TW201343728A - Method of manufacturing adhesive composition, adhesive composition, and adhesive film - Google Patents

Abstract

This invention provides an adhesive composition which can prevent the occurrence of residues on a wafer through solvent dissolution and cleaning after bonding of the wafer with a wafer support. The manufacturing method for the adhesive composition used for bonding the wafer with the wafer support comprises a purification step for removing an adhesion resister contained in the adhesive composition.

Description

Method for producing a subsequent composition, an adhesive composition, and an adhesive film

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

With the increase in functionality of mobile phones, digital AV devices, and IC cards, the semiconductor wafers (hereinafter referred to as wafers) to be mounted have been miniaturized and thinned, and the demand for high integration in the package has increased. For example, an integrated circuit in which a plurality of wafers represented by CSP (wafer size package) or MCP (multi-chip package) are packaged in a single package is required to be thinned. In order to achieve high integration of the wafer in the package, the thickness of the wafer must be as thin as 25 to 150 μm.

However, since a semiconductor wafer (hereinafter referred to as a wafer) which is a base of a crystal grain is thinned by grinding, the strength thereof is weak, and the wafer is likely to be cracked or warped. In addition, since the strength is weakened by the thinning, it is difficult to automatically carry the wafer, and it is necessary to carry it by hand, and the work is complicated.

Therefore, it has been developed by a glass that will be called a support plate. A wafer processing system in which a plate made of a hard plastic or the like is attached to a wafer to be ground while maintaining wafer strength and preventing cracking and wafer warpage. Since the strength of the wafer can be maintained by the wafer processing system, the handling of the thinned semiconductor wafer can be automated.

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

Among them, hydrocarbon-based adhesives have been developed as the above-mentioned adhesives in recent years (Patent Documents 1 and 2).

[Previous Technical Literature]

[Patent Literature]

[Patent Document 1] Special Table 2009-529065 (published on August 13, 2009)

[Patent Document 2] Special Table 2010-506406 (publicized on February 25, 2010)

However, the materials used in the hydrocarbon-based adhesives of the prior art are mostly granular, and the adhesion preventing agent used in the step of molding into a granular form ( The slip agent) will be included in the adhesive. When such an adhesive containing an anti-adhesive agent is used in the subsequent step of the support of the wafer and the wafer, even if it is washed by solvent dissolution after use, a residue remains on the cleaned wafer. When such a residue is generated on the wafer, the electrical characteristics or yield of the substrate are lowered.

The present invention has been made in view of the above problems, and its main object is to provide a method for producing an adhesive composition and the adhesive composition, which is used after a wafer and a support of the wafer. When dissolved in a solvent and washed, residues on the wafer can be prevented.

In order to solve the above problems, the method for producing an adhesive composition for adhering a wafer to a support of the wafer of the present invention is characterized by comprising a purification step of removing the adhesion preventing agent contained in the adhesive composition.

The adhesive composition for adhering the wafer to the support of the wafer of the present invention is characterized in that the content of the metal component derived from the adhesion preventing agent is 10 ppb or more and 2 ppm or less based on the total solid weight.

The adhesive film of the present invention for adhering the wafer to the support of the wafer is characterized in that the film is formed on the film by the adhesive composition of the present invention for supporting the wafer and the support of the wafer. Then the layer.

The method for producing an adhesive composition for adhering a wafer to a support of the wafer of the present invention comprises a purification step of removing the adhesion preventing agent contained in the adhesive composition. For this purpose, it can be fabricated and used in wafers and crystals. After the round support, the binder composition which prevents residue on the wafer is dissolved and washed in a solvent. Further, it is possible to provide an adhesive composition for preventing a residue from occurring on the wafer after being dissolved in a solvent and washed after the wafer and the support of the wafer.

[Binder composition]

The adhesive composition of the present invention is an adhesive composition having the adhesion preventing agent removed, and the content of the metal component derived from the adhesion preventing agent is 10 ppb or more and 2 ppm or less based on the total solid weight of the adhesive composition. The adhesive composition of the present invention may also contain a hydrocarbon resin or an elastomer.

The adhesive composition of the present invention contains a resin for imparting adhesion. The resin preferably contains at least one selected from the group consisting of a hydrocarbon resin and an elastomer.

(hydrocarbon resin)

The hydrocarbon resin has a hydrocarbon skeleton and is a resin obtained by polymerizing a monomer component. The hydrocarbon resin is exemplified by, for example, a cycloolefin polymer (hereinafter also referred to as "resin A"), and at least one resin selected from the group consisting of a terpene resin, a rosin resin, and a petroleum resin (hereinafter also referred to as "resin." B").

The cycloolefin polymer is a resin obtained by polymerizing a cycloolefin monomer of a monomer component. The cycloolefin is exemplified by a tricyclic ring such as norbornene or norbornadiene, a tricyclic ring such as dicyclopentadiene or hydroxydicyclopentadiene, or a tetracyclic ring. a pentacyclic ring such as a tetracyclic ring such as dodecene or a cyclopentadienyl trimer; a heptacyclic ring such as tetracyclopentadiene or an alkyl group of the polycyclic ring (methyl, ethyl, propyl, or the like). a butyl group or the like, a substituent, an alkenyl group (vinyl group) or the like, an alkylene group (such as an ethylene group), a aryl group (phenyl group, a tolyl group, a naphthyl group or the like), or the like. The resin (A) may be one obtained by polymerizing only one of the cycloolefin monomers, or may be one obtained by copolymerizing two or more kinds.

In addition, the monomer component contained in the resin (A) is not limited to cycloolefin The hydrocarbon monomer may also contain other monomers copolymerizable with the cycloolefin monomer. The other monomer is exemplified by, for example, a linear or branched chain olefin monomer, and the olefin monomers are exemplified by α-olefins such as ethylene, propylene, 1-butene, isobutylene, and 1-hexene. Further, the olefin monomers may be used alone or in combination of two or more.

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

Further, the monomer component constituting the resin (A) has high heat resistance (low Thermal decomposition. From the viewpoint of the thermogravimetric reduction, it is preferably 5 mol% or more of a cycloolefin monomer, more preferably 10 mol% or more of a cycloolefin monomer, more preferably 20 mol% or more. The upper limit is not particularly limited, but is preferably 80 mol% or less, more preferably 70 mol% or less from the viewpoint of solubility and stability with respect to the solution. As for other monomers, in the case of a linear or branched chain olefin monomer, from the viewpoint of solubility and flexibility The total amount of the monomer components constituting the resin (A) is preferably from 10 to 90 mol%, more preferably from 20 to 85 mol%, most preferably from 30 to 80 mol%.

The polymerization method and polymerization conditions of the monomer components are not particularly limited The system can be carried out by using a conventional method.

A commercially available product which can be used as the resin (A) is exemplified as, for example, Mitsui. "APEL (trade name)" manufactured by Chemicals Co., "TOPAS (trade name)" manufactured by POLYPLASTIC, "ZEONOR (trade name)" and "ZEONEX (trade name)" manufactured by Japan ZEON Co., Ltd., and JSR company "ARTON (trade name)".

The resin (B) is a terpene resin or a rosin tree as described above. At least one resin selected from the group consisting of a fat and a petroleum resin. The terpene-based resin is exemplified by, for example, a terpene resin, a terpene phenol resin, a modified terpene resin, a hydrogenated terpene resin, and a hydrogenated terpene phenol resin. The rosin-based resin is exemplified by, for example, rosin, rosin ester, hydrogenated rosin, hydrogenated rosin ester, polymerized rosin, polymerized rosin ester, and modified rosin. Petroleum resin is exemplified by, for example, an aliphatic or aromatic petroleum resin, a hydrogenated petroleum resin, a modified petroleum resin, an alicyclic petroleum resin, and a coumarone.茚 petroleum resin, etc. Among these, a hydrogenated terpene resin and a hydrogenated terpene phenol resin are preferable.

The molecular weight of the resin (B) is not particularly limited, but for example, The weight average molecular weight (Mw) measured by polystyrene in terms of GPC is 300 to 10,000, preferably 500 to 5,000. When the weight average molecular weight of the resin (B) is within the above range, cracking hardly occurs after film formation, and high heat resistance (thermal decomposition property, resistance to sublimation property) is obtained.

Further, the resin (A) and the resin (B) may be used in combination. Resin The content of the (A) is preferably 40 parts by weight or more, more preferably 60 parts by weight or more based on the total of the hydrocarbon resin. When the content of the resin (A) is 40 parts by weight or more based on the total amount of the hydrocarbon resin, flexibility and high heat resistance (low thermal decomposition property) can be exhibited.

(elastomer)

The adhesive composition of the present invention preferably comprises an elastomer. The elastomer contained in the adhesive composition of the present invention preferably contains a styrene unit as a constituent unit of the main chain. Specifically, the content of the styrene unit is preferably 15% by weight or more and 50% by weight or less, and the weight average molecular weight is preferably in the range of 10,000 or more and 200,000 or less.

The term "constituting unit" as used in this specification means a constituent polymerization. In the structure of matter, it is caused by the structure of a single molecule. 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. The substituent is, for example, 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 ethoxy group, a carboxyl group or the like.

If the content of the styrene unit is 14% by weight or more, 50 weight When the weight average molecular weight of the elastomer is in the range of 10,000 or more and 200,000 or less, it is easily dissolved in a hydrocarbon solvent to be described later, so that it can be removed more easily and quickly. Further, by setting the content of the styrene unit and the weight average molecular weight to the above range, it is possible to exhibit a photoresist (for example, PGMEA, PGME, etc.) and an acid (hydrogen) which are exposed when the wafer is supplied to the photoresist lithography step. Excellent resistance to fluoric acid, etc., alkali (TMAH, etc.).

The content of the styrene unit is preferably 17% by weight or more, and More preferably, it is 40% by weight or less.

The weight average molecular weight is preferably in the range of 20,000 or more, and more preferably in the range of 150,000 or less.

As for the elastomer, various elastomers can be used as long as the styrene unit content 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. For example, polystyrene-poly(ethylene/propylene) block copolymer (SEP), styrene-isoprene-styrene block copolymer (SIS), styrene-butadiene-styrene can be used. Segment copolymer (SBS), styrene-butadiene-butene-styrene block copolymer (SBBS), ethylene-propylene terpolymer (EPT), and hydrides, styrene-ethylene-butyl Alkene-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 block is a reaction crosslinked type styrene-ethylene-ethylene-propylene-styrene block copolymer (Septon V9461 (Kuraray)), styrene The block is a styrene unit of a reaction-crosslinked type styrene-ethylene-butylene-styrene block copolymer (Septon V9827 (manufactured by Kuraray Co., Ltd.) having a reactive polystyrene-based hard block) And the weight average molecular weight is in the above range.

Further, the hydride is more preferable in the elastomer. In the case of a hydride, the stability to heat is improved, and it is less likely to cause deterioration such as decomposition or polymerization. Further, it is also preferable from the viewpoints of solubility in a hydrocarbon solvent and resistance to a photoresist solvent.

In addition, the elastomer is preferably a block of styrene at both ends. polymer. This is because the styrene having high thermal stability due to both end blocks can exhibit higher heat resistance.

More specifically, it is better to embed styrene and conjugated diene a hydride of the segment copolymer. It can improve the stability of heat, and it is not easy to cause deterioration of decomposition or polymerization. Further, high heat resistance can be exhibited by the styrene having high thermal stability at both end blocks. Further, it is also preferable from the viewpoints of solubility in a hydrocarbon solvent and resistance to a photoresist solvent.

It can be used as an elastomer contained in the composition of the adhesive of the present invention. Commercial products to be used are, for example, "Septon (trade name)" manufactured by Kuraray Co., Ltd., "HYBRAR (trade name)" manufactured by Kuraray Co., Ltd., "TUFTEC (trade name)" manufactured by Asahi Kasei Co., Ltd., and "DYNARON" manufactured by JSR Corporation. Name)" and so on.

The content of the elastomer contained in the adhesive composition of 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, more preferably 20 parts by weight or more and 60 parts by weight or less.

In addition, the elastomer may be mixed in a plurality of types. That is, this hair The adhesive composition of the present invention may also contain a plurality of elastomers. When at least one of the plurality of elastomers contains a styrene unit as a constituent unit of the main chain and the styrene unit content is in a range of 14% by weight or more and 50% by weight or less, the weight average molecular weight is in the range of 10,000 or more and 200,000 or less. It is within the scope of the invention. Further, in the composition of the adhesive of the present invention, when a plurality of elastomers are contained, the result of mixing may be adjusted to a styrene unit. The content is in the above range. For example, Septon 8007 of Septon (trade name) manufactured by Kuraray Co., Ltd. having a styrene unit content of 1:1 by weight in a weight ratio of 1 to 1, and Septon (trade name) of Septon having a styrene unit content of 13% by weight. At 2063, the styrene content is 21 to 22% by weight, and 14% by weight or more, based on the entire elastomer contained in the adhesive composition. Further, for example, when the styrene unit is mixed in a ratio of 1 to 1, 10% by weight and 60% by weight in the case of 60% by weight, it is within the above range. The invention may also be in this form. Further, it is preferable that all of the plurality of elastomers contained in the adhesive composition of the present invention contain styrene units in the above range, and have a weight average molecular weight in the above range.

(solvent)

The adhesive composition of the present invention preferably contains a solvent which dissolves the hydrocarbon resin or the elastomer. As such a solvent, for example, a nonpolar hydrocarbon solvent, a polar and nonpolar hydrocarbon solvent, or the like can be used.

Preferred solvents may contain condensed polycyclic hydrocarbons. By making the solvent contain By condensing a polycyclic hydrocarbon, it is possible to avoid white turbidity which may occur when the adhesive composition is stored in a liquid form (especially at a low temperature), and the stability of the product can be improved.

The hydrocarbon solvent is exemplified by a linear, branched or cyclic hydrocarbon. For example, it is a linear hydrocarbon such as hexane, heptane, octane, decane, methyl octane, decane, undecane, dodecane or tridecane, or a branched hydrocarbon having 3 to 15 carbon atoms; P -menthane, o-menthane, m-menthane, diphenyl menthane, α -terpinene, β -terpinene, γ -terpinene, 1,4-product, 1,8- Products, bornane, norbornane, pinane, alpha-pinene, beta-pinene, thujane, alpha-terbinone, beta-terbinone, decane (carane), longifolene, and the like.

Further, the petroleum solvent is exemplified by, for example, cyclohexane, cycloheptane, cyclooctane, naphthalene, decalin, tetrahydronaphthalene or the like.

Further, the condensed polycyclic hydrocarbon is a hydrocarbon in which two or more single rings are supplied to each other only to the condensed ring of each ring, and it is preferred to use a hydrocarbon obtained by condensing two single rings.

The hydrocarbons are listed as a combination of a 5-membered ring and a 6-membered ring, or a combination of two 6-membered rings. The hydrocarbons combining the 5-membered ring and the 6-membered ring are exemplified by, for example, anthracene, pentene, indane, tetrahydroanthracene, etc., and the hydrocarbons combining the two 6-membered rings are exemplified by, for example, naphthalene, tetraline, and decalin. (decaline) and so on.

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 a saturated aliphatic hydrocarbon. In this case, the content of the condensed polycyclic hydrocarbon is preferably 40 parts by weight or more, and more preferably 60 parts by weight or more based on the total of the hydrocarbon-based solvent. When the content of the condensed polycyclic hydrocarbon is 40 parts by weight or more of the total of the hydrocarbon-based solvent, the resin can exhibit high solubility. When 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.

The above saturated aliphatic hydrocarbon is exemplified by a linear hydrocarbon such as hexane, heptane, octane, nonane, methyl octane, decane, undecane, dodecane or tridecane, and carbon. a branched hydrocarbon of from 3 to 15, p-menthane, o-menthane, m-menthane, diphenylmethane, 1,4-deuterate, 1,8-fluorene, bornane, Norbornane, pinane, side Thujane, carane, longifolene, and the like.

Further, the solvent content in the adhesive composition of the present invention is only The thickness of the adhesive layer formed by using the adhesive composition may be appropriately adjusted. For example, when the total amount of the adhesive composition is 100 parts by weight, the range is preferably 20 parts by weight or more and 90 parts by weight or less. When the content of the solvent is within the above range, the viscosity adjustment becomes easy.

(thermal polymerization inhibitor)

The adhesive composition of the present invention may also contain a thermal polymerization inhibitor. The thermal polymerization inhibitor has a function of preventing radical polymerization caused by heat. Specifically, since the thermal polymerization inhibitor exhibits high reactivity with respect to radicals, it is more preferentially reacted than the monomer to suppress polymerization of the monomer. The polymerization composition containing such a thermal polymerization inhibitor is inhibited in a high temperature environment (especially at 250 ° C to 350 ° C).

For example, in the semiconductor manufacturing step, there is included The wafer was then heated at 250 ° C for 1 hour in a high temperature process. At this time, when the adhesive composition is polymerized due to high temperature, the solubility of the peeling liquid from the wafer peeling support plate after the high-temperature process is low, and the support plate cannot be favorably peeled off from the wafer. However, the adhesive composition of the present invention containing a thermal polymerization inhibitor suppresses oxidation due to heat and the subsequent polymerization reaction, so that the support plate can be easily peeled off even after a high-temperature process, and the generation of residue can be suppressed.

The thermal polymerization inhibitor can effectively prevent self-induced heat The radical polymerization reaction is not particularly limited, but a thermal polymerization inhibitor having a phenol Preferably. Accordingly, good solubility can be ensured after high temperature treatment in the atmosphere. The thermal polymerization inhibitor may use a hindered phenol-based antioxidant such as pyrogallol, benzoquinone, hydroquinone, methylene blue, t-butylcatechol, monobenzyl ether, methylhydroquinone, amyl hydrazine. , pentyloxyhydroquinone, 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)benzene Ethylene]bisphenol, 4,4',4"-ethylene thiophene (2-methylphenol), 4,4',4"-ethylene phenol, 1,1,3-parameter (2,5-Dimethyl-4-hydroxyphenyl)-3-phenylpropane, 2,6-di-t-butyl-4-methylphenol, 2,2'-methylene double (4 -methyl-6-tert-butylphenol), 4,4'-butylene bis(3-methyl-6-tert-butylphenol), 4,4'-thiobis(3-methyl- 6-tert-butylphenol), 3,9-bis[2-(3-(3-t-butyl-4-hydroxy-5-methylphenyl)-propenyloxy)-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-t-butyl-4-hydroxyphenyl)propionate, pentaerythritol 肆[3-(3, 5-di-t-butyl-4-hydroxyphenyl)propionate] (trade name: IRGANOX1010, manufactured by Ciba, Japan), ginseng (3,5-di-t-butylhydroxybenzyl) isocyanuric acid Acid ester, thiodiethylidene bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate]. The thermal polymerization inhibitor may be used singly or in combination of two or more.

The content of the thermal polymerization inhibitor is as long as it depends on the hydrocarbon resin or elasticity. The type of the body, the use of the adhesive composition, and the use environment may be appropriately determined. For example, when the amount of the hydrocarbon resin or the elastomer is 100 parts by weight, it is preferably 0.1 part by weight or more and 10 parts by weight or less. Thermal polymerization inhibitor When the content is within the above range, the effect of suppressing polymerization by heat can be satisfactorily exhibited, and after the high-temperature process, the decrease in the solubility of the adhesive composition to the peeling liquid can be further suppressed.

Further, the adhesive composition of the present invention may also be dissolved An anti-heat polymerization inhibitor and a composition for adding a solvent to a composition in which a solvent for dissolving a hydrocarbon resin or an elastomer is different. The solvent to be added is not particularly limited, and an organic solvent which dissolves the components contained in the adhesive composition can be used.

The organic solvent is, for example, a composition of an adhesive composition. The solution may be dissolved in a homogeneous solution, and any one or a combination of two or more may be used.

Specific examples of the organic solvent are exemplified by having an oxygen atom, for example. A terpene solvent which is a polar group such as a carbonyl group or an ethoxylated group, and is exemplified by, for example, geraniol, nerol, linalool, citral, citronellol. ), menthol, isomenthol, neomenthol, alpha-terpineol, beta-terpineol, gamma-terpineol, terpineol-1-ol, terpineol-4-ol, dihydrogeninol B Acid esters, 1,4- oleol, 1,8-nonyl oleyl alcohol, borneol, carvone, ionone, flavonoids, camphor. Further, examples thereof include lactones such as γ-butyrolactone; and ketones such as acetone, methyl ethyl ketone, cyclohexanone (CH), methyl n-amyl ketone, methyl isoamyl ketone, and 2-heptanone. Polyols such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol; ethylene glycol monoacetate, diethylene glycol monoacetate, propylene glycol monoacetate, or dipropylene glycol monoacetate a compound having an ester bond, a monoalkyl ether or a monophenyl ether of the above polyol or a monomethyl ether, monoethyl ether, monopropyl ether or monobutyl ether of the above compound having an ester bond a compound having an ether bond, etc. a derivative of a polyhydric alcohol (preferably propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME)), a cyclic ether such as dioxane, or methyl lactate, Ethyl lactate (EL), methyl acetate, ethyl acetate, butyl acetate, methyl propionate, ethyl propionate, methyl methoxypropionate, ethyl ethoxy propionate, etc.; An aromatic organic solvent such as ether, ethylbenzyl ether, tolyl methyl ether, diphenyl ether, dibenzyl ether, phenethyl alcohol or butylphenyl ether.

The content of the added solvent is as long as it depends on the kind of the thermal polymerization inhibitor The type of the thermal polymerization inhibitor may be appropriately determined. For example, when the thermal polymerization inhibitor is used in an amount of 1 part by weight, the solvent is preferably 1 part by weight or more and 50 parts by weight or less, more preferably 1 to 30 parts by weight, still more preferably 1 to 15 parts by weight. Parts by weight. 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 of the present invention may further contain other substances in combination within a range not impairing the essential characteristics of the present invention. For example, various additives such as an additional resin for improving the performance of the adhesive, a plasticizer, an auxiliary agent, a stabilizer, a colorant, and a surfactant can be used.

(modulation method of the composition of the adhesive)

The method for preparing the adhesive composition before adjusting the content of the adhesion preventing agent is not particularly limited as long as a conventional method can be used, for example, by dissolving a hydrocarbon resin or an elastomer in a solvent, stirring using an existing stirring device. Each composition was obtained to obtain an adhesive composition.

Further, when a thermal polymerization inhibitor is added to the adhesive composition, It is preferred to add a thermal polymerization inhibitor in advance in an additive solvent for dissolving the thermal polymerization inhibitor.

Then, the thus prepared adhesive composition can be supplied The adhesive composition of the present invention is obtained by a purification step in the method for producing an adhesive composition of the present invention to be described later. Further, even if it is a method other than the method for producing an adhesive composition of the present invention to be described later, the adhesive composition of the present invention can be produced as long as it is a method of removing the adhesion preventing agent.

(adhesive preventive agent)

In the purification step, the adhesion preventing agent removed from the adhesive composition is also referred to as a slip agent, and is a resin composition in which the resin (hydrocarbon resin, elastomer) used in the adhesive composition is formed into a pellet form. Included. As a result, when the adhesive composition is prepared using the resin, the adhesion preventive agent is finally contained in the adhesive composition. Commercially available resins are mostly supplied in the form of granules, so most of the adhesive composition contains a sticking inhibitor.

Examples of the adhesion preventing agent are exemplified by, for example, 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), etc., salt minerals, lead stearate, zinc stearate, calcium stearate, magnesium stearate And other alkanes such as stearates, liquid alkanes, paraffin waxes, stearic acid, decylamine stearate, decyl oleate, decyl methylene bis-stearate, ethyl bis-stearic acid A fatty acid guanamine such as guanamine or erucylamine.

The adhesive composition of the present invention reduces the adhesive composition The amount of the adhesion preventing agent contained in the product. The amount of the adhesion preventing agent contained in the subsequent composition can be expressed by the content of the metal component derived from the adhesion preventing agent. The metal component derived from the adhesion preventing agent is exemplified by, for example, sodium, magnesium, aluminum, potassium, calcium, chromium, manganese, iron, nickel, copper, lead, zinc, or the like.

The content of the metal component derived from the adhesion preventing agent of the adhesive composition of the present invention is 10 ppb or more and 2 ppm or less based on the total solid weight of the adhesive composition.

In the subsequent composition, the content of the metal component derived from the adhesion preventing agent is 2 ppm or less based on the total solid weight of the adhesive composition, and the adhesive composition is used next to the wafer and the support, and the solution is dissolved and washed. After the net, it is not preferable to produce residue on the wafer. Further, the lower limit of the content of the metal component derived from the gel-preventing agent contained in the adhesive composition is preferably [0], but may be substantially the detection limit value (generally 10 ppb) of the metal component. Therefore, the lower limit of the content of the metal component derived from the contained adhesion preventing agent in the adhesive composition was 10 ppb with respect to the total solid weight of the adhesive composition.

The content of the metal component derived from the adhesion preventive agent contained in the subsequent composition can be determined by, for example, quantifying the metal component in the adhesive composition by ICP-MS (inductively coupled plasma mass spectrometry). . Specifically, in the solution containing the adhesive composition, the measurement result of the metal content measured by the above method is converted into a value relative to the total solid weight of the adhesive composition, and the gel-preventing prevention in the adhesive composition can be calculated. The content of the metal component of the agent is used as the concentration in the composition of the adhesive.

Further, the adhesive composition of the present invention is derived from the adhesive group In the metal component of the adhesion preventing agent contained in the product, the content of the metal component containing the most is 10 ppb or more and 2 ppm or less with respect to the total solid weight of the adhesive composition.

(Use of the adhesive composition)

The adhesive composition of the present invention is used to support the wafer and the support of the wafer.

The support is, for example, a role of supporting the wafer in the step of thinning the wafer, and the composition of the adhesive of the present invention is applied to the wafer. In one embodiment, the support system is formed, for example, of glass or ruthenium having a film thickness of 500 to 1000 μm.

Further, in one embodiment, a hole penetrating the thickness direction of the support body is provided on the support. The solvent that dissolves the adhesive composition flows between the support and the wafer through the hole, whereby the support and the substrate can be easily separated.

Further, in another embodiment, a reaction layer other than the adhesion layer may be interposed between the support and the wafer. The reaction layer is deteriorated by absorbing light irradiated through the support, and the reaction layer is degraded by irradiating light or the like to the reaction layer, whereby the support and the wafer can be easily separated. In this case, it is preferable to use a support body which is not provided with a hole penetrating in the thickness direction.

The light irradiated to the reaction layer is suitably used as a solid laser such as a YAG laser, a ruby laser, a glass laser, a YVO ₄ laser, an LD laser, a fiber laser, or the like, depending on the wavelength of the absorbable reaction layer. Laser lasers such as CO ₂ lasers, excimer lasers, Ar lasers, He-Ne lasers, semiconductor lasers, free electron lasers, or non-laser light. The wavelength of all light absorbed by the reaction layer is not limited to these, and may be, for example, light having a wavelength of 600 nm or less.

The reaction layer may also contain light absorption which is decomposed by, for example, light or the like. Agent. As the light absorbing agent, for example, a fine metal powder such as graphite powder, iron, aluminum, copper, nickel, cobalt, manganese, chromium, zinc or bismuth, a metal oxide powder such as black titanium oxide, carbon black, or an aromatic diamine metal can be used. Complex, fatty diamine metal complex, aromatic dithiol metal complex, nonylphenol metal complex, squaraine compound, cyanine dye, methine dye, naphthoquinone A dye or pigment such as a pigment or an anthraquinone dye. Such a reaction layer can be formed by, for example, mixing with a binder resin and coating it on a support. Further, a resin having a light absorbing group can also be used.

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

The adhesive composition of the present invention is preferably suitable for use in The support is then supplied to the wafer and the support in the thinning step. As described above, the support system maintains the strength of the wafer as the wafer is thinned. The adhesive composition of the present invention is preferably applied to the wafer and the support.

Moreover, the adhesive composition of the present invention is preferably used in the support The support is then supplied to the wafer and the support in the electrode formation step.

If the adhesive composition contains a gel inhibitor, it is derived from The metal component of the adhesion preventive agent remains on the wafer, adversely affecting the electrical characteristics of the wafer on which the electrode is formed. On the other hand, since the adhesive composition of the present invention removes the adhesion preventing agent, the wafer and the support are subsequently dissolved, washed, and no residue is generated on the wafer. Therefore, when the adhesive composition of the present invention is used in the subsequent step of the wafer and the support, the electrical characteristics of the wafer provided with the electrode or the like, in particular, the connection characteristics are excellent.

An adhesive composition according to the present invention, used in wafers and Subsequent to the support of the wafer, the occurrence of residues on the wafer when dissolved and washed by the solvent can be prevented.

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

The adhesive composition of the present invention is subsequently separated from the support by degrading the reaction layer or the like, and when the adhesive layer is removed, the solvent can be easily removed by using a solvent which dissolves the adhesive composition. Further, by using the above reaction layer or the like without supplying the solvent directly to the adhesive layer in a state in which the wafer and the support are next, the adhesive layer can be easily dissolved to remove the adhesive layer, and the wafer can be removed. Separated from the support. In this case, in order to improve the supply efficiency of the solvent to the adhesive layer, it is more preferable to provide a through hole in the support.

[Method of Manufacturing Adhesive Composition]

The manufacturing method for the adhesive composition of the present invention for supporting the wafer and the support of the wafer comprises removing the adhesive contained in the adhesive composition The purification step of the agent. Further, in the method for producing an adhesive composition of the present invention, in the above purification step, the content of the metal component derived from the adhesion preventing agent contained in the adhesive composition is preferably relative to the total solid weight of the adhesive composition. It is 2 ppm or less. In addition, the lower limit of the content of the metal component of the adhesion preventing agent contained in the adhesive composition is desirably "0", but it is only required to be a detection limit value (generally 10 ppb) of the metal component.

(purification step)

In the purification step, the method of removing the adhesion preventing agent contained in the adhesive composition is specifically exemplified by (1) a method of removing the adhesion preventing agent by filtering the adhesive composition.

In the method of filtering the adhesive composition to remove the adhesion preventing agent, 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 remove the adhesion preventing agent from the solution. The pore diameter of the filter can be appropriately selected depending on the kind of the adhesion preventing agent contained in the adhesive composition. That is, the filter may be any pore size that can filter the adhesion preventing agent.

The material of the filter is exemplified by, for example, polypropylene, nylon (polyamide), polytetrafluoroethylene (PTFE), or the like. The pore diameter may be appropriately selected from 0.01 to 10 μm, preferably from 0.1 to 10 μm.

Further, as for the treatment step (2) before the purification step (1), the resin solution obtained by dissolving the resin used in the adhesive composition in a solvent may be added dropwise to the resin solution as a weak solvent such as water. In the alcohol, the resin is reprecipitated (precipitated). The alcohol is preferably an alcohol having 1 to 4 carbon atoms, which is exemplified as an example. For example, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, and the like. The solvent in which the resin is dissolved is exemplified by a terpene solvent such as p-menthane or a petroleum solvent such as cyclohexane or decalin. Then, the precipitated resin is taken out from the solution in which the above-mentioned adhesion preventing agent is dispersed, and the adhesion preventing agent is removed from the resin. The adhesive composition is prepared using the resin from which the adhesion preventing agent has been removed. Next, the adhesive composition is further purified by the above purification step (1), and an adhesive composition having the adhesion preventing agent removed can be produced.

The resin precipitated in the solution can be filtered and removed only The liquid solution (decanting), centrifugation, resin reprecipitation, etc. are taken out from the solution.

Further, as the purification step (1), the treatment step (2) is also The adhesion preventing agent can be removed by washing the granular resin. First, the granular resin is washed with a weak solvent such as water or an alcohol (preferably an alcohol having 1 to 4 carbon atoms) while stirring to remove the adhesion preventing agent adhering to the surface of the particulate resin. Next, the solution in which the particles are dispersed is filtered by, for example, a mesh filter having a relatively large mesh size of 10 to 200 μm, and the release preventing agent is removed from the resin. The adhesive composition is prepared using the resin from which the adhesion preventing agent has been removed. Next, the adhesive composition is further purified by the above purification step (1), and an adhesive composition having the adhesion preventing agent removed can be produced.

Moreover, it is the same as the above washing with water, alcohol, etc. The granulated resin is immersed in an acid such as hydrofluoric acid to dissolve and remove the adhesion preventing agent, and the acid can be washed to remove the adhesion preventing agent.

Also, a wind screening machine (jet separation machine) can be used to wind The force will be lighter and the anti-collection agent will collect dust, and only the heavier particles will be recovered. The resin removes the adhesion preventing agent.

And, as the above-mentioned processing step (2) of the above purification step (1) Alternatively, the adhesion preventing agent may be removed by ultrasonic cleaning while immersing the resin in the solution. The solution impregnated with the resin is exemplified as a weak solvent. The weak solvent is exemplified by, for example, glycol ether propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, methanol having a carbon number of 1 to 5, methanol, ethanol, propanol or the like. By using these weak solvents, the resin itself is substantially insoluble, but the adhesion preventing agent can be removed by swelling the resin. Further, 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 longer and 60 minutes or shorter. The adhesive composition is prepared using such a resin from which the adhesion preventing agent has been removed. Next, by further purifying the adhesive composition by the above purification step (1), an adhesive composition having the adhesion preventing agent removed can be produced.

Ultrasonic washing in a state where the resin is immersed in a solution For the net, just use the conventional ultrasonic cleaning machine.

As described above, the adhesion prevention contained in the adhesive composition is removed. The methods of the agents may be carried out separately or in combination with a plurality of methods. In other words, a method of removing the adhesion preventing agent by removing the adhesion preventing agent contained in the resin by a method of precipitating and removing the adhesion preventing agent, and then removing the adhesion preventing agent may be provided.

When the resin is reprecipitated (precipitated) or when the resin is washed, After filtering through a mesh filter having a relatively large mesh size, the resin may be recovered by dissolving it in a terpene solvent such as p-menthane, a petroleum solvent such as cyclohexane or decalin. When the adhesive composition is filtered to remove the adhesion preventing agent, The solution obtained by filtration was used as an adhesive composition.

a method for producing an adhesive composition according to the present invention, The removal of the adhesion preventing agent contained in the adhesive composition by the purification step can be performed by using the support for the wafer and the wafer to prevent the residue on the wafer from being washed and dissolved in the solvent. The resulting adhesive composition. Further, an adhesive composition for preventing the generation of residues on the wafer when dissolved in a solvent and washed after the support of the wafer and the wafer can be provided.

Further, in order to use the manufacturer of the adhesive composition of the present invention A method for removing an adhesion preventing agent as a target, and a method for producing a laminate in which a wafer and a support are bonded using the adhesive composition of the present invention, and an electrode for forming an electrode on a wafer of the laminate The method, the stripping method of the wafer stripping support from the laminate, the method of stripping the support, and the cleaning of the washed wafer are all within the scope of the present invention.

[Next film]

The adhesive composition of the present invention can be used in various utilization forms depending on the use. For example, a method of directly applying a liquid to a workpiece such as a semiconductor wafer to form an adhesive layer may be used, and the adhesive film of the present invention may be used, that is, a film formed on a film such as a flexible film may be used in advance. After the adhesive layer of any of the above-mentioned adhesive compositions is dried, the film (subsequent film) is attached to the object to be processed (following the film method).

Thus, the adhesive film of the present invention is provided on the film An adhesive layer containing any of the above-described adhesive compositions.

The film can then be coated on the adhesive layer and then covered with a protective film. Use as a film. In this case, after the protective film on the adhesive layer is peeled off and the exposed adhesive layer is superimposed on the workpiece, the film is peeled off from the adhesive layer, whereby the adhesive layer can be easily provided on the workpiece.

Therefore, if the adhesive film is used, it is compared to the direct When the adhesive composition is applied to the processed body to form an adhesive layer, an adhesive layer having good film thickness uniformity and surface smoothness can be formed.

As for the above film used in the manufacture of the film, The release film which is formed by peeling off the film on the film from the film and transferring the adhesive layer to the surface to be processed such as a protective substrate or a wafer is not particularly limited. For example, it is a flexible film made of a synthetic resin film of polyethylene terephthalate having a film thickness of 15 to 125 μm, polyethylene, polypropylene, polycarbonate, or polyvinyl chloride. The above film may also be subjected to a release treatment as needed to facilitate transfer.

The method of forming an adhesive layer on the above film is listed as The film thickness or uniformity of the desired adhesive layer is applied to the adhesive composition of the present invention by a suitable and conventional method so that the dried film thickness of the adhesive layer on the film is 10 to 1000 μm.

Moreover, when a protective film is used, as a protective film, The peeling from the adhesive layer is not limited, and is preferably, for example, a polyethylene terephthalate film, a polypropylene film, or a polyethylene film. In addition, each of the protective films is preferably coated or heat bonded to the crucible. The reason for this is that the peeling from the adhesive layer is facilitated. The thickness of the protective film is not particularly limited, but is preferably 15 to 125 μm. The reason for this is that the flexibility of the adhesive film having the protective film can be ensured.

The method of using the film is not particularly limited, for example, When the protective film is used, the adhesive layer is superposed on the object to be peeled off, and the heat roller is moved from the film (the back surface of the surface on which the adhesive layer is formed), and the adhesive layer is heat-pressed. The method of the surface of the body to be processed. At this time, the protective film peeled off from the film can be stored and reused by winding a roll such as a roll or the like in a roll shape.

[Examples]

[Preparation of the composition of the adhesive]

The resins (hydrocarbon resin or elastomer), polymerization inhibitor, main solvent, and added solvent used in Examples 1 to 10 and Comparative Examples 1 to 4 are shown in Tables 1 and 2 below. In addition, the "parts" in Table 2 are all parts by weight.

Hydrocarbon resin is made by POLYPLASTIC. TOPAS (trade name) 8007X10, Mw=95,000, Mw/Mn=1.9, m:n=35:65 (Morby) (hereinafter referred to as COC A), and "APEL (trade name) manufactured by Mitsui Chemicals Co., Ltd.) 8008T COC, Mw = 100,000, Mw / Mn = 2.1, m: n = 80: 20 (mole ratio)" (hereinafter referred to as COC 1).

As for the elastic system, Sepatum (made by Kuraray) is used. Trade name) HG252 (SEEPS-OH: polystyrene-poly(ethylene-ethylene/propylene) block-polystyrene terminal hydroxyl modification), HG253, and Septon8007 (SEBS: polystyrene-poly(ethylene/butyl) (A) block-polystyrene), H1051 (SEBS, hydrogenated styrene-based thermoplastic elastomer) of TUFTEC (trade name) manufactured by Asahi Kasei Corporation, and H1053 (SEBS, hydrogenated styrene thermoplastic elastomer). Further, the "hydrogenation" in the present embodiment is a polymer obtained by hydrogenating a 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.

Further, as a thermal polymerization inhibitor, BASF Corporation was used. "IRGANOX (trade name) 1010". Further, as the main solvent, decalin represented by the following chemical formula (I) is used. Further, butyl acetate was used as an additive solvent.

The preparation of the adhesive composition of Example 1 was carried out 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. Then, a butyl acetate solution to which a thermal polymerization inhibitor is added is added so that the thermal polymerization inhibitor becomes 1 part by weight and the butyl acetate becomes 45 parts by weight with respect to 100 parts by weight of the elastomer. Use aperture 1μm A PTFE filter (manufactured by PALL Co., Ltd.) was used to filter the thus obtained adhesive composition. The content (metal content) of the metal component derived from the adhesion preventing agent in the obtained adhesive composition was measured by ICP-MS (manufactured by Agilent Technology Co., Ltd., product name: 7500 cs).

Moreover, by measuring the turbidity for the adhesive composition, Adhesives prevent the removal effect. Turbidity was determined using SHIMADZU UV-3600.

The content of the metal component in the composition of the subsequent agent is sodium, Among the ten elements of magnesium, aluminum, potassium, calcium, chromium, manganese, iron, nickel and copper, the content of the metal component having the highest content in the adhesive composition is shown. The metal content in the subsequent composition is shown in Table 2. Further, in Examples 2 to 4 and 6, an adhesive composition was obtained in the same manner. Examples 5 and 7 were stirred by a three-in-one motor (THREE-ONE MOTOR) while the adhesive resin component was immersed in methanol at 23 °C. After washing, the adhesion preventing agent was also removed by filtration. In Example 8, except that the decalin solution (10% by weight concentration) of the adhesive resin component was used as a weak solvent, it was added dropwise to water/methanol (weight ratio 2). /8) An adhesive composition was obtained in the same manner as in Example 1 except that the adhesive resin component was reprecipitated and filtered in the same manner to remove the adhesion preventing agent. Further, in the ninth embodiment, a wind-screening machine (jet separation machine (Jet Separator CFS) manufactured by ACO Co., Ltd.) was used, and after the binder resin component was collected as a dust-preventing agent, the same was carried out by filtration to remove the adhesion preventing agent. The adhesive composition was obtained in the same manner as in Example 1.

In Example 10, the adhesive resin component was immersed at 35 ° C. The state of propylene glycol monomethyl ether acetate was washed in an ultrasonic cleaner (AIWA Medical Industry, model: AU-70C, oscillation output: 100 W, frequency: 28 kHz) for 30 minutes to remove the adhesion preventing agent. The adhesive composition was obtained in the same manner as in Example 1 except that the filtration was carried out.

For the resin of Example 5, 7-10, the above specific After the treatment, the treated resin was used to prepare the adhesive composition. Here, Examples 5, 7, 9, and 10 directly treat the particles. In Example 8, after the particles were dissolved once, a reprecipitation treatment was carried out.

Metal content in each of the adhesive compositions of Examples 1 to 10. The total solid weight relative to the adhesive composition is 10 ppb or more and 2 ppm or less. Further, the turbidity of the adhesive composition was also preferably 5% or less.

In Comparative Examples 1 to 4, in addition to filtering the adhesive composition and measuring The adhesive composition was obtained in the same manner as in Example 1 except for the predetermined metal content.

[Formation of adhesive layer]

Each of the adhesive compositions was spin-coated on a 12 Å Si wafer, and each was sintered at 100 ° C, 160 ° C, and 200 ° C for 5 minutes to form an adhesive layer (film thickness: 50 μm).

A reaction layer which is subsequently deformed by irradiation with a laser to peel the support from the wafer is disposed on one of the supports. As for the reaction layer, 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 2,500 W, and a film formation temperature of 240 ° C, in a support plate (12 吋 glass, thickness: 700 μm) A fluorocarbon film (1 μm) was formed thereon.

[Thinning treatment of laminate]

The laminate of the wafer and the support is used to perform thinning of the wafer, photolithography, and the like.

[cleaning of the adhesive layer]

Irradiation of the 532 nm laser separates the wafer from the support. The wafer on which the support was removed was washed with a p-menthane spray to remove the adhesive layer. The surface of the wafer after removing the adhesive layer was observed under a microscope to confirm the generation of residue. The results are shown in Table 2. Further, in Table 2, the result of "○" indicates that no residue was confirmed, and the result of "△" indicates that a small or small amount of residue was confirmed, and the result of "x" indicates that large or large amount of residue was confirmed. Things.

As shown in Table 2, the wafer after cleaning in the example did not occur. Residue, the residue of crystals of 1 to 100 μm was confirmed on the surface of the wafer after washing in the comparative example. Further, in the comparative examples, the turbidity of the adhesive composition was more than 5%.

The present invention is not limited to the above embodiment, and can be applied for Various modifications are possible in the range indicated by the scope of the invention, and embodiments obtained by appropriately combining the technical means disclosed in the embodiments are also included in the technical scope of the present invention.

[Industrial availability]

The production method, the adhesive composition, and the adhesive film of the present invention can be preferably used in, for example, a manufacturing step of a miniaturized semiconductor device.

Claims (12)

A method for producing a composition for bonding a wafer to a support of the wafer, characterized by comprising a purification step of removing an adhesion preventing agent contained in the adhesive composition. The method for producing an adhesive composition for causing a wafer and a support of the wafer according to claim 1, wherein the purification step is derived from a metal component of the adhesion preventing agent contained in the adhesive composition. The content is 2 ppm or less based on the total solid weight of the above-mentioned adhesive composition. A method of producing an adhesive composition for replenishing a wafer and a support of the wafer according to claim 1 or 2, wherein in the above purification step, the solution containing the above-described adhesive composition is filtered. A method for producing a binder composition for causing a wafer and a support of the wafer according to claim 3, wherein, before the purifying step, in a resin solution containing a resin forming the above-mentioned adhesive composition, After the resin is reprecipitated, the above-mentioned adhesive composition contains a resin taken out from the resin solution. The method for producing a binder composition for causing a wafer and a support of the wafer according to claim 3, wherein, after the step of purifying, the resin forming the adhesive composition is washed in the solution, The subsequent composition contains a resin taken out from the solution containing the resin. The method for producing an adhesive composition for replenishing a wafer and a support of the wafer according to claim 3, wherein the anti-adhesion agent contained in the adhesive composition is used by wind filtering before the purifying step. Dust collection. A method for producing a composition for replenishing a wafer and a support of the wafer according to claim 3, wherein the resin forming the adhesive composition is immersed in a solution before the purification step After the ultrasonic cleaning, the above-mentioned adhesive composition contains a resin taken out from the solution containing the resin solution. A composition for bonding a wafer to a support of the wafer, characterized in that the content of the metal component derived from the adhesion preventing agent is 10 ppb or more and 2 ppm or less based on the total solid weight. The adhesive composition for requesting the wafer and the support of the wafer, wherein the wafer system and the support are subsequently supplied to the electrode forming step. The adhesive composition for interposing the wafer and the support of the wafer, as in claim 8 or 9, comprises a hydrocarbon resin. The adhesive composition for causing the wafer and the support of the wafer to be followed by an adhesive composition according to any one of claims 8 to 10, which comprises an elastomer. An adhesive film characterized by forming an adhesive layer formed on the film by the adhesive composition for adhering the wafer to the support of the wafer according to any one of claims 8 to 11.