, hydrogenated terpene resins and hydrogenated terpenephenol 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, more preferably 500 to 5,000. When the weight average molecular weight of the resin (B) is within the above range, cracks are less likely to occur after film formation, and high heat resistance (resistance to thermal decomposition and sublimation properties) is obtained.

Moreover, you may mix and use resin (A) and resin (B). The content of the resin (A) is preferably 40 parts by weight or more, and more preferably 60 parts by weight or more of the entire hydrocarbon resin. When the content of the resin (A) is 40 parts by weight or more of the entire hydrocarbon resin, it is possible to exhibit flexibility and high heat resistance (low thermal decomposition).

[solvent]

The solvent contained in the adhesive composition according to the present invention may be any one having a function of dissolving an elastomer, a hydrocarbon resin, and an acrylic resin. For example, a non-polar hydrocarbon-based solvent, a polar and non-polar petroleum-based solvent, and the like can be used.

Preferably the solvent may contain a condensed polycyclic hydrocarbon. When the solvent contains a condensed polycyclic hydrocarbon, clouding that may occur when the adhesive composition is stored in a liquid form (especially at low temperatures) can be avoided, and product stability can be improved.

Examples of the hydrocarbon solvent include linear, branched or cyclic hydrocarbons. For example, linear hydrocarbons such as hexane, heptane, octane, nonane, methyloctane, decane, undecane, dodecane, and tridecane, and branched chain hydrocarbons having 4 to 15 carbon atoms; Saturated aliphatic aliphatic acids such as p-mentane, o-mentane, m-mentane, diphenylmentane, 1,4-terpine, 1,8-terpine, bornan, norbornane, refuge, bulljan, karan, longipolene, etc. Hydrocarbons, α-terpinene, β-terpinene, γ-terpinene, α-pinene, β-pinene, α-towzone, β-towzone, and the like.

Moreover, as a petroleum-type solvent, cyclohexane, cycloheptane, cyclooctane, naphthalene, decahydronaphthalene, tetrahydronaphthalene, etc. are mentioned, for example.

In addition, the condensed polycyclic hydrocarbon is a condensed ring hydrocarbon formed by supplying only one side of each ring of two or more monocyclic rings, and it is preferable to use a hydrocarbon formed by condensation of two monocyclic rings.

Examples of such hydrocarbons include a combination of a five-membered ring and a six-membered ring, or a combination of two six-membered rings. Examples of the hydrocarbon in which a five-membered ring and a six-membered ring are combined include indene, pentalene, indane, tetrahydroindene, and the like, and as a hydrocarbon combining two six-membered rings, for example , Naphthalene, tetrahydronaphthaline (tetraline), and decahydronaphthaline (decalin).

Further, when the solvent contains the condensed polycyclic hydrocarbon, the component contained in the solvent may be only the condensed polycyclic hydrocarbon, and may contain other components such as, for example, a saturated aliphatic hydrocarbon. In this case, it is preferable that the content of the condensed polycyclic hydrocarbon is 40 parts by weight or more, and more preferably 60 parts by weight or more of the total hydrocarbon solvent. When the content of the condensed polycyclic hydrocarbon is 40 parts by weight or more of the total hydrocarbon solvent, high solubility in the resin can be exhibited. 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 alleviated.

In addition, the content of the solvent in the adhesive composition of the present invention may be appropriately adjusted according to the thickness of the adhesive layer formed by using the adhesive composition, but, for example, when the total amount of the adhesive composition is 100 parts by weight. , It is preferably in the range of 20 parts by weight or more and 90 parts by weight or less. 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. The thermal polymerization inhibitor has a function of preventing radical polymerization reaction due to heat. Specifically, since the thermal polymerization inhibitor exhibits high reactivity with respect to radicals, it reacts preferentially over the monomer to inhibit polymerization of the monomer. In the adhesive composition containing such a thermal polymerization inhibitor, a polymerization reaction is suppressed in a high-temperature environment (particularly, 250°C to 350°C).

For example, in a semiconductor manufacturing process, there is a high-temperature process in which a wafer to which a support plate (support) is adhered is heated at 250° C. for 1 hour. At this time, if polymerization of the adhesive composition occurs due to high temperature, the solubility in the peeling solution for peeling the support plate from the wafer after the high temperature process is lowered, and the support plate cannot be removed satisfactorily from the wafer. However, in the adhesive composition of the present invention containing a thermal polymerization inhibitor, since oxidation by heat and the accompanying polymerization reaction are suppressed, the support plate can be easily peeled even if it has undergone a high-temperature process, thereby reducing the occurrence of residues. Can be suppressed.

The thermal polymerization inhibitor is not particularly limited as long as it is effective for preventing a radical polymerization reaction due to heat, but a thermal polymerization inhibitor having phenol is preferable. Thereby, good solubility can be ensured even after high-temperature treatment in the atmosphere. As such a thermal polymerization inhibitor, a hindered phenol-based antioxidant can be used, for example, pyrogallol, benzoquinone, hydroquinone, methylene blue, tert-butylcatechol, monobenzyl ether, methylhydroquinone, amyl Quinone, amyloxyhydroquinone, n-butylphenol, phenol, hydroquinone monopropyl ether, 4,4'-(1-methylethylidene)bis(2-methylphenol), 4,4'-(1-methyl Ethylidene)bis(2,6-dimethylphenol), 4,4'-[1-[4-(1-(4-hydroxyphenyl)-1-methylethyl)phenyl]ethylidene]bisphenol, 4, 4',4"-ethylidenetris(2-methylphenol), 4,4',4"-ethylidenetrisphenol, 1,1,3-tris(2,5-dimethyl-4-hydroxyphenyl) )-3-phenylpropane, 2,6-di-tert-butyl-4-methylphenol, 2,2'-methylenebis(4-methyl-6-tert-butylphenol), 4,4'-butylidene Bis(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, penta Erythryltetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (trade name IRGANOX1010, manufactured by BASF), tris(3,5-di-tert-butylhydroxy Benzyl) isocyanurate and thiodiethylenebis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] are mentioned. 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 elastomer, type of hydrocarbon resin, type of acrylic resin, and the use and use environment of the adhesive composition. For example, elastomer, hydrocarbon resin, and acrylic resin When the amount of the combined resin is 100 parts by weight, it is preferably 0.1 parts 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 suppressing polymerization due to heat is exhibited favorably, and a decrease in the solubility of the adhesive composition in the peeling solution after the high-temperature process can be further suppressed.

(Additive solvent)

In addition, the adhesive composition according to the present invention may be configured to contain an additive solvent having a composition different from the solvent for dissolving the thermal polymerization inhibitor and dissolving the elastomer, hydrocarbon resin and acrylic resin. Although it does not specifically limit as an additive solvent, An organic solvent which dissolves the component contained in an adhesive composition can be used.

As the organic solvent, for example, it is sufficient to dissolve each component of the adhesive composition to form a uniform solution, and any one type or two or more types can be used in combination.

Specific examples of the organic solvent include, for example, a terpene solvent having an oxygen atom, a carbonyl group or an acetoxy group as a polar group. For example, geraniol, nerol, linalol, citral, citro Nelol, menthol, isomentol, neomentol, α-terpineol, β-terpineol, γ-terpineol, terpinen-1-ol, terpinen-4-ol, dihydroterpinyl acetate, 1, 4-cineol, 1,8-cineol, borneol, carbon, yonone, bullfighting zone, and campha. Moreover, lactones, such as γ-butyrolactone; Ketones such as acetone, methyl ethyl ketone, cyclohexanone (CH), methyl-n-pentyl ketone, methyl isopentyl ketone, and 2-heptanone; Polyhydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol, and dipropylene glycol; Compounds having an ester bond, such as ethylene glycol monoacetate, diethylene glycol monoacetate, propylene glycol monoacetate, or dipropylene glycol monoacetate, monomethyl ether, monoethyl ether of the polyhydric alcohols or compounds having the ester bond, Derivatives of polyhydric alcohols, such as monoalkyl ethers such as monopropyl ether and monobutyl ether, or compounds having an ether bond such as monophenyl ether (in particular, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME) is preferred); Cyclic ethers such as dioxane, esters such as methyl lactate, ethyl lactate (EL), methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, and ethyl ethoxypropionate; And aromatic organic solvents such as anisole, ethyl benzyl ether, cresyl methyl ether, diphenyl ether, dibenzyl ether, phenetol, and butylphenyl ether.

The content of the additive solvent may be appropriately determined depending on the type of thermal polymerization inhibitor, but, for example, a solvent that dissolves the elastomer, hydrocarbon resin, and acrylic resin (main solvent) and a solvent that dissolves the thermal polymerization inhibitor (additive solvent When the total of) 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 additive solvent is within the above range, the thermal polymerization inhibitor can be sufficiently dissolved.

(Other ingredients)

The adhesive composition may further contain other miscible substances within the range not impairing the essential properties in the present invention. For example, various commonly used additives such as additional resins, plasticizers, adhesion aids, stabilizers, colorants, and surfactants for improving the performance of the adhesive may be additionally used.

(Method of preparing adhesive composition)

The method for preparing the adhesive composition according to the present embodiment is not particularly limited, and a known method may be used, but 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 according to the present embodiment can be obtained.

In addition, when adding a thermal polymerization inhibitor to the adhesive composition according to the present embodiment, it is preferable to add the thermal polymerization inhibitor previously dissolved in an additive solvent for dissolving the thermal polymerization inhibitor.

(Use of the adhesive composition according to this embodiment)

The adhesive composition according to the present embodiment is used for bonding the wafer (substrate) to the support of the wafer.

The support is, for example, a member that serves to support the wafer in a process of thinning the wafer, and is adhered to the wafer by the adhesive composition according to the present embodiment. In one embodiment, the support is formed of, for example, glass or silicon having a film thickness of 500 to 1,000 µm.

In addition, in one embodiment, a hole is formed in the support body through the support body in the thickness direction. By pouring a solvent for dissolving the adhesive composition through the hole between the support and the wafer, the support and the wafer can be easily separated.

The adhesion between the wafer and the support by the adhesive composition may be performed, for example, by applying the adhesive composition on the wafer, heating the wafer to form an adhesive layer, and attaching the support to the wafer through the adhesive layer. The film thickness of the adhesive layer is not particularly limited, but may be, for example, 5 µm or more and 200 µm or less. In addition, the heating conditions may be appropriately set according to the adhesive composition to be used, and although not particularly limited, for example, the adhesive layer is efficiently formed by baking stepwise while raising the temperature in the range of 50°C to 250°C. can do.

In addition, for the affixing of the support to the wafer, for example, by superimposing the support on the side where the adhesive layer of the wafer is formed and pressing in a vacuum at a high temperature (for example, 215°C), the support is applied to the wafer. Can be attached. However, the method of attaching may be appropriately selected from various conventionally known methods depending on the state of the substrate (surface irregularities, strength, etc.), the composition of the adhesive composition, and the material of the support.

Further, in another embodiment, a reactive layer may be interposed between the support and the wafer in addition to the adhesive layer. The reaction layer is deteriorated by absorbing the light irradiated through the support, and the support and the wafer can be easily separated by deteriorating the reaction layer by irradiating the reaction layer with light or the like. In this case, it is preferable to use a support that does not have a hole penetrating through the thickness direction.

As the light irradiated to the reaction layer, depending on the wavelength that the reaction layer can absorb, for example, liquid such as YAG laser, Livi laser, glass laser, YVO ₄ laser, LD laser, solid laser such as fiber laser, and dye laser. A gas laser such as a laser, a CO ₂ laser, an excimer laser, an Ar laser, or a He-Ne laser, a laser light such as a semiconductor laser or a free electron laser, or a non-laser light may be appropriately used. The wavelength of light to be absorbed by the reaction layer is not limited thereto, but may be, for example, light having a wavelength of 600 nm or less.

The reaction layer may contain, for example, a light absorbing agent that is decomposed by light or the like. As the light absorbing agent, for example, fine particle metal powder such as graphite powder, iron, aluminum, copper, nickel, cobalt, manganese, chromium, zinc, tellurium, metal oxide powder such as black titanium oxide, carbon black, or aromatic dia. Dyes such as mino-based metal complex, aliphatic diamine-based metal complex, aromatic dithiol-based metal complex, mercaptophenol-based metal complex, squarylium-based compound, cyanine-based dye, methine-based dye, naphthoquinone-based dye, and anthraquinone-based dye, or Pigments can be used. Such a reaction layer can be formed, for example, by mixing it with a binder resin and applying it on a support. In addition, a resin having a light absorbing group can also be used.

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

In addition, the adhesive composition according to the present embodiment is preferably used for bonding the support to the wafer provided in the thinning step after being adhered to the support. As described above, this support maintains the strength of the wafer when thinning the wafer. The adhesive composition according to the present embodiment is preferably used for adhesion between such a wafer and a support.

That is, the adhesive composition according to the present embodiment can be used in a method for treating a substrate including a step of attaching a support to a substrate via an adhesive layer made of the adhesive composition. The substrate treatment method may further include a step of heat-treating the substrate to which the support is attached at 100°C or more and 400°C or less.

In particular, since the adhesive composition according to the present embodiment has excellent heat resistance, it is preferably used for bonding the support to a wafer exposed to an environment of 150° C. or higher after being adhered to the support. Specifically, it can be preferably used in an environment of 180°C or higher, and further 220°C or higher.

In addition, a method of manufacturing a laminate in which a wafer and a support are adhered at 220°C or lower using the adhesive composition according to the present embodiment, a method of thinning a wafer for thinning the wafer of the laminate, and the laminate at a temperature of 220°C or higher. The method of heating is also a category of this embodiment.

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

When removing the adhesive layer after separating the wafer and the support adhered by the adhesive composition according to the present embodiment by altering the reaction layer, it can be easily dissolved and removed by using the above-described solvent. . In addition, by directly supplying a solvent to the adhesive layer in a state in which the wafer and the support are adhered without using the reaction layer, etc., the adhesive layer is easily dissolved and the adhesive layer is removed, so that the wafer and the support can be separated. . In this case, in order to increase the efficiency of supplying the solvent to the adhesive layer, it is more preferable that a through hole is formed in the support.

As described above, the substrate processing method according to the present 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 according to the present invention can adopt various types of use depending on the application. For example, a method of forming an adhesive layer by applying it on a workpiece such as a semiconductor wafer in a liquid state may be used, or any of the above adhesives on the adhesive film according to the present invention, that is, a film such as a flexible film in advance. After forming the adhesive layer containing the composition, it is allowed to dry, and you may use the method (adhesive film method) in which this film (adhesive film) is affixed to a workpiece and used.

In this way, the adhesive film according to the present invention includes an adhesive layer containing any of the above adhesive compositions on the film.

The adhesive film may be used by further covering the adhesive layer with a protective film. In this case, the protective film on the adhesive layer is peeled off, the exposed adhesive layer is overlaid on the object to be processed, and then the film is peeled from the adhesive layer, whereby an adhesive layer can be easily formed on the workpiece.

Therefore, when this adhesive film is used, an adhesive layer having good film thickness uniformity and surface smoothness can be formed as compared to the case of forming an adhesive layer by directly applying the adhesive composition on a workpiece.

The film used in the production of an adhesive film may be a release film capable of peeling the adhesive layer formed on the film from the film, and transferring the adhesive layer onto a surface to be treated such as a protective substrate or a wafer. , It is not particularly limited. For example, a flexible film made of a synthetic resin film such as polyethylene terephthalate, polyethylene, polypropylene, polycarbonate, and polyvinyl chloride having a film thickness of 15 to 125 µm is mentioned. It is preferable that a release treatment is applied to the film so as to facilitate transfer as necessary.

As a method for forming an adhesive layer on the film, according to the film thickness or uniformity of the desired adhesive layer, a known method is appropriately used, so that the dry film thickness of the adhesive layer on the film is 10 to 1,000 µm. The method of applying the related adhesive composition is mentioned.

Moreover, in the case of using a protective film, the protective film is not limited as long as it can be peeled from the adhesive layer, but, for example, a polyethylene terephthalate film, a polypropylene film, and a polyethylene film are preferable. Moreover, it is preferable that each protective film is coated or baked with silicone. This is because peeling from the adhesive layer becomes easy. The thickness of the protective film is not particularly limited, but is preferably 15 to 125 µm. This is because the flexibility of the adhesive film provided with the protective film can be secured.

Although the method of using the adhesive film is not particularly limited, for example, when a protective film is used, after peeling it, the exposed adhesive layer on the object to be processed is superimposed on the film (on the surface on which the adhesive layer is formed). By moving the heating roller on the back side), a method of thermocompression bonding the adhesive layer to the surface of the workpiece can be mentioned. At this time, the protective film peeled off from the adhesive film can be stored and reused by sequentially winding it up in a roll shape with a roller such as a winding roller.

Examples are shown below, and embodiments of the present invention will be described in more detail. Of course, the present invention is not limited to the following examples, and it is needless to say that various aspects are possible for details. In addition, the present invention is not limited to the above-described embodiments, and various modifications are possible within the range indicated in the claims, and embodiments obtained by appropriately combining the disclosed technical means are also included in the technical scope of the present invention.

Example

[Preparation of adhesive composition]

First, an adhesive composition was prepared as Examples 1 to 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. In addition, "parts" in Tables 1 and 2 are all parts by weight. In addition, in Tables 1 and 2, the elastomers, hydrocarbon resins, and acrylic resins represent respective ratios to these total amounts. The polymerization inhibitor represents the amount when the total of the elastomer, the hydrocarbon resin, and the acrylic resin is 100 parts, and the additive solvent is an amount based on 100 parts of the main solvent.

For example, in Example 1, with respect to 70 parts of the hydrogenated styrene elastomer Septon8007L (manufactured by Kuraray Co., Ltd.), 10 parts of Septon2004 (manufactured by Kuraray Co., Ltd.), 10 parts of TOPAS TM (manufactured by Polyplastic Corporation), as an acrylic resin 10 parts of A1 (details will be described later) were dissolved in decahydronaphthalin at a concentration of 25%, and IRGANOX1010 as a polymerization inhibitor and butyl acetate as an additive solvent were added to obtain an adhesive composition.

As the elastomer in Examples 1 to 20, Septon8007L (SEP: polystyrene-poly(ethylene/propylene) block copolymer; styrene content 30%, Mw = 80,000) manufactured by Kuraray Co., Ltd. manufactured by Septon (brand name), manufactured by Kuraray Co., Ltd. Septon (brand name) of Septon2004 (SEP: polystyrene-poly(ethylene/propylene) block copolymer; styrene content 18% by weight, Mw = 90,000) and Septon V9827 (SEBS: styrene block) manufactured by Kuraray Co., Ltd. Reaction crosslinked styrene-ethylene-butylene-styrene block copolymer; styrene content 30%, Mw = 90,000), Septon 2002 (SEPS: styrene-isoprene-styrene triblock copolymer manufactured by Kuraray Co., Ltd.) ; Styrene content 30%, Mw = 53000), Asahi Chemical Co., Ltd. Tuftec (brand name) H1051 (SEBS; hydrogenated styrene thermoplastic elastomer; styrene content 42%, Mw = 78,000) was used.

Moreover, as a hydrocarbon resin in Examples 1-20, TOPAS (brand name) TM (cycloolefin copolymer; ethylene-norbornene copolymer, Mw = 10,000, Mw/Mn = 2.08, nor Bornene:ethylene = 50:50 (weight ratio)) was used. In addition, 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 (in the formula, l/m/n = 60/20/20).

[Formula 1]

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

[Formula 2]

In addition, "IRGANOX (brand name) 1010" manufactured by BASF was used as the thermal polymerization inhibitor. In addition, decahydronaphthalene represented by the following general formula (I) was used as the main solvent. Moreover, butyl acetate was used as an additive solvent.

[Formula 3]

Adhesive compositions were prepared as Comparative Example 1 and Comparative Example 2. Compositions of the resin, polymerization inhibitor, main solvent, and additive solvent used in Comparative Example 1 and Comparative Example 2 are shown in Tables 1 and 2 below.

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

[Formation of adhesive film]

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 an applicator CAG-750 manufactured by Labo Co., Ltd., the adhesive composition after viscosity adjustment was applied to a PET film manufactured by Toray Corporation (brand name: Lumirror S10 (thickness 100 um) (base film)) by wet coating (slot die) in a roll-to-roll method. ) Method, the coating was applied in a width of 500 mm at a coating speed of 1 m/min, and then dried by passing through a drying furnace at 150° C. to obtain an adhesive film 1 having an adhesive layer having a thickness of 50 μm. Next, the exposed surface of the adhesive layer A polyethylene protective film (cover film) was superimposed on and wound up in a roll shape, and the adhesive film was made into a roll shape for easy storage In the same manner for the adhesive compositions of Examples 2 to 20, the adhesive film having a thickness of the adhesive layer of 50 um 2-20 were obtained, and it was set as a roll shape.

[Formation of adhesive layer]

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

Further, the surface from which the cover film in the adhesive film 1 was removed was superimposed on another semiconductor wafer substrate (12 inches, silicon), and the adhesive layer was laminated under conditions of 100°C, 0.2 MPa, and 0.5 m/min using a laminator. I did. Thereafter, the base film was removed to form an adhesive layer having a thickness of 50 µm on the semiconductor wafer substrate. That is, an adhesive layer was formed on a semiconductor wafer substrate using an adhesive film. In the same manner, for the adhesive films 2 to 20, an adhesive layer was formed on the semiconductor wafer substrate by the same method.

[Attachment]

Bare's glass support (12 inches) with a fluorocarbon layer (thickness 0.5 μm) as a reaction layer exhibiting laser absorption of 532 nm for 5 minutes under vacuum, at 215°C, and at 4,000 kg, and each of the above-described vandope wafer substrates Was bonded to a laminate. In short, a laminate in which an adhesive layer was formed on a semiconductor wafer substrate by spin coating, and a laminate in which an adhesive layer was formed on a semiconductor wafer substrate using an adhesive film was produced. At that time, it was confirmed that there were no defects (non-adhesive portions) leading to damage to the wafer or a decrease in the in-plane uniformity of the wafer in the subsequent thinning process and the thermal process. Further, the reaction layer was formed by a CVD method using C ₄ F ₈ as a reactive 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 side of the wafer was thinned (50 μm) with a back grinding device manufactured by DISCO, and then immersed in NMP (N-methyl-2-pyrrolidone) to see whether swelling of the adhesive composition or peeling of the support has occurred. Was confirmed.

[Peeling]

The wafer was irradiated with a 532 nm laser from the glass surface to separate the wafer between the glass support and the adhesive layer. The wafer from which the glass support was removed was spin-cleaned with p-mentane to remove the adhesive 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 same results were obtained in a laminate in which an adhesive layer was formed on a semiconductor wafer substrate by spin coating and a laminate in which an adhesive layer was formed on a semiconductor wafer substrate using an adhesive film.

Whether or not film formation is possible is judged by whether or not application of 15 µm or more is possible on the wafer substrate in the adhesive composition according to the Example or Comparative Example, and the case where application is possible is referred to as "○", and the case where application is not possible is determined as " X".

Whether or not grinding is possible is judged by the presence or absence of in-plane uniformity of the wafer after thinning the back surface of the wafer with a back grinding device, and the case where the thinned wafer surface is uniform is referred to as "○", and the case of non-uniformity is determined as "x". I did.

With respect to heat resistance, the laminate formed using the adhesive composition according to the Examples or Comparative Examples was heated at 220°C for 1 hour in a reduced pressure environment (10 Pa). Thereby, the heat resistance of the adhesive composition was evaluated. Heat resistance was evaluated as "o" if there was no foaming or peeling between the wafer and the support, and "x" if there was.

The chemical resistance was judged by whether or not it swelled after immersing the adhesive composition according to the Examples or Comparative Examples in NMP, and the case where it did not swell was set to "○", and the case where it was swollen was set to "×".

In the adhesive compositions according to Examples 1 to 20, swelling of the adhesive composition did not occur even when immersed in NMP, and as a result, peeling of the adhesive composition from the glass support did not occur. On the other hand, in the adhesive compositions according to Comparative Examples 1 and 2, swelling of the adhesive composition occurred by immersing in NMP, and as a result, peeling of the adhesive composition from the glass support occurred. Therefore, it was shown that even if the laminate formed from the adhesive composition according to Examples 1 to 20 was immersed in NMP, no swelling of the adhesive composition occurred and no peeling of the adhesive composition from the glass support occurred.

Industrial availability

The adhesive composition and adhesive film according to the present invention can be preferably used, for example, in a manufacturing process of a micronized semiconductor device.

Claims (11)

An elastomer containing a styrene unit as a structural unit of the main chain and having a content of the styrene unit of 14% by weight or more and 50% by weight or less;
A hydrocarbon resin,
Contains acrylic resin,
The hydrocarbon resin is a cycloolefin polymer,
The cycloolefin polymer is characterized in that it contains, as a monomer component, at least one selected from the group consisting of norbornene, norbornadiene, and their alkyl substituents, alkenyl substituents, alkylidene substituents, and aryl substituents. Adhesive composition made of. The method of claim 1,
Adhesive composition, characterized in that the weight average molecular weight of the hydrocarbon resin is 10,000 to 200,000. The method of claim 1,
The adhesive composition, wherein the acrylic resin contains an alkyl (meth)acrylate having a chain structure, a (meth)acrylate having an aliphatic ring, and styrene as structural units. The method of claim 1,
With respect to the total amount of the elastomer, the hydrocarbon resin and the acrylic resin,
The content rate of the elastomer is in the range of 50% by weight or more and 98% by weight or less,
The content rate of the hydrocarbon resin is in the range of 1% by weight or more and 49% by weight or less,
The adhesive composition, wherein the content of the acrylic resin is in the range of 1% by weight or more and 49% by weight or less. The method of claim 1,
The adhesive composition, wherein the content of the styrene unit contained as a structural unit of the main chain of the elastomer is 17% by weight or more and 40% by weight or less. The method of claim 1,
Adhesive composition, characterized in that the elastomer contains at least two types of styrene-based elastomers having different contents of styrene units contained as structural units of the main chain The method of claim 1,
Adhesive composition, characterized in that the weight average molecular weight of the elastomer is 20,000 or more and 200,000 or less. The method of claim 1,
Adhesive composition, characterized in that the elastomer is a hydrogenated material. The method of claim 1,
Adhesive composition, characterized in that both ends of the elastomer are block polymers of styrene. The method of claim 1,
Adhesive composition, characterized in that the elastomer is a hydrogenated product of a block copolymer of styrene and conjugated diene. An adhesive film, wherein an adhesive layer comprising the adhesive composition according to claim 1 is formed on the film.