TWI589656B - Adhesive composition and adhesive film - Google Patents

Description

Subsequent composition and subsequent film

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

With the high functionality of mobile phones, digital audio-video devices, and wafer cards, and the miniaturization and thinning of the mounted semiconductor wafers (hereinafter referred to as wafers), the requirements for high integration in the package are required. improve. For example, in an integrated circuit in which a plurality of wafers such as a chip size package (CSP) or a multi-chip package (MCP) are integrally packaged, thinning is required. In order to achieve high integration of the wafer in the package, the thickness of the wafer must be reduced to a range of 25 to 150 μm.

However, since the semiconductor wafer (hereinafter referred to as a wafer) which is the basis of the wafer is thinned by grinding, the strength thereof is weakened, and cracking or warpage is likely to occur on the wafer. Further, since it is difficult to automatically transfer a wafer having a weakened strength due to thinning, it is necessary to carry it by hand, and the processing thereof is complicated.

Therefore, the development of a wafer handling system (wafer The handling system; WHS) maintains the strength of the wafer by bonding a sheet made of glass, hard plastic or the like called a support plate to the wafer to be ground to prevent cracking and Warpage of the wafer. Since the strength of the wafer can be maintained by the wafer transfer system, the transfer of the thinned semiconductor wafer can be automated.

In the wafer transfer system, the wafer and the support sheet 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 cut. When the bonding agent is used to bond the wafer to the support plate, the adhesive is dissolved to peel the wafer from the support plate.

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

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Gazette Patent Gazette "Special Publication No. 2009-529065 (public form on August 13, 2009)"

However, when the prior art hydrocarbon-based adhesive is used in the WHS, in the photoresist peeling step, the swell of the adhesive is caused by immersing the wafer to which the support plate is attached in the photoresist solvent, and The problem of peeling of the support plate occurs.

The adhesive composition and the adhesive film of the present invention have been completed in view of the above problems, and a main object thereof is to provide an adhesive composition and a bonding film which can reduce swelling by a photoresist solvent and peeling from a support.

In order to solve the above problems, the adhesive composition of the present invention is characterized in that it contains an elastomer and a hydrocarbon resin, and the elastic system contains a styrene unit as a structural unit of a main chain, and the content of the styrene unit is 14% by weight or more and 50%. The content of the elastomer is in the range of 50% by weight or more and 99% by weight or less based on the total amount of the elastomer and the hydrocarbon resin, and the content of the hydrocarbon resin is 1% by weight or more. Within the range of 50% by weight or less.

According to the above configuration, it is achieved that an effect of an adhesive composition capable of reducing swelling due to a photoresist solvent and peeling from a support can be provided.

Hereinafter, embodiments of the present invention will be described in detail. An adhesive composition according to an embodiment of the present invention contains an elastomer and a hydrocarbon resin, and the elastic system contains a styrene unit as a structural unit of a main chain, and the content of the styrene unit is 14% by weight or more and 50% by weight. In the following, the content of the elastomer is in the range of 50% by weight or more and 99% by weight or less based on the total amount of the elastomer and the hydrocarbon resin, and the content of the hydrocarbon resin is 1% by weight or more and 50% by weight. % below the range. Thereby, the adhesive composition of the present invention can reduce the swelling of the composition and the peeling of the support by the photoresist.

In addition, the adhesive composition of the embodiment of the present invention preferably has a content of the elastomer of 60% by weight or more and 95% by weight or less based on the total amount of the elastomer and the hydrocarbon resin. The content of the hydrocarbon resin is in the range of 5 wt% or more and 40 wt% or less. Thereby, the adhesive composition of the present invention can more appropriately reduce the swelling of the composition due to the photoresist solvent and the peeling of the support.

[elastomer]

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

In the present specification, the term "structural unit" means a structure of a monomer which is caused by one molecule in a structure constituting a polymer.

In the present specification, the "styrene unit" is a structural unit derived from the styrene contained in the polymer after polymerization of styrene or a styrene derivative. The "styrene unit" may have a substituent. Examples of the substituent group 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 ethoxy group, and a carboxyl group.

By the content of the styrene unit being 14% by weight or more, The process of thinning, mounting, and the like is not performed because the adhesion or the machinability of the substrate is not lowered. By the content of the styrene unit being 50% by weight or less, the chemical resistance of the adhesive composition of the present invention can be appropriately maintained.

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

When the content of the styrene unit is in the range of 14% by weight or more and 50% by weight or less, and the weight average molecular weight of the elastomer is in the range of 20,000 or more and 200,000 or less, it is easily dissolved in a hydrocarbon solvent to be described later. The adhesive composition is removed more easily and quickly. Further, by making the weight average molecular weight within the above range, the photoresist solvent (for example, PGMEA, PGME, NMP, etc.) and acid (when the wafer (substrate) is supplied to the photoresist lithography step) Hydrogen fluoride or the like, and alkali (TMAH, etc.) exhibit excellent resistance.

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

In the case of the elastomer, when the content of the styrene unit is in the range of 14% by weight or more and 50% by weight or less, various elastomers can be used. For example: polystyrene-poly(ethylene/propylene) block copolymer (SEP), styrene-isoprene-styrene block copolymer (SIS), styrene-butadiene-styrene block copolymerization (SBS), styrene-butadiene-butene-styrene block copolymer (SBBS), and the like, hydride, styrene-ethylene-butylene-styrene block copolymer (SEBS), Styrene-ethylene-propylene Alkene-styrene block copolymer (styrene-isoprene-styrene block copolymer) (SEPS), styrene-ethylene-ethylene-propylene-styrene block copolymer (SEEPS), styrene embedded The styrene-ethylene-ethylene-propylene-styrene block copolymer (Septon V9461 (manufactured by KURARAY Co., Ltd.), Septon V9475 (manufactured by KURARAY Co., Ltd.)), and the styrene block are reactive cross-linking. a styrene-ethylene-butylene-styrene block copolymer (Septon V9827 (manufactured by KURARAY Co., Ltd.) having a reactive polystyrene-based hard block), etc., and the content of the styrene unit can be used as described above. Within the scope.

The elastomer contained in the adhesive composition of the present invention is preferably a styrene-based elastomer containing two or more kinds of styrene units contained in a structural unit as a main chain. For example, an elastomer having different contents of styrene units such as Septon 8007L and Septon 2004 of Septon (trade name) manufactured by KURARAY Co., Ltd. may be included.

That is, the adhesive composition of the present invention may also contain a plurality of types of elastomers. It is within the scope of the invention that at least one of the plurality of types of elastomers contains a styrene unit as a structural unit of the main chain, and the content of the styrene unit is in the range of 14% by weight or more and 50% by weight or less. Further, when a plurality of types of elastomers are contained in the adhesive composition of the present invention, the results of the mixing may be adjusted so that the content of the styrene unit is within the above range. For example, if the content of the styrene unit is 30% by weight, the Septon 4033 of the Septon (trade name) manufactured by KURARAY Co., Ltd., and the content of the styrene unit When Sepenton 2063 of 13% by weight of Septon (trade name) is mixed at a weight ratio of 1:1, the styrene content is 21 to 22% by weight based on the entire elastomer contained in the adhesive composition, and becomes 14 More than weight%. In addition, when the styrene unit is 10% by weight and 60% by weight, if it is mixed at 1:1, it is 35% by weight, and it is within the above range. The invention may also be in such a form. Further, it is more preferable that all of the plurality of types of elastomers contained in the adhesive composition of the present invention contain styrene units in the above range.

When the content of the two types of styrene units is different from each other, the styrene-based elastomer having a large content of the styrene unit preferably has a styrene unit content of 20% by weight or more and 80% by weight or less. Within the scope. Further, the styrene-based elastomer having a small content of the styrene unit is preferably in a range of from 1% by weight to 30% by weight based on the styrene unit. By using a styrene-based elastomer having a large content of a styrene unit, it is possible to reduce the adhesion or the machinability of the substrate, and to provide a process such as thinning and mounting. By using a styrene-based elastomer having a small content of styrene units, the chemical resistance of the adhesive composition of the present invention can be appropriately maintained.

Further, when the content of the two types of styrene units is different from each other, the styrene-based elastomer having a large content of the styrene unit is preferably 20 in comparison with the total amount of the styrene-based elastomer. It is in the range of % by weight or more and 80% by weight or less.

Then, even among the elastomers, a hydride is preferable. If it is a hydride, it will further improve the stability of heat, and It is not easy to cause deterioration of decomposition or polymerization. Further, it is also more preferable from the viewpoints of solubility in a hydrocarbon solvent and resistance to a photoresist solvent.

Further, even among the elastomers, those having a styrene block polymer at both ends are preferred. This is because the styrene having high thermal stability is blocked at both ends to exhibit higher heat resistance.

More specifically, the elastomeric system is more preferably a hydride of a block copolymer of styrene and a conjugated diene. Thereby, the stability to heat is further improved, and it is not easy to cause deterioration of decomposition or polymerization. Further, by heat-stabilizing styrene having high thermal stability at both ends, it exhibits higher heat resistance. Further, it is more preferable from the viewpoints of solubility in a hydrocarbon solvent and resistance to a photoresist solvent.

For example, "Septon (trade name)" manufactured by KURARAY Co., Ltd. and "HYBRAR (trade name) manufactured by KURARAY Co., Ltd.) can be used as a commercially available product of the elastomer contained in the adhesive composition of the present invention. "Tuftec (trade name)" manufactured by Asahi Kasei Co., Ltd., "DYNARON (trade name)" manufactured by JSR Co., Ltd., etc.

[hydrocarbon resin]

The hydrocarbon resin is a resin having a hydrocarbon skeleton and polymerizing a monomer component. The hydrocarbon resin contained in the adhesive composition of the present embodiment is, for example, a cycloolefin polymer (hereinafter also referred to as "resin A"), and a terpene resin, a rosin resin, and a petroleum resin. A resin (hereinafter also referred to as "resin B") constituting at least one selected from the group.

The cycloolefin polymer is a resin obtained by polymerizing a cycloolefin monomer of a monomer component. Examples of the cyclic olefin mono-system include a tetracyclic ring such as norbornene and norbornadiene, a tricyclic ring such as dicyclopentadiene or hydroxydicyclopentadiene, and a tetracyclic ring such as tetracyclododecene. Substituted by a pentacyclic ring such as a pentacyclopentadiene terpolymer or tetracyclopentadiene or an alkyl group (methyl, ethyl, propyl, butyl, etc.) of such a polycyclic ring a substituent of a compound, an alkenyl group (vinyl group, etc.), a substituent of an alkylene group (such as an ethylene group), a substituent of an aryl group (such as a phenyl group, a tolyl group, or a naphthyl group). The resin (A) may be one obtained by polymerizing only one of these cycloolefin monomers, or may be obtained by copolymerizing two or more kinds.

Further, the monomer component contained in the resin (A) is not limited to the cycloolefin monomer, and may contain another monomer copolymerizable with the cycloolefin monomer. Examples of the other monomer include a linear or branched chain olefinic monomer. Examples of the olefinic single system include ethylene, propylene, 1-butene, isobutylene, and 1-hexene. Alpha-olefin. Further, the olefinic single system may be used alone or in combination of two or more.

Although the molecular weight of the resin (A) is not particularly limited, for example, the weight average molecular weight (Mw) measured by a polystyrene equivalent value by gel permeation chromatography (GPC) is in the range of 50,000 to 200,000. It is preferably in the range of 50,000 to 150,000. When the weight average molecular weight of the resin (A) is within the above range, cracking is less likely to occur 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 property, thermal weight) in which 5 mol% or more is a cycloolefin monomer. It is preferable from the viewpoint of reducing the amount of the cycloolefin monomer to be more than 10 mol%, more preferably 20 mol% or more. The upper limit is not particularly limited, but 80 mol% or less is preferable from the viewpoint of solubility and stability of the solution over time, and more preferably 70 mol% or less. When the other monomer is a linear or branched chain olefinic monomer, it is soluble and soft in the range of 10 to 90 mol% based on the entire monomer component constituting the resin (A). It is preferable from the viewpoint of sex, and it is preferably in the range of 20 to 85 mol%, and particularly preferably in the range of 30 to 80 mol%.

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

For example, "APEL (trade name)" manufactured by Mitsui Chemicals Co., Ltd., "TOPAS (trade name)" manufactured by Polyplastics Co., Ltd., and Japan ZEON Co., Ltd. are available. "ZEONOR (trade name)" and "ZEONEX (trade name)" manufactured by the company, and "ARTON (trade name)" manufactured by JSR Co., Ltd.

The resin (B) is a resin selected from the group consisting of the above terpene resin, rosin resin, and petroleum resin. Examples of the terpene-based resin include a terpene resin, a terpene phenol resin, a modified terpene resin, a hydrogenated terpene resin, and a hydrogenated terpene phenol resin. Examples of the rosin-based resin include rosin, rosin ester, hydrogenated rosin, hydrogenated rosin ester, polymerized rosin, polymerized rosin ester, and modified rosin. Examples of the petroleum resin include aliphatic or aromatic petroleum resins, hydrogenated petroleum resins, modified petroleum resins, alicyclic petroleum resins, and benzofuran-oxime (coumarone- Indene) petroleum resin and the like. Among these, a hydrogenated terpene resin and a hydrogenated terpene phenol resin are particularly preferable.

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

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

(solvent)

The solvent contained in the adhesive composition of the present invention may be a function of dissolving the elastomer and the hydrocarbon resin. For example, a non-polar hydrocarbon solvent, a polar or non-polar petroleum solvent may be used.

Preferably, the solvent is capable of containing a condensed polycyclic hydrocarbon. Since the solvent contains a condensed polycyclic hydrocarbon, it is possible to avoid white clouding which occurs when the adhesive composition is stored in a liquid form (particularly at a low temperature), and the stability of the product can be improved.

The hydrocarbon solvent system may be a linear, branched or cyclic hydrocarbon. For example, hexane, heptane, octane, decane, methyl octane, a linear hydrocarbon such as decane, undecane, dodecane or tridecane; a branched hydrocarbon having 4 to 15 carbon atoms; p-menthane, o-menthane, m-menthane, and diphenyl Saturated aliphatic hydrocarbons such as mentholane, 1,4-decanediol, 1,8-nonanediol, decane, norbornane, decane, oxane, decane, and longene, α-萜Terpene, β-terpinene, γ-terpinene, α-pinene, β-pinene, α-terbinone, β-terbinone, and the like.

Further, examples of the petroleum solvent include cyclohexane, cycloheptane, cyclooctane, naphthalene, decahydronaphthalene, and tetrahydronaphthalene.

Further, the condensed polycyclic hydrocarbon means that two or more single rings are hydrocarbons which can supply only one condensed ring of the respective rings, and it is preferred to use a hydrocarbon obtained by condensing two single rings.

Such a hydrocarbon system may be a combination of a 5-member ring and a 6-member ring, or a combination of two 6-member rings. Examples of the hydrocarbon system in which a 5-membered ring and a 6-membered ring are combined include hydrazine, cyclopentadiene, indoline, tetrahydroanthracene, etc., and a hydrocarbon system in which two 6-membered rings are combined may, for example, be naphthalene or tetra. Hydronaphthalene (tetrahydronaphthalene) and decahydronaphthalene (decahydronaphthalene).

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

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

(thermal polymerization inhibitor)

In the present invention, the adhesive composition may also contain a thermal polymerization inhibitor. The thermal polymerization inhibitor has a function of preventing radical polymerization due to heat. Specifically, the thermal polymerization inhibitor exhibits high reactivity with respect to the radical, and therefore reacts more preferentially than the monomer to suppress polymerization of the monomer. The composition of the adhesive 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 a high-temperature process in which a wafer having a support plate (support) is heated at 250 ° C for 1 hour. At this time, if the polymerization of the adhesive composition is caused by the high temperature, the solubility of the stripping liquid for peeling the support sheet from the wafer is lowered after the high-temperature process, and the support sheet 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 sheet can be easily peeled off even after a high-temperature process, and Suppress the occurrence of residue.

Thermal polymerization inhibitor, as long as it is effective to prevent heat The radical polymerization reaction is not particularly limited, but a thermal polymerization inhibitor having a phenol skeleton is preferred. Thereby, good solubility can be ensured even after high temperature treatment in the atmosphere. As such a thermal polymerization inhibitor, a hindered phenol-based antioxidant can be used, and examples thereof include gallic phenol, benzoquinone, hydroquinone, methylene blue, tert-butyl catechol, and monobenzyl ether. Methyl hydroquinone, amyl hydrazine, pentyl hydroquinone, n-butyl phenol, phenol, hydroquinone monopropyl ether, 4,4'-(1-methylethylene) 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"-ethylene thiophene (2-methylphenol), 4,4',4 "-Ethylene phenol, 1,1,3-glycol (2,5-dimethyl-4-hydroxyphenyl)-3-phenylpropane, 2,6-di-tert-butyl-4- Methylphenol, 2,2'-methylenebis(4-methyl-6-tert-butylphenol), 4,4'-butylenebis(3-methyl-6-tert-butylphenol) , 4,4'-thiobis(3-methyl-6-tert-butylphenol), 3,9-bis[2-(3-(3-tert-butyl-4-hydroxy-5-methyl) Phenyl)-propenyloxy)-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro(5,5)undecane, triethylene glycol-double-3 -(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate, n-octyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl) Propionate, pentaerythritol bismuth [3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (trade name: IRGANOX1010, manufactured by BASF), ginseng (3,5-di-tert) -butylhydroxybenzyl)isocyanurate, thiodiethylidene bis[3-(3,5-di-tert-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 depends on the type of the elastomer, the type of the hydrocarbon resin, and the use and environment of the adhesive composition. In the case where the amount of the elastomer and the resin combined with the hydrocarbon resin is 100 parts by weight, for example, it is preferably 0.1 part by weight or more and 10 parts by weight or less. When the content of the thermal polymerization inhibitor is within the above range, the effect of suppressing polymerization by heat can be satisfactorily exhibited, and after the high-temperature process, the decrease in solubility of the adhesive composition to the peeling liquid can be further suppressed.

(add solvent)

Further, the adhesive composition of the present invention may have a structure containing an additive solvent composed of a composition which is dissolved by a thermal polymerization inhibitor and which is different from a solvent for dissolving the elastomer and the hydrocarbon resin. 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 may be used alone or in combination of two or more kinds as long as it can dissolve the components of the adhesive composition to form a uniform solution.

Specific examples of the organic solvent include, for example, a terpene solvent having a polar group such as an oxygen atom, a carbonyl group or an ethoxylated group, and examples thereof include geranyl alcohol, nerol, linalool, limonyl aldehyde, and fragrant Molly, menthol, isomenthol, neomenthol, α-terpineol, β-terpineol, γ-terpineol, terpinene-1-ol, terpinen-4-ol, dihydrogen Rosin alcohol acetate, 1,4-nonyl oleyl alcohol, 1,8-nonyl oleyl alcohol, borneol, fragrant celery ketone, ionone, flavonoids, camphor. Further, lactones such as γ-butyrolactone; acetone, methyl ethyl ketone, cyclohexanone (CH), methyl-n-amyl ketone, methyl isoamyl ketone, a ketone of 2-heptanone or the like; a polyhydric alcohol such as ethylene glycol, diethylene glycol, propylene glycol or dipropylene glycol; ethylene glycol monoacetate, diethylene glycol monoacetate, propylene glycol monoacetate Or a compound having an ester bond such as dipropylene glycol monoacetate, a monomethyl ether, a monoethyl ether, a monopropyl ether or a monobutyl ether of the above polyhydric alcohol or a compound having the above ester bond; a derivative of a polyol such as an alkyl ether or a monophenyl ether having an ether bond or the like (such as propylene glycol monomethyl ether acetate (PGMEA) or propylene glycol monomethyl ether (PGME)) a cyclic ether of dioxane or methyl lactate, ethyl lactate (EL), methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate, methoxypropionic acid Ester of methyl ester, ethyl ethoxy propionate, etc.; anisole, ethyl benzyl ether, cresyl methyl ether, diphenyl ether, dibenzyl ether, phenyl ether, butyl phenyl ether An aromatic organic solvent or the like.

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

(other ingredients)

The adhesive composition may further contain other substances having a miscibility insofar as it does not impair the essential characteristics of the present invention. For example, various conventional additives such as an additive resin, a plasticizer, an auxiliary adhesive, a stabilizer, a colorant, and a surfactant for improving the performance of the adhesive can be further used.

(modulation method of the composition of the adhesive)

The method for preparing the adhesive composition of the present invention is not particularly limited, and a known method may be used. For example, the elastomer and the hydrocarbon resin are dissolved in a solvent, and the respective components are stirred using an existing stirring device. Thus, the adhesive composition of this embodiment can be obtained.

Further, when a thermal polymerization inhibitor is added to the adhesive composition of the present embodiment, it is preferred to add an additive solvent for dissolving the thermal polymerization inhibitor in advance to dissolve the thermal polymerization inhibitor.

(Use of the adhesive composition of the present embodiment)

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

The support is, for example, a member that functions to support the wafer in the step of thinning the wafer, and is then attached to the wafer by the adhesive composition of the present embodiment. In one embodiment, the support system is formed, for example, of glass or tantalum having a film thickness of 500 to 1,000 μm.

Further, in one embodiment, a hole that penetrates the support body in the thickness direction is provided in the support system. The solvent for dissolving the adhesive composition flows between the support and the wafer through the hole, whereby the support can be easily separated from the wafer.

After the wafer and the support are adhered to by the adhesive composition, for example, the adhesive composition is applied onto the wafer, an adhesive layer is formed by heating, and the support is pasted through the adhesive layer. Attached to the wafer. The film thickness of the subsequent layer is not particularly limited, but may be, for example, in the range of 5 μm or more and 200 μm or less. Further, the heating condition is not particularly limited as long as it is appropriately set in accordance with the composition of the adhesive to be used, but the temperature can be raised by, for example, 50 ° C or more and 250 ° C or less. The stage baking is performed, and the adhesive layer is efficiently formed into a film.

Further, the support is attached to the wafer. For example, the support may be superposed on the side of the wafer on which the film is formed with the adhesive layer, and pressurized at a high temperature (for example, 215 ° C). The support is attached to the wafer. However, the method of attaching can be appropriately selected from various conventionally known methods depending on the state of the substrate (concavity and unevenness of the surface, strength, etc.), the composition of the adhesive composition, and the material of the support. .

Further, in another embodiment, other reaction layers may be interposed between the support and the wafer in addition to the adhesive layer. The reaction layer is degraded by absorbing light irradiated through the support, and the reaction layer is degraded by irradiating light or the like to the reflective layer, whereby the support and the wafer can be easily separated. At this time, it is preferable that the support system use a support body which is not provided with a hole penetrating in the thickness direction.

The light that is incident on the reaction layer is appropriately used, for example, a YAG laser, a Libbey laser, a glass laser, a YVO ₄ laser, an LD laser, a fiber laser, etc., depending on the wavelength that the reaction layer can absorb. Laser lasers such as solid lasers, pigment lasers, CO ₂ lasers, excimer lasers, Ar lasers, He-Ne lasers, semiconductor lasers, free electron lasers, etc. Or non-laser light. The wavelength of light to be absorbed by the reaction layer is not limited thereto, and may be, for example, light having a wavelength of 600 nm or less.

The reaction layer may also contain a light absorbing agent which is decomposed by, for example, light or the like. As the light absorber, for example, graphite powder, fine metal powder such as iron, aluminum, copper, nickel, cobalt, manganese, chromium, zinc or bismuth, metal oxide powder such as black titanium oxide, carbon black, or aromatic can be used. Diamine metal complex, aliphatic diamine metal complex, aromatic dithiol metal complex, nonylphenol metal complex, squaraine compound, cyanine dye, sub- A dye or pigment such as a base dye, a naphthoquinone dye, or an anthraquinone dye. Such a reaction layer can be formed, for example, by being mixed with a binder resin and applied to a support. Further, 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 also be used. As the inorganic film system, for example, a metal film can be used. Further, as the organic film, for example, a fluorocarbon film can be used. Such a reaction film can be formed on a support by, for example, a plasma CVD method.

Further, the adhesive composition of the present embodiment is preferably used after the support and the support for the wafer for the thinning step. As described above, this support system maintains the strength of the wafer as it is thinned. The adhesive composition of this embodiment is suitable for use in such a wafer and a support.

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

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

Further, a method of manufacturing a laminate in which a wafer and a support are carried out at 220 ° C or lower, and a method of thinning a wafer in which the wafer of the laminate is thinned, using the adhesive composition of the present embodiment, The method of heating the laminate at a temperature of 220 ° C or higher is within the scope of the embodiment.

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

When the reaction layer is modified or the like, the wafer next to the adhesive composition of the present embodiment is separated from the support, and when the adhesive layer is removed, the solvent can be easily dissolved and removed. Further, without using the above-mentioned reaction layer or the like, the solvent is directly supplied to the adhesive layer in the state in which the wafer and the support are next, and the adhesive layer can be easily dissolved to remove the adhesive layer, and the wafer can be removed. The support is separated. At this time, in order to increase the supply efficiency of the solvent to the adhesive layer, it is more preferable to provide a hole penetrating through the support.

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

[Next film]

The adhesive composition of the present invention can be used in various forms depending on the application. For example, a method of directly applying a liquid to a workpiece such as a semiconductor wafer to form an adhesive layer can be used, and it can also be used in the adhesive film of the present invention, that is, a film which is previously coated with a flexible film or the like. After the adhesive layer containing the adhesive composition of any of the above is formed, it is dried, and the film (subsequent film) is attached to the object to be processed (following the film method).

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

The film may then be further coated with a protective film over the adhesive layer. In this case, the protective film on the adhesive layer is peeled off, and the exposed adhesive layer is superposed on the workpiece, and then the film is peeled off from the adhesive layer, whereby the adhesive can be easily used. The layer is placed on the object to be processed.

Therefore, when the adhesive film is used, an adhesive layer having good film thickness uniformity and surface smoothness can be formed as compared with the case where the adhesive composition is directly applied to the workpiece to form an adhesive layer.

The film used in the subsequent production of the film is peeled off from the film as long as the adhesive layer which can be formed on the film is formed. Further, the release film which can be transferred onto the surface to be treated such as a support or a wafer is not particularly limited. For example, a flexible film composed of a polyethylene terephthalate having a film thickness of 15 to 125 μm, a synthetic resin film such as polyethylene, polypropylene, polycarbonate, or polyvinyl chloride may be used. For the above film, it is preferred to apply a release treatment as needed to facilitate transfer.

The method of forming an adhesive layer on the above-mentioned film is a method in which a known method is suitably used in accordance with the film thickness or uniformity of the desired adhesive layer, so that the dry film thickness of the adhesive layer is 10 to 1000 μm. A method of applying the adhesive composition of the present invention to a film.

Further, when the protective film is used, the protective film is not particularly limited as long as it can be peeled off from the adhesive layer, but is preferably, for example, a polyethylene terephthalate film, a polypropylene film, or a polyethylene film. Further, it is preferable that each of the protective films is coated or baked with ruthenium. Therefore, peeling from the adhesive layer becomes easy. The thickness of the protective film is not particularly limited, but is preferably 15 to 125 μm. Therefore, 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 a protective film is used, after the peeling is performed, the exposed adhesive layer is superposed on the object to be processed, and the heating roll is formed on the film. The back surface of the surface of the adhesive layer is moved, whereby the adhesive layer is thermally pressed against the surface of the object to be processed. At this time, the protective film which has been peeled off from the film can be stored in a roll shape by a roll such as a take-up roll, and can be stored and reused.

The embodiments are shown below, and further embodiments of the present invention will be described in detail. Of course, the present invention is not limited to the following embodiments, and various details may be present regarding the details, and needless to say. Further, the present invention is not limited to the above-described embodiments, and various modifications can be made within the scope of the claims. The embodiments obtained by appropriately combining the technical means disclosed separately are also included in the technology of the present invention. Within the scope of sex.

[Examples] [Preparation of the composition of the adhesive]

First, the adhesive composition was prepared as Example 1 and Example 2. The compositions of the elastomer, the hydrocarbon resin, the polymerization inhibitor, the main solvent, and the additive solvent used in Examples 1 and 2 are shown in Table 1 below. In addition, the "parts" in Table 1 are all parts by weight. In addition, in Table 1, the elastomer and the hydrocarbon resin show the ratio of each of these total amounts. The polymerization inhibitor is an amount when the total of the elastomer and the hydrocarbon resin is 100 parts, and the solvent is added in an amount of 100 parts based on the main solvent.

For example, in Example 1, 60 parts of a hydrogenated styrene-based elastomer, Septon 8007L (manufactured by KURARAY Co., Ltd.), 10 parts of Septon 2004 (manufactured by KURARAY Co., Ltd.), and TOPAS TM (manufactured by Polyplastics Co., Ltd.) 30 were used. The fraction was dissolved in decalin at a concentration of 25%, and IRGANOX 1010 as a polymerization inhibitor and butyl acetate as an additive solvent were added to prepare an adhesive composition.

The elastomers in Examples 1 and 2 were Septon 8007L (SEP: polystyrene-poly(ethylene/propylene) block copolymer of Septon (trade name) manufactured by KURARAY Co., Ltd.; styrene content 30 %, Mw = 80,000), and Septon 2004 (SEP: polystyrene-poly(ethylene/propylene) block copolymer of Septon (trade name) manufactured by KURARAY Co., Ltd.; styrene content: 18% by weight, Mw = 90,000) .

Further, in the hydrocarbon resins of Examples 1 and 2, TOPAS (trade name) TM (cycloolefin copolymer; ethylene-norbornene copolymer, manufactured by Polyplastics Co., Ltd., Mw = 10,000, Mw/) was used. Mn = 2.08, norbornene: ethylene = 50: 50 (weight ratio)).

Further, as the thermal polymerization inhibitor, "IRGANOX (trade name) 1010" manufactured by BASF Corporation was used. Further, the main solvent is decahydronaphthalene represented by the following chemical formula (I). Further, butyl acetate was used as the solvent to be added.

The composition of the adhesive was prepared as Comparative Example 1 and Comparative Example 2. The compositions of the resin, polymerization inhibitor, main solvent and additive solvent used in Comparative Example 1 and Comparative Example 2 are shown in Table 2 below.

In Comparative Example 1, only the Septon 8007L (SEP) of Septon (trade name) manufactured by KURARAY Co., Ltd. was used as the resin component. : Polyethylene-poly(ethylene/propylene) block copolymer; styrene content: 30%, Mw = 80,000). In Comparative Example 2, only the Tuftec (trade name) H1051 (SEBS) manufactured by Asahi Kasei Co., Ltd. was used as the resin component. Hydrogenated styrene-based thermoplastic elastomer; styrene content 42%, Mw = 78,000).

[Formation of adhesive layer]

The adhesive composition was spin-coated on a semiconductor wafer substrate (12 Å, 矽), and baked at 100 ° C, 160 ° C, and 220 ° C for 5 minutes to form an adhesive layer having a film thickness of 50 μm.

[attached]

The bare glass support (12 Å) having a fluorocarbon layer (thickness: 0.5 μm) having a reaction layer for 532 nm laser absorption was bonded to the wafer under vacuum at 215 ° C under a condition of 4000 kg for 5 minutes. The laminate is made. At this time, it was confirmed that there was no adhesion failure (not followed) in the subsequent thinning step and thermal step, which was associated with breakage of the wafer or reduction in the in-plane uniformity of the wafer. Further, the reaction layer was formed 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 2,800 W, and a film formation temperature of 240 °C.

Next, the back surface of the wafer was thinned (50 μm) by a back grinding apparatus manufactured by DISCO, and then immersed in NMP (N-methyl-2-pyrrolidone) to confirm whether or not the swelling or support of the adhesive composition was generated. Stripping of the body.

[stripping]

For the wafer, laser irradiation at 532 nm was performed from the glass surface to separate between the glass support and the adhesive layer. The wafer from which the glass support was removed was spin-washed by p-menthane, and the adhesive layer was removed without residue. The results of Example 1 and Comparative Example 2 are shown in Table 1, and the results of Comparative Example 1 and Comparative Example 2 are shown in Table 2.

Whether or not the film forming property is possible is determined by whether or not the coating composition of the embodiment or the comparative example can be applied to a wafer substrate by 15 μm or more. Next, the case where the coating is possible is regarded as "○", and the case where the coating is impossible is regarded as "x".

The heat resistance was evaluated by heating the laminate formed using the adhesive composition of the example or the comparative example under a reduced pressure atmosphere (10 Pa) at 220 ° C for 1 hour. The evaluation of heat resistance is regarded as "○" if there is no foaming or peeling between the wafer and the support, and if it is, it is regarded as "x".

Whether or not the chemical resistance is immersed in the NMP after the immersion of the adhesive composition of the example or the comparative example is judged by swelling or not. Next, the case of no swelling is regarded as "○", and the case of swelling is regarded as "x".

In the adhesive compositions of Examples 1 and 2, even if immersed in NMP, swelling of the adhesive composition did not occur, and as a result, peeling from the adhesive composition of the glass support did not occur. On the other hand, in the adhesive compositions of Comparative Example 1 and Comparative Example 2, swelling of the adhesive composition was caused by immersion in NMP, and as a result, peeling from the adhesive composition of the glass support was caused. Therefore, it has been revealed that even if the laminate formed of the adhesive compositions of Examples 1 and 2 is immersed in NMP, the swelling of the adhesive composition does not occur, and the composition of the adhesive from the glass support does not occur. Stripping of things.

[Industrial availability]

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

Claims (9)

An adhesive composition comprising an elastomer and a cycloolefin polymer, wherein the elastic system contains a styrene unit as a structural unit of a main chain, and the content of the styrene unit is 14% by weight or more and 50% by weight or less, and The content of the elastomer is in the range of 50% by weight or more and 99% by weight or less based on the total amount of the elastomer and the cycloolefin polymer, and the content of the cycloolefin polymer is 1% by weight or more and 50%. Within the range of % by weight or less. The adhesive composition according to claim 1, which further comprises a solvent containing a condensed polycyclic hydrocarbon. The adhesive composition according to the first or second aspect of the invention, wherein the content of the styrene unit contained in the structural unit as the main chain of the elastomer is 17% by weight or more and 40% by weight or less. The adhesive composition according to the first or second aspect of the invention, wherein the elastomer comprises two or more types of styrene units having a styrene unit contained in a structural unit as a main chain. A vinyl elastomer. The adhesive composition according to the first or second aspect of the invention, wherein the elastomer has a weight average molecular weight of 20,000 or more and 200,000 or less. The adhesive composition according to claim 1 or 2, wherein the elastomer is a hydride. The adhesive composition according to claim 1 or 2, wherein both ends of the elastomer are block polymers of styrene. The adhesive composition according to claim 1 or 2, wherein the elastomer is a hydride of a block copolymer of styrene and a conjugated diene. An adhesive film characterized in that an adhesive layer composed of the adhesive composition as described in claim 1 or 2 of the patent application is formed on the film.