JP6128837B2 - Method for producing adhesive composition, adhesive composition and adhesive film - Google Patents

Description

  The present invention relates to a method for producing an adhesive composition, an adhesive composition, and an adhesive film.

  As mobile phones, digital AV devices, IC cards, etc. have become more sophisticated, there is an increasing demand for highly integrated silicon in the package by reducing the size and thickness of semiconductor silicon chips (hereinafter referred to as chips). ing. For example, an integrated circuit that integrates a plurality of chips into a single package as represented by a CSP (chip size package) or an MCP (multi-chip package) is required to be thin. In order to achieve high integration of chips in the package, it is necessary to reduce the thickness of the chip to a range of 25 to 150 μm.

  However, since a semiconductor wafer (hereinafter referred to as a wafer) that becomes a base of a chip becomes thin by grinding, its strength is weakened, and the wafer is likely to be cracked or warped. Further, since it is difficult to automatically transport a wafer whose strength has been reduced by making it thin, it has to be transported manually, and the 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, or the like, to the wafer to be ground. . Since the wafer strength can be maintained by the wafer handling system, the transport of the thinned semiconductor wafer can be automated.

  In the wafer handling system, the wafer and the support plate are bonded together using an adhesive tape, a thermoplastic resin, an adhesive, or the like. Then, after thinning the wafer to which the support plate is attached, 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 to peel the wafer from the support plate.

  Here, in recent years, hydrocarbon adhesives have been developed as the adhesive (Patent Documents 1 and 2).

Special table 2009-529065 (released on August 13, 2009) Special table 2010-506406 (released February 25, 2010)

  However, the material used for the hydrocarbon-based adhesive according to the prior art is often in the form of pellets, and the adhesive contains an anti-sticking agent (lubricant) used in the process of molding into pellets. End up. When such an adhesive containing an anti-sticking agent is used for bonding the wafer and the wafer support, even if the wafer is dissolved and washed with a solvent after use, a residue is generated on the washed wafer. When such a residue is generated on the wafer, the electrical characteristics and yield of the substrate are reduced.

  The present invention has been made in view of the above problems, and is used for adhesion between a wafer and a support for the wafer, and then bonded to prevent generation of residues on the wafer when dissolved and washed with a solvent. The main object is to provide a method for producing an adhesive composition and the adhesive composition.

  In order to solve the above-described problems, a method for producing an adhesive composition for bonding a wafer and a support of the wafer according to the present invention is a purification method for removing an anti-sticking agent contained in the adhesive composition. It is characterized by including a process.

  The adhesive composition for adhering a wafer and the support of the wafer according to the present invention is such that the content of the metal component derived from the anti-sticking agent is 10 ppb or more and 2 ppm or less with respect to the total solid weight. It is characterized by being.

  An adhesive film for adhering a wafer and the support of the wafer according to the present invention is an adhesive comprising an adhesive composition for adhering the wafer according to the present invention and the support of the wafer on the film. It is characterized in that a layer is formed.

  The manufacturing method of the adhesive composition for adhere | attaching the wafer and the support body of the said wafer based on this invention includes the refinement | purification process which removes the anti-sticking agent contained in an adhesive composition. Therefore, it is possible to produce an adhesive composition that prevents generation of residues on the wafer when it is used for bonding the wafer and the wafer support and then dissolved and washed with a solvent. Further, it is possible to provide an adhesive composition that prevents generation of residues on a wafer when it is used for bonding between a wafer and a support of the wafer and then dissolved and washed with a solvent.

[Adhesive composition]
The adhesive composition according to the present invention is an adhesive composition from which the anti-sticking agent has been removed, and the content of the metal component derived from the anti-sticking agent is 10 ppb with respect to the total solid weight of the adhesive composition. Above, it is 2 ppm or less. The adhesive composition according to the present invention may contain a hydrocarbon resin or an elastomer.

  The adhesive composition according to the present invention contains a resin for imparting adhesiveness. The resin preferably includes at least one selected from hydrocarbon resins and elastomers.

(Hydrocarbon resin)
The hydrocarbon resin is a resin having a hydrocarbon skeleton and polymerizing monomer components. Examples of the hydrocarbon resin include cycloolefin polymer (hereinafter also referred to as “resin A”), and at least one resin selected from the group consisting of terpene resin, rosin resin, and petroleum resin (hereinafter referred to as “resin”). B ”).

  The cycloolefin polymer is a resin obtained by polymerizing a cycloolefin monomer as a monomer component. Examples of the cycloolefin monomer include bicyclics such as norbornene and norbornadiene, tricyclics such as dicyclopentadiene and hydroxydicyclopentadiene, tetracyclics such as tetracyclododecene, and pentacycles such as cyclopentadiene trimer. , Heptacycles such as tetracyclopentadiene, or alkyl (methyl, ethyl, propyl, butyl, etc.), alkenyl (vinyl, etc.), alkylidene (ethylidene, etc.), aryl (phenyl) , Tolyl, naphthyl and the like) and the like. The resin (A) may be one obtained by polymerizing only one of these cycloolefin monomers, or may be obtained by copolymerizing two or more.

  Moreover, the monomer component contained in resin (A) is not limited to a cycloolefin monomer, You may contain the other monomer copolymerizable with the said cycloolefin monomer. Examples of other monomers include linear or branched alkene monomers, and examples of such alkene monomers include α- such as ethylene, propylene, 1-butene, isobutene, and 1-hexene. Examples include olefins. The alkene monomer may be used alone or in combination of two or more.

  Although the molecular weight of resin (A) is not specifically limited, For example, the weight average molecular weight (Mw) measured as a polystyrene conversion value by gel permeation chromatography (GPC) is 50,000-200,000, More preferably Is from 50,000 to 150,000. When the weight average molecular weight of the resin (A) is within the above range, cracks hardly occur after film formation, and solubility in a specific solvent can be obtained.

  The monomer component constituting the resin (A) is preferably 5 mol% or more of cycloolefin monomer from the viewpoint of high heat resistance (low thermal decomposability / thermal weight reduction), and 10 mol%. The above is more preferably a cycloolefin monomer, and more preferably 20 mol% or more. The upper limit is not particularly limited, but it is preferably 80 mol% or less from the viewpoint of solubility and stability over time in a solution, and more preferably 70 mol% or less. When a linear or branched alkene monomer is contained as another monomer, the solubility and flexibility should be 10 to 90 mol% with respect to the whole monomer component constituting the resin (A). From the point, 20 to 85 mol% is more preferable, and 30 to 80 mol% is particularly preferable.

  The polymerization method and polymerization conditions for 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 the resin (A) include “APEL (trade name)” manufactured by Mitsui Chemicals, “TOPAS (trade name)” manufactured by Polyplastics, and “ZEONOR (trade name) manufactured by Nippon Zeon Co., Ltd. Product name) "and" ZEONEX (product name) ", and" ARTON (product name) "manufactured by JSR Corporation.

  The resin (B) is at least one resin selected from the group consisting of a terpene resin, a rosin resin, and a petroleum resin as described above. Examples of the terpene resin include terpene resins, terpene phenol resins, modified terpene resins, hydrogenated terpene resins, and hydrogenated terpene phenol resins. Examples of the rosin resin 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 Maron Inden petroleum resins. Among these, hydrogenated terpene resins and hydrogenated terpene phenol resins are particularly preferable.

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

  In addition, you may mix and use resin (A) and resin (B). The content of the resin (A) is preferably 40 parts by weight or more, more preferably 60 parts by weight or more based on the entire hydrocarbon resin. When the content of the resin (A) is 40 parts by weight or more of the entire hydrocarbon resin, high heat resistance (low thermal decomposability) can be exhibited together with flexibility.

(Elastomer)
The adhesive composition according to the present invention preferably contains an elastomer. The elastomer contained in the adhesive composition according to the present invention preferably contains a styrene unit as a constituent unit of the main chain. Specifically, the content of the styrene unit may be in the range of 15% by weight to 50% by weight, and the weight average molecular weight may be in the range of 10,000 to 200,000.

  In the present specification, the “structural unit” refers to a structure resulting from a single molecule monomer in a structure constituting a polymer. In the present specification, the “styrene unit” is a constituent unit derived from the styrene contained in the polymer when the styrene 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.

  If 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 10,000 or more and 200,000 or less, it is easy for a hydrocarbon solvent described later. Therefore, it can be removed more easily and quickly. Further, since the content of the styrene unit and the weight average molecular weight are in the above ranges, a resist solvent (eg, PGMEA, PGME, etc.), acid (hydrofluoric acid) exposed when the wafer is subjected to a resist lithography process. Etc.) and excellent resistance to alkali (TMAH etc.).

  The content of styrene units is more preferably 17% by weight or more, and more preferably 40% by weight or less.

  A more preferable range of the weight average molecular weight is 20,000 or more, and a more preferable range is 150,000 or less.

  As the elastomer, various elastomers are used as long as the content of styrene units is in the range of 14% by weight to 50% by weight and the weight average molecular weight of the elastomer is in the range of 10,000 to 200,000. be able to. 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). , Ethylene-propylene terpolymer (EPT) 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), and styrene-ethylene-styrene having a styrene block reactively crosslinked. Tylene-propylene-styrene block copolymer (Septon V9461 (manufactured by Kuraray Co., Ltd.)), a styrene block having a reactive crosslinking type styrene-ethylene-butylene-styrene block copolymer (Septon V9827 (manufactured by Kuraray Co., Ltd.)) The styrene unit content and the weight average molecular weight are in the above-mentioned ranges.

  Of the elastomers, hydrogenated products are more preferable. If it is a hydrogenated product, the stability to heat is improved, and degradation such as decomposition and polymerization hardly occurs. Moreover, it is more preferable from the viewpoint of solubility in hydrocarbon solvents and resistance to resist solvents.

  Further, among elastomers, those having both ends of a styrene block polymer are more preferable. This is because styrene having high thermal stability is blocked at both ends, thereby exhibiting higher heat resistance.

  More specifically, it is more preferably a hydrogenated product of a block copolymer of styrene and conjugated diene. Stability against heat is improved, and degradation such as decomposition and polymerization hardly occurs. Moreover, higher heat resistance is exhibited by blocking styrene having high thermal stability at both ends. Furthermore, it is more preferable from the viewpoint of solubility in hydrocarbon solvents and resistance to resist solvents.

  Examples of commercially available products that can be used as an elastomer contained in the adhesive composition according to the present invention include “Septon (trade name)” manufactured by Kuraray Co., Ltd., “Hibler (trade name)” manufactured by Kuraray Co., Ltd. and “Tuftec” manufactured by Asahi Kasei Co., Ltd. (Trade name) ”,“ Dynalon (trade name) ”manufactured by JSR Corporation, and the like.

  As content of the elastomer contained in the adhesive composition according to the present invention, for example, the total amount of the adhesive composition is 100 parts by weight, preferably 10 parts by weight or more and 80 parts by weight or less, preferably 20 parts by weight or more and 60 parts by weight. Part or less is more preferable.

  A plurality of types of elastomers may be mixed. That is, the adhesive composition according to the present invention may include a plurality of types of elastomers. At least one of the plurality of types of elastomers includes a styrene unit as a main chain constituent unit, 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 is 10,000 or more. The range of 200,000 or less is within the scope of the present invention. Moreover, in the adhesive composition which concerns on this invention, when several types of elastomer is included, as a result of mixing, you may prepare so that content of a styrene unit may become said range. For example, Septon 8007 of Kuraray Septon (trade name) having a styrene unit content of 30% by weight and Septon 2063 of Septon (trade name) having a styrene unit content of 13% by weight is 1 pair by weight. When mixed at 1, the styrene content with respect to the whole elastomer contained in the adhesive composition is 21 to 22% by weight, which is 14% by weight or more. For example, when a styrene unit of 10% by weight and 60% by weight are mixed on a one-to-one basis, the result is 35% by weight, which is within the above range. The present invention may be in such a form. Moreover, it is most preferable that the plurality of types of elastomers contained in the adhesive composition according to the present invention all contain styrene units in the above range and have a weight average molecular weight in the above range.

(solvent)
The adhesive composition according to the present invention preferably contains a solvent that dissolves the hydrocarbon resin or elastomer. As such a solvent, for example, a nonpolar hydrocarbon solvent, a polar or nonpolar petroleum solvent, or the like can be used.

  Preferably, the solvent can comprise a condensed polycyclic hydrocarbon. When the solvent contains a condensed polycyclic hydrocarbon, it is possible to avoid white turbidity that may occur when the adhesive composition is stored in a liquid form (especially at a low temperature), thereby improving product stability. .

  Examples of the hydrocarbon solvent include linear, branched or cyclic hydrocarbons. For example, straight chain hydrocarbons such as hexane, heptane, octane, nonane, methyloctane, decane, undecane, dodecane, tridecane, etc., branched hydrocarbons having 3 to 15 carbon atoms; p-menthane, o-menthane, m -Menthane, diphenylmenthane, alpha-terpinene, beta-terpinene, gamma-terpinene, 1,4-terpine, 1,8-terpine, bornane, norbornane, pinane, alpha-pinene, beta-pinene, tujan, alpha-tujon, β-Tujon, Karan, Longifolene and the like can be mentioned.

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

  The condensed polycyclic hydrocarbon is a condensed ring hydrocarbon formed by two or more monocycles supplying only one side of each ring to each other, and is a carbon obtained by condensing two monocycles. It is preferable to use hydrogen.

  Such hydrocarbons include combinations of 5-membered and 6-membered rings, or combinations of two 6-membered rings. Examples of hydrocarbons combining 5-membered and 6-membered rings include indene, pentalene, indane, tetrahydroindene and the like. Examples of hydrocarbons combining two 6-membered rings include naphthalene, tetrahydronaphthalene ( Tetralin) and decahydronaphthalene (decalin).

  Further, when the solvent contains the condensed polycyclic hydrocarbon, the component contained in the solvent may be only the condensed polycyclic hydrocarbon, or contains other components such as saturated aliphatic hydrocarbon, for example. You may do it. In this case, the content of the condensed polycyclic hydrocarbon is preferably 40 parts by weight or more, more preferably 60 parts by weight or more based on the entire hydrocarbon solvent. When the content of the condensed polycyclic hydrocarbon is 40 parts by weight or more of the entire 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.

  Examples of the saturated aliphatic hydrocarbon include straight chain hydrocarbons such as hexane, heptane, octane, nonane, methyloctane, decane, undecane, dodecane, tridecane, branched hydrocarbons having 3 to 15 carbon atoms, Examples thereof include p-menthane, o-menthane, m-menthane, diphenylmenthane, 1,4-terpine, 1,8-terpine, bornane, norbornane, pinane, tsujang, kalan, longifolene and the like.

  The content of the solvent in the adhesive composition according to the present invention may be appropriately adjusted according to the thickness of the adhesive layer formed using the adhesive composition. For example, the adhesive composition When the total amount is 100 parts by weight, it is preferably in the range of 20 to 90 parts by weight. If the content of the solvent is within the above range, the viscosity can be easily adjusted.

(Thermal polymerization inhibitor)
The adhesive composition according to the present invention 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 is highly reactive to radicals, it reacts preferentially over the monomer and inhibits polymerization of the monomer. In the adhesive composition containing such a thermal polymerization inhibitor, the polymerization reaction is suppressed under a high temperature environment (particularly, 250 ° C. to 350 ° C.).

  For example, a semiconductor manufacturing process may include a high temperature process in which a wafer to which a support is bonded is heated at 250 ° C. for 1 hour. At this time, if polymerization of the adhesive composition occurs at a high temperature, the solubility in a peeling solution for peeling the support plate (support plate) from the wafer after the high-temperature process is lowered, and the support plate cannot be peeled well from the wafer. . However, in the adhesive composition of the present invention containing a thermal polymerization inhibitor, since the oxidation due to heat and the polymerization reaction accompanying it are suppressed, the support plate can be easily peeled off even after a high temperature process, Generation of residue can be suppressed.

  Although it will not specifically limit if it is effective in preventing the radical polymerization reaction by heat | fever as a thermal-polymerization inhibitor, The thermal-polymerization inhibitor which has a phenol is preferable. Thereby, good solubility can be ensured even after high temperature treatment in the atmosphere. As such a thermal polymerization inhibitor, it is possible to use a hindered phenol antioxidant, for example, pyrogallol, benzoquinone, hydroquinone, methylene blue, tert-butylcatechol, monobenzyl ether, methylhydroquinone, amylquinone, Amyloxyhydroquinone, n-butylphenol, phenol, hydroquinone monopropyl ether, 4,4 ′-(1-methylethylidene) bis (2-methylphenol), 4,4 ′-(1-methylethylidene) bis (2,6 -Dimethylphenol), 4,4 '-[1- [4- (1- (4-hydroxyphenyl) -1-methylethyl) phenyl] ethylidene] bisphenol, 4,4', 4 "-ethylidene tris (2- Methylphenol), 4,4 ', 4 "-ethylident Sphenol, 1,1,3-tris (2,5-dimethyl-4-hydroxyphenyl) -3-phenylpropane, 2,6-di-tert-butyl-4-methylphenol, 2,2′-methylenebis ( 4-methyl-6-tert-butylphenol), 4,4′-butylidenebis (3-methyl-6-tert-butylphenol), 4,4′-thiobis (3-methyl-6-tert-butylphenol), 3,9 -Bis [2- (3- (3-tert-butyl-4-hydroxy-5-methylphenyl) -propionyloxy) -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro (5 , 5) Undecane, triethylene glycol-bis-3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate, n Octyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, pentaerythryltetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (trade name) IRGANOX 1010 (manufactured by Ciba Japan), tris (3,5-di-tert-butylhydroxybenzyl) isocyanurate, thiodiethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] Is mentioned. Only one type of thermal polymerization inhibitor may be used, or two or more types may be used in combination.

  The content of the thermal polymerization inhibitor may be appropriately determined according to the type of the hydrocarbon resin or elastomer and the application and use environment of the adhesive composition. For example, the amount of the hydrocarbon resin or elastomer is 100 parts by weight. Is preferably 0.1 parts by weight or more and 10 parts by weight or less. If the content of the thermal polymerization inhibitor is within the above range, the effect of suppressing the polymerization due to heat is satisfactorily exerted, and the decrease in the solubility of the adhesive composition in the stripping solution can be further suppressed after the high temperature process. .

  Moreover, the structure which contains the addition solvent which consists of a composition different from the solvent for melt | dissolving a thermal polymerization inhibitor and melt | dissolving a hydrocarbon resin or an elastomer may be sufficient as the adhesive composition which concerns on this invention. Although it does not specifically limit as an additive solvent, The organic solvent which melt | dissolves the component contained in an adhesive composition can be used.

  As an organic solvent, what is necessary is just to melt | dissolve each component of an adhesive composition, for example, and it can be set as a uniform solution, and it can use it combining arbitrary 1 type (s) or 2 or more types.

  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, for example, geraniol, nerol, linalool, citral, citronellol, menthol, isomenthol, neomenthol, α-terpineol, β-terpineol, γ-terpineol, terpinen-1-ol, terpinen-4-ol, dihydroterpinyl acetate, 1,4-cineole, 1,8-cineole, borneol, carvone, yonon, thuyon, For example, camphor. Lactones such as γ-butyrolactone; Ketones such as acetone, methyl ethyl ketone, cyclohexanone (CH), methyl-n-pentyl ketone, methyl isopentyl ketone, 2-heptanone; ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol Polyhydric alcohols such as ethylene glycol monoacetate, diethylene glycol monoacetate, propylene glycol monoacetate, dipropylene glycol monoacetate, etc., compounds having an ester bond, monohydric ethers of the above polyhydric alcohols or compounds having an ester bond A monoalkyl ether such as monoethyl ether, monopropyl ether, monobutyl ether or an ether bond such as monophenyl ether Derivatives of polyhydric alcohols such as propylene glycol monomethyl ether acetate (PGMEA) and propylene glycol monomethyl ether (PGME) are preferred among them; cyclic ethers such as dioxane, methyl lactate, lactic acid Esters such as ethyl (EL), methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, ethyl ethoxypropionate; anisole, ethyl benzyl ether, cresyl methyl ether, diphenyl ether, di Aromatic organic solvents such as benzyl ether, phenetole, and butyl phenyl ether can be exemplified.

  The content of the additive solvent may be appropriately determined according to the type of the thermal polymerization inhibitor and the like. For example, when the thermal polymerization inhibitor is 1 part by weight, it is 1 part by weight or more and 50 parts by weight or less. 1 to 30 parts by weight is more preferable, and 1 to 15 parts by weight is most preferable. When the content of the thermal polymerization inhibitor is within the above range, the thermal polymerization inhibitor can be sufficiently dissolved.

(Other ingredients)
The adhesive composition according to the present invention may further contain other miscible substances as long as the essential characteristics of the present invention are not impaired. For example, various commonly used additives such as an additional resin for improving the performance of the adhesive, a plasticizer, an adhesion aid, a stabilizer, a colorant, and a surfactant can be further used.

(Method for preparing adhesive composition)
The method for preparing the adhesive composition before adjusting the content of the anti-sticking agent is not particularly limited, and a known method may be used. For example, a hydrocarbon resin or an elastomer is dissolved in a solvent, and the existing stirring is performed. An adhesive composition can be obtained by stirring each composition using an apparatus.

  Moreover, when adding a thermal polymerization inhibitor to an adhesive composition, it is preferable to add what was previously dissolved in an additive solvent for dissolving the thermal polymerization inhibitor.

  And the adhesive composition prepared in this way can be used for the refinement | purification process in the manufacturing method of the adhesive composition which concerns on this invention mentioned later, and the adhesive composition which concerns on this invention can be obtained. In addition, even if it is methods other than the manufacturing method of the adhesive composition which concerns on this invention mentioned later, if it is a method which can remove an anti-sticking agent, the adhesive composition which concerns on this invention can be manufactured.

(Anti-glue agent)
In the refining process, the anti-sticking agent removed from the adhesive composition may be referred to as a lubricant, and when the resin (hydrocarbon resin, elastomer) used for the adhesive composition is molded into a pellet, It is contained. As a result, when an adhesive composition is prepared using the resin, an anti-sticking agent is finally contained in the adhesive composition. Since many commercially available resins are supplied in pellet form, many adhesive compositions contain an anti-sticking agent.

Examples of anti-tackiness agents include talc _{(Mg 3 Si 4 O 10 (} OH) 2), hydrotalcite _{(Mg 6 Al 2 (CO 3} ) (OH) 16 · 4H 2 O, Mg 6 Fe 2 (CO 3 _{) (OH) 16 · 4H 2} O, Mg 6 Mn 2 (CO 3) (OH) 16 · 4H 2 O) salts such as minerals, lead stearate, zinc stearate, calcium stearate, stearic acid and magnesium stearate Paraffins such as salts, liquid paraffin and paraffin wax, and fatty acid amides such as stearic acid, stearic acid amide, oleic acid amide, methylene bis stearic acid amide, ethylene bis stearic acid amide, and erucic acid amide.

  In the adhesive composition according to the present invention, the amount of the anti-sticking agent contained in the adhesive composition is reduced. The amount of the anti-sticking agent contained in the adhesive composition can be represented by the content of the metal component derived from the anti-sticking agent. Examples of the metal component derived from the anti-sticking agent include sodium, magnesium, aluminum, potassium, calcium, chromium, manganese, iron, nickel, copper, lead, and zinc.

  In the adhesive composition according to the present invention, the content of the metal component derived from the anti-sticking agent is 10 ppb or more and 2 ppm or less with respect to the total solid weight of the adhesive composition.

  If the content of the metal component derived from the anti-sticking agent contained in the adhesive composition is 2 ppm or less with respect to the total solid weight of the adhesive composition, using this adhesive composition, the wafer, the support, Even after bonding, dissolving and washing, it is preferable because no residue is generated on the wafer. Although the lower limit of the content of the metal component derived from the anti-sticking agent contained in the adhesive composition is desirably “0”, the detection limit value of the metal component (generally 10 ppb in general) )And it is sufficient. Therefore, the lower limit of the content of the metal component derived from the anti-sticking agent contained in the adhesive composition is 10 ppb with respect to the total solid weight of the adhesive composition.

  The content of the metal component derived from the anti-sticking agent contained in the adhesive composition can be determined, for example, by quantifying the metal component in the adhesive composition by ICP-MS (Dielectric Coupled Plasma Mass Spectrometry). it can. Specifically, in the solution containing the adhesive composition, the measurement result obtained by measuring the metal content by the above method is converted into a value for the total solid weight of the adhesive composition, and the content concentration in the adhesive composition is The content of the metal component derived from the anti-sticking agent in the adhesive composition can be calculated.

  In the adhesive composition according to the present invention, among the metal components derived from the anti-sticking agent contained in the adhesive composition, the content of the most abundant metal component is the total solid weight of the adhesive composition. On the other hand, it may be 10 ppb or more and 2 ppm or less.

(Use of adhesive composition)
The adhesive composition according to the present invention is used for bonding a wafer and a support of the wafer.

  For example, the support plays a role of supporting the wafer in the step of thinning the wafer, and is bonded to the wafer by the adhesive composition according to the present invention. In one Embodiment, the support body is formed with the glass or silicon whose film thickness is 500-1000 micrometers, for example.

  In one embodiment, the support is provided with a hole penetrating the support in the thickness direction. By pouring a solvent that dissolves the adhesive composition through the holes between the support and the wafer, the support and the substrate can be easily separated.

  In another embodiment, a reaction layer may be interposed between the support and the wafer in addition to the adhesive layer. The reaction layer is altered by absorbing light irradiated through the support, and the support and wafer can be easily altered by irradiating the reaction layer with light or the like to alter the reaction layer. Can be separated. In this case, it is preferable to use a support in which a hole penetrating in the thickness direction is not provided.

The light applied to the reaction layer may be, for example, a solid laser such as a YAG laser, Libby laser, glass laser, YVO ₄ laser, LD laser, or fiber laser, or a liquid laser such as a dye laser, depending on the wavelength that can be absorbed by the reaction layer. A gas laser such as a CO ₂ laser, an excimer laser, an Ar laser, or a He—Ne laser, a laser beam such as a semiconductor laser or a free electron laser, or a non-laser beam may be used as appropriate. 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 a light absorber that is decomposed by light or the like, for example. Examples of the light absorber include graphite powder, fine metal powder such as iron, aluminum, copper, nickel, cobalt, manganese, chromium, zinc, tellurium, metal oxide powder such as black titanium oxide, carbon black, or aromatic. Dyes or pigments such as diamino metal complexes, aliphatic diamine metal complexes, aromatic dithiol metal complexes, mercaptophenol metal complexes, squarylium compounds, cyanine dyes, methine dyes, naphthoquinone dyes, anthraquinone dyes Can be used. Such a reaction layer can be formed, for example, by mixing with a binder resin and coating on a support. 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 a plasma CVD method may be used. For example, a metal film can be used as the inorganic film. As the organic film, a fluorocarbon film can be used. Such a reaction film can be formed on a support by a plasma CVD method, for example.

  The adhesive composition according to the present invention is suitably used for adhesion between a wafer and a support which are subjected to a thinning process after being bonded to the support. As described above, the support retains the strength of the wafer when the wafer is thinned. The adhesive composition according to the present invention is suitably used for bonding such a wafer and a support.

  In addition, the adhesive composition according to the present invention is suitably used for bonding a wafer to be used in an electrode forming process after being bonded to a support and the support.

  If the adhesive composition contains an anti-sticking agent, metal components derived from the anti-sticking agent remain on the wafer, which adversely affects the electrical characteristics of the wafer on which the electrode is formed. On the other hand, since the anti-sticking agent is removed from the adhesive composition according to the present invention, no residue is formed on the wafer after the wafer and the support are bonded, dissolved and washed. Therefore, if the adhesive composition according to the present invention is used for bonding the wafer and the support, the electrical characteristics, particularly the connection characteristics, of the wafer provided with electrical elements such as electrodes are good.

  According to the adhesive composition of the present invention, it is possible to prevent the generation of residues on the wafer when it is used for bonding the wafer and the support of the wafer and then dissolved and washed with a solvent.

(Removal of the adhesive layer formed by the adhesive composition)
In the case of removing the adhesive layer after separating the wafer and the substrate bonded by the adhesive composition according to the present invention by altering the above reaction layer, a solvent for dissolving the adhesive composition is used. If used, it can be easily dissolved and removed. In addition, by directly supplying a solvent to the adhesive layer in a state where the wafer and the support are bonded without using the reaction layer, the adhesive layer is easily dissolved and the adhesive layer is removed. 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 the support is provided with a through hole.

[Method for producing adhesive composition]
The manufacturing method of the adhesive composition for adhere | attaching the wafer and the support body of the said wafer based on this invention includes the refinement | purification process which removes the anti-sticking agent contained in an adhesive composition. Further, in the method for producing an adhesive composition according to the present invention, in the purification step, the content of the metal component derived from the anti-sticking agent contained in the adhesive composition is determined based on the total solid weight of the adhesive composition. It is preferable to make it 2 ppm or less. Although the lower limit of the content of the metal component derived from the anti-sticking agent contained in the adhesive composition is desirably “0”, the detection limit value of the metal component (generally 10 ppb in general) ).

(Purification process)
Specific examples of the method for removing the anti-sticking agent contained in the adhesive composition in the purification step include (1) a method of removing the anti-sticking agent by filtering the adhesive composition.

  In the method of removing the anti-sticking agent by filtering the adhesive composition, first, the adhesive composition is passed through a filter having a pore diameter of 0.01 to 10 μm (preferably 0.1 to 10 μm) to prevent sticking. Remove the agent from the solution. The pore size of the filter can be appropriately selected according to the type of anti-sticking agent contained in the adhesive composition. That is, the filter may have any pore diameter that can filter the anti-sticking agent.

  Examples of the material of the filter include polypropylene, nylon (polyamide), polytetrafluoroethylene (PTFE), and the like. The pore diameter may be appropriately selected from 0.01 to 10 μm, preferably from 0.1 to 10 μm.

  In addition, as the pretreatment step (2) of the purification step (1), a resin solution obtained by dissolving a resin used for the adhesive composition in a solvent becomes a poor solvent for the resin solution, for example, water or alcohol The resin may be re-precipitated (deposited) by dropping into the inside. Such alcohol is preferably an alcohol having 1 to 4 carbon atoms, and examples thereof include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, and 2-butanol. Examples of the solvent for dissolving the resin include terpene solvents such as p-menthane described above, and petroleum solvents such as cyclohexane and decahydronaphthalene described above. Then, by removing the precipitated resin from the solution in which the anti-sticking agent is dispersed, the anti-sticking agent is removed from the resin. Thus, an adhesive composition is prepared using the resin from which the anti-sticking agent has been removed. And the adhesive composition from which the anti-sticking agent was removed can be manufactured by further refine | purifying an adhesive composition by the said refinement | purification process (1).

  The resin precipitated in the solution can be taken out of the solution by methods such as filtration, removal of the supernatant (decantation), centrifugation, and reprecipitation of the resin.

  Further, as the pretreatment step (2) of the purification step (1), the pelletized resin can be washed to remove the anti-sticking agent. First, the pellet-shaped resin is washed with stirring in a poor solvent such as water or alcohol (preferably an alcohol having 1 to 4 carbon atoms) to remove the anti-sticking agent adhering to the surface of the pellet-shaped resin. Let go. Then, the solution in which the pellets are dispersed is filtered through a coarse mesh filter having a pore diameter of 10 to 200 μm, for example, to remove the anti-sticking agent detached from the resin. Thus, an adhesive composition is prepared using the resin from which the anti-sticking agent has been removed. And the adhesive composition from which the anti-sticking agent was removed can be manufactured by further refine | purifying an adhesive composition by the said refinement | purification process (1).

  Similarly to the above-described washing with water, alcohol, etc., the anti-sticking agent is dissolved and removed by an acid washing removal method in which the pelletized resin is immersed in an acid such as hydrofluoric acid to dissolve and remove the anti-sticking agent. May be.

  Alternatively, the anti-sticking agent may be removed from the resin by collecting relatively light pellets by collecting the relatively light anti-sticking agent with wind power using a wind separator (jet separator).

  Further, as the pretreatment step (2) of the purification step (1), the anti-sticking agent can be removed by ultrasonic cleaning while the resin is immersed in the solution. Examples of the solution in which the resin is immersed include a poor solvent. Examples of the poor solvent include glycol ethers such as propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, and lower alcohols having 1 to 5 carbon atoms such as methanol, ethanol, and propanol. By using these poor solvents, the resin itself is not substantially dissolved, but the anti-sticking agent can be removed by swelling the resin. Furthermore, the temperature at which the resin is immersed in the solution is preferably 20 degrees or more and 50 degrees or less. The ultrasonic cleaning time is preferably 5 minutes or more and 60 minutes or less. Thus, an adhesive composition is prepared using the resin from which the anti-sticking agent has been removed. And the adhesive composition from which the anti-sticking agent was removed can be manufactured by further refine | purifying an adhesive composition by the said refinement | purification process (1).

  When ultrasonic cleaning is performed while the resin is immersed in the solution, a known ultrasonic cleaner may be used.

  The method for removing the anti-sticking agent contained in the adhesive composition as described above may be performed alone or in combination with a plurality of methods. That is, the adhesive composition from which the anti-sticking agent contained in the resin has been removed by the method of precipitating and removing the anti-sticking agent may be subjected to a method of further filtering to remove the anti-sticking agent.

  When the above-mentioned resin is reprecipitated (deposited), or when the resin is washed, after filtration through a coarse mesh filter, a terpene solvent such as p-menthane, a petroleum system such as cyclohexane or decahydronaphthalene The resin may be recovered by dissolving in a solvent. When the adhesive composition is filtered to remove the anti-sticking agent, the solution obtained by filtration is used as the adhesive composition.

  According to the method for producing an adhesive composition according to the present invention, since the anti-sticking agent contained in the adhesive composition is removed by a purification process, it is dissolved in a solvent after being used for adhesion between the wafer and the wafer support. Thus, it is possible to produce an adhesive composition that prevents generation of residues on the wafer when washed. Further, it is possible to provide an adhesive composition that prevents generation of residues on a wafer when it is used for bonding between a wafer and a support of the wafer and then dissolved and washed with a solvent.

  Note that, by the method for producing an adhesive composition according to the present invention, the wafer and the support are bonded using the adhesive composition from which the anti-sticking agent is removed and the adhesive composition according to the present invention. The manufacturing method of the laminated body, the electrode forming method for forming electrodes on the wafer of the laminated body, the peeling method for peeling the support from the wafer of the laminated body, and the cleaning method for cleaning the wafer from which the support has been peeled are also within the scope of the present invention. It is.

[Adhesive film]
The adhesive composition according to the present invention can employ various usage forms depending on the application. For example, a method of forming an adhesive layer by coating on a workpiece such as a semiconductor wafer in a liquid state may be used, or an adhesive film according to the present invention, that is, a film such as a flexible film in advance. After forming an adhesive layer containing any one of the above-mentioned adhesive compositions on the top, it is dried, and a method (adhesive film method) in which this film (adhesive film) is applied to a workpiece is used. May be.

  Thus, the adhesive film which concerns on this invention is equipped with the adhesive bond layer containing one of the said adhesive composition on a 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 workpiece, and then the above-mentioned film is peeled off from the adhesive layer to remove the adhesive on the workpiece. Layers can be easily provided.

  Therefore, when this adhesive film is used, an adhesive having better film thickness uniformity and surface smoothness than the case where an adhesive composition is applied directly on a workpiece to form an adhesive layer. A layer can be formed.

  As the film used for the production of the adhesive film, the adhesive layer formed on the film can be peeled off from the film, and the adhesive layer can be transferred onto a surface to be treated such as a protective substrate or a wafer. It is not limited as long as it is a mold film. For example, the flexible film which consists of synthetic resin films, such as a polyethylene terephthalate with a film thickness of 15-125 micrometers, polyethylene, a polypropylene, a polycarbonate, and a polyvinyl chloride, is mentioned. It is preferable that a release treatment is performed on the film as necessary to facilitate transfer.

  As a method of forming the adhesive layer on the film, a known method is used according to the desired thickness and uniformity of the adhesive layer, and the dry thickness of the adhesive layer on the film is 10 to 10. The method of apply | coating the adhesive composition which concerns on this invention so that it may be set to 1000 micrometers is mentioned.

  Moreover, when using a protective film, as a protective film, although not limited as long as it can peel from an adhesive bond layer, a polyethylene terephthalate film, a polypropylene film, and a polyethylene film are preferable, for example. Each protective film is preferably coated or baked with silicon. This is because peeling from the adhesive layer is facilitated. Although the thickness of a protective film is not specifically limited, 15-125 micrometers is preferable. It is because the softness | flexibility of the adhesive film provided with the protective film can be ensured.

  The method of using the adhesive film is not particularly limited. For example, when a protective film is used, the film is peeled off and the exposed adhesive layer is overlaid on the workpiece to form a film. A method of thermocompression bonding the adhesive layer to the surface of the workpiece by moving the heating roller from above (the back surface of the surface on which the adhesive layer is formed) can be mentioned. At this time, the protective film peeled off from the adhesive film can be stored and reused by winding it in a roll with a roller such as a winding roller.

(Preparation of adhesive composition)
The resins (hydrocarbon resins or elastomers), polymerization inhibitors, main solvents and additive solvents used in Examples 1 to 10 and Comparative Examples 1 to 4 are shown in Tables 1 and 2 below. In Table 2, all “parts” are parts by weight.

  As the hydrocarbon resin, “TOPAS (trade name) 8007X10, Mw = 95,000, Mw / Mn = 1.9, m: n = 35: 65 (molar ratio)” manufactured by Polyplastics Co., Ltd. (hereinafter referred to as COC) "APEL (trade name) 8008T COC, Mw = 100,000, Mw / Mn = 2.1, m: n = 80: 20 (molar ratio)" (hereinafter referred to as COC) manufactured by Mitsui Chemicals, Inc. 1).

  As the elastomer, Kuraray Septon (trade name) HG252 (SEEPS-OH: polystyrene-poly (ethylene-ethylene / propylene) block-polystyrene terminal hydroxyl group-modified), HG253, and Septon 8007 (SEBS: polystyrene-poly (ethylene) / Butylene block-polystyrene), Tuftec (trade name) H1051 (SEBS, hydrogenated styrene-based thermoplastic elastomer) and H1053 (SEBS, hydrogenated styrene-based thermoplastic elastomer) manufactured by Asahi Kasei Corporation. The “hydrogenation” in this example is a polymer obtained by hydrogenating the double bond of a block copolymer of styrene and butadiene.

  The styrene content in the elastomer used and the weight average molecular weight of the elastomer are shown in Table 1 below.

  As the thermal polymerization inhibitor, “IRGANOX (trade name) 1010” manufactured by BASF was used. As the main solvent, decahydronaphthalene represented by the following chemical formula (I) was used. Moreover, butyl acetate was used as an additive solvent.

  The adhesive composition of Example 1 was prepared as follows. First, 100 parts by weight of the resin shown in Table 2 was dissolved in 255 parts by weight of the main solvent. Next, a butyl acetate solution containing a thermal polymerization inhibitor was added to 100 parts by weight of the elastomer so that the thermal polymerization inhibitor was 1 part by weight and the butyl acetate was 45 parts by weight. The adhesive composition thus obtained was filtered using a PTFE filter (manufactured by PALL) having a pore size of 1 μm. The content (metal content) of the metal component derived from the anti-sticking agent in the obtained adhesive composition was measured by ICP-MS (manufactured by Agilent Technologies, product name: 7500 cs).

  Moreover, about the adhesive composition, the anti-sticking agent removal effect was confirmed by measuring turbidity. Turbidity was measured using SHIMADZU UV-3600.

  The content of the metal component in the adhesive composition is the most contained in the adhesive composition among the 10 elements of sodium, magnesium, aluminum, potassium, calcium, chromium, manganese, iron, nickel, and copper. It was expressed as the content of the metal component. Table 2 shows the metal content in the adhesive composition. Moreover, about Examples 2-4 and 6, the adhesive composition was obtained with the same method. For Examples 5 and 7, removal of the anti-sticking agent was performed by stirring and washing with a three-one motor in a state where the adhesive resin component was immersed in methanol at 23 ° C., followed by filtration in the same manner. For anti-sticking agent, the adhesive resin component was re-precipitated by dropping it into water / methanol (weight ratio 2/8) using the decahydronaphthalene solution (10 w% concentration) of the adhesive resin component as a poor solvent. An adhesive composition was obtained in the same manner as in Example 1, except that the filtration was performed in the same manner. For Example 9, the anti-sticking agent was removed in the same manner after collecting the anti-sticking agent from the adhesive resin component using a wind separator (jet separator (ACO, Jet Separator CFS)). An adhesive composition was obtained in the same manner as in Example 1 except that the filtration was performed.

  In Example 10, the adhesive resin component was immersed in propylene glycol monomethyl ether acetate at 35 ° C. in an ultrasonic cleaning machine (manufactured by Aiwa Medical Industry, model number: AU-70C, oscillation output: 100 W, frequency: 28 kHz) The adhesive composition was obtained in the same manner as in Example 1 except that the anti-sticking agent was removed by washing for 30 minutes and then filtered in the same manner.

  After performing the said predetermined process with respect to resin of Example 5, 7-10, the adhesive composition was prepared using resin after a process. Here, in Examples 5, 7, 9, and 10, the pellets were processed as they were. In Example 8, the pellet was once dissolved and re-precipitated.

  The metal content in each adhesive composition of Examples 1 to 10 was 10 ppb or more and 2 ppm or less with respect to the total solid weight of the adhesive composition. Also, the turbidity of the adhesive composition was all good at 5% or less.

  About Comparative Examples 1-4, the adhesive composition was obtained with the method similar to Example 1 except filtering the adhesive composition and measuring metal content.

(Formation of adhesive layer)
Each adhesive composition was spin-coated on a 12-inch Si wafer and baked at 100 ° C., 160 ° C., and 200 ° C. for 5 minutes each to form an adhesive layer (film thickness 50 μm).

On the other hand, the support was provided with a reaction layer for peeling off the support and the wafer by changing the quality by irradiating the laser later. As a reaction layer, a fluorocarbon film (1 μm) is applied to a support plate (12-inch glass) by a CVD method using C ₄ F ₈ as a reaction gas under the conditions of a flow rate of 400 sccm, a pressure of 700 mTorr, a high-frequency power of 2500 W, and a film formation temperature of 240 ° C. And a thickness of 700 μm).

[Thinning thinning process]
Using a laminate of the wafer and the support, wafer thinning, photolithography, and the like were performed.

[Cleaning the adhesive layer]
The wafer and the support were separated by irradiation with a 532 nm laser. The wafer from which the support was removed was spray-cleaned with p-menthane to remove the adhesive layer. The surface of the wafer after the removal of the adhesive layer was observed with a microscope, and generation of residues was confirmed. The results are shown in Table 2. In Table 2, the result indicated by “◯” indicates that no residue was confirmed, the result indicated by “Δ” indicates that a small or small amount of residue was confirmed, and “×” The results shown indicate that large or large amounts of residue have been identified.

  As shown in Table 2, in the example, no residue was generated on the cleaned wafer, but in the comparative example, a crystal residue of 1 to 100 μm was confirmed on the cleaned wafer surface. In the comparative examples, the turbidity of the adhesive composition was all over 5%.

  The present invention is not limited to the above-described embodiment, and various modifications are possible within the scope shown in the claims, and the present invention is also applied to an embodiment obtained by appropriately combining technical means disclosed in the embodiment. It is included in the technical scope of the invention.

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

Claims (11)

Including a purification step of removing an anti-sticking agent containing a metal component contained in the adhesive composition;
In the said refinement | purification process, the solution containing the said adhesive composition is filtered, The manufacturing method of the adhesive composition for adhere | attaching the wafer and the support body of the said wafer characterized by the above-mentioned.   The content of the metal component derived from the anti-sticking agent contained in the adhesive composition in the purification step is 2 ppm or less based on the total solid weight of the adhesive composition. A method for producing an adhesive composition for adhering the wafer according to 1 and the support of the wafer.   Before the purification step, the resin composition is reprecipitated in a resin solution containing a resin forming the adhesive composition, and then the resin taken out from the resin solution is contained in the adhesive composition. A method for producing an adhesive composition for bonding the wafer according to claim 1 or 2 and a support of the wafer.   The resin that is taken out of the solution containing the resin after the resin that forms the adhesive composition is washed in the solution before the purification step, is contained in the adhesive composition. Or the manufacturing method of the adhesive composition for adhere | attaching the wafer of Claim 2, and the support body of the said wafer.   3. The wafer according to claim 1 or 2, wherein the anti-sticking agent contained in the adhesive composition is collected by wind sorting prior to the purification step. Method of manufacturing an adhesive composition for the purpose.   Prior to the purification step, the resin forming the adhesive composition is ultrasonically washed in a state where the resin is immersed in the solution, and then the resin taken out from the solution containing the resin is contained in the adhesive composition. The manufacturing method of the adhesive composition for adhere | attaching the wafer of Claim 1 or 2 and the support body of the said wafer characterized by the above-mentioned. As anti-tackiness agent contains only anti-tackiness agent containing a metal component, a wafer in which the content of the metal component derived from the anti-sticking agent, relative to the total solid weight, and wherein the above 10 ppb, is 2ppm or less And an adhesive composition for bonding the wafer support.   8. The adhesive composition for bonding a wafer and the wafer support according to claim 7, wherein the wafer is subjected to an electrode forming step after being bonded to the support.   The adhesive composition for bonding the wafer according to claim 7 or 8 and a support of the wafer, comprising a hydrocarbon resin.   The adhesive composition for bonding the wafer according to any one of claims 7 to 9 and a support of the wafer, comprising an elastomer.   An adhesive film comprising an adhesive composition for adhering the wafer according to any one of claims 7 to 10 to a support of the wafer is formed on the film. .