KR101799613B1 - Method of producing adhesive composition, adhesive composition, and adhesive film - Google Patents

Abstract

Provided is an adhesive composition for preventing adhesion of residues on a wafer when it is dissolved in a solvent and used for adhesion between a wafer and a support of the wafer.
The method for producing an adhesive composition for bonding a wafer and a support of the wafer includes a purification process for removing an anticaking agent contained in the adhesive composition.

Description

TECHNICAL FIELD [0001] The present invention relates to a method for producing an adhesive composition, an adhesive composition, and an adhesive film,

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

There has been a growing demand for highly integrated silicon in a package by making a semiconductor silicon chip (hereinafter, referred to as a chip) mounted on the mobile phone, a digital AV device, an IC card, etc. more compact and thinner. For example, in an integrated circuit that packages a plurality of chips typified by a CSP (chip size package) or an MCP (multi-chip package), a thin circuit is required. In order to realize high integration of chips in a package, it is necessary to make the thickness of the chip thin to a range of 25 to 150 mu m.

However, since the semiconductor wafer (hereinafter referred to as a wafer) serving as the base of the chip is thinned by grinding, its strength becomes weak, and the wafer tends to crack or warp. In addition, since it is difficult to automatically transport a wafer whose strength is weakened by thinning (thinning) the wafer, it must be carried by a person's hand, and handling thereof is troublesome.

Therefore, a wafer handling system has been developed that maintains the strength of the wafer by bonding a plate made of glass, hard plastic, or the like called a support plate to the wafer to be ground, thereby preventing occurrence of cracks and warping of the wafer. Since the strength of the wafer can be maintained by the wafer handling system, it is possible to automate the transportation of the thinned semiconductor wafer.

In the wafer handling system, the wafer and the support plate are bonded using an adhesive tape, a thermoplastic resin, an adhesive, or the like. After the wafer with the support plate attached thereto is thinned, the support plate is peeled from the substrate before dicing the wafer. When an adhesive is used for bonding the wafer and the support plate, the adhesive is dissolved and the wafer is peeled from the support plate.

Recently, hydrocarbon adhesives have been developed as adhesives (Patent Documents 1 and 2).

Japan Specification 2009-529065 (Released on August 13, 2009) Japan Special Feature 2010-506406 (Released on February 25, 2010)

However, many of the materials used for the hydrocarbon-based adhesives related to the prior art are in the form of pellets, so that the adhesive contains an anti-sticking agent (lubricant) used in the process of molding into a pellet. When an adhesive containing such an anticaking agent is used for bonding a wafer and a support to a wafer, residues are formed on the wafer after cleaning even if the wafer is dissolved in a solvent after use and washed. Such a residue on the wafer leads to deterioration of the electrical characteristics of the substrate and the yield of the product.

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above problems and provides a method of producing an adhesive composition for preventing the occurrence of residues on a wafer when the wafer is used for adhering a wafer and a support of the wafer and then washed with a solvent, The main purpose is to do.

In order to solve the above problems, a method for manufacturing an adhesive composition for adhering a wafer according to the present invention and a support of the wafer includes a purification step for removing the antireflection agent contained in the adhesive composition.

The adhesive composition for bonding the wafer according to the present invention and the support of the wafer is characterized in that the content of the metal component originating from the antiglare agent is 10 ppb or more and 2 ppm or less with respect to the total solid weight.

The adhesive film for bonding the wafer according to the present invention and the support of the wafer is characterized in that an adhesive layer made of an adhesive composition for bonding the wafer according to the present invention and the support of the wafer is formed on the film.

The method for producing an adhesive composition for adhering a wafer according to the present invention to a support of the wafer includes a purification step for removing an anticaking agent contained in the adhesive composition. Therefore, it is possible to produce an adhesive composition which prevents the occurrence of residues on the wafer when it is used to adhere the wafer to a support of a wafer and then dissolved in a solvent and cleaned. In addition, it is possible to provide an adhesive composition which is used for adhesion between a wafer and a support of the wafer, and then prevents the residue from being formed on the wafer when the wafer is dissolved and cleaned with a solvent.

[Adhesive composition]

The adhesive composition according to the present invention is an adhesive composition from which an antistacking agent has been removed. The content of the metal component derived from the antistatic agent is 10 ppb or more and 2 ppm or less based on the total solid weight of the adhesive composition. The adhesive composition according to the present invention may contain a hydrocarbon resin or an elastomer.

The adhesive composition according to the present invention includes a resin for imparting adhesiveness. It is preferable that the resin includes at least one kind selected from 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. Examples of the hydrocarbon resin include at least one resin selected from the group consisting of a cycloolefin polymer (hereinafter also referred to as " resin A ") and a terpene resin, a rosin resin and a petroleum resin B ").

The cycloolefin polymer is a resin obtained by polymerizing a cycloolefin monomer as a monomer component. Examples of the cycloolefin monomers include bifunctional compounds such as norbornene and norbornadiene, trifunctional compounds such as dicyclopentadiene and hydroxydicyclopentadiene, tetracyclines such as tetracyclododecene, cyclopentadiene 3 (Methyl, ethyl, propyl, butyl, etc.) substituents, alkenyl (vinyl) substituents, alkylidene (ethylidene etc.) substituents, aryl (Phenyl, tolyl, naphthyl, etc.), and the like. As the resin (A), only one kind of these cycloolefin monomers may be polymerized, or two or more kinds of them may be copolymerized.

The monomer component contained in the resin (A) is not limited to a cycloolefin monomer but may contain other monomer copolymerizable with the cycloolefin monomer. Examples of other monomers include straight chain or branched chain alkene monomers. Examples of such alkene monomers include ethylene, propylene, 1-butene, isobutene, 1-hexene, . The alkene 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, the weight average molecular weight (Mw) measured as a polystyrene conversion value by gel permeation chromatography (GPC) is 50,000 to 200,000, more preferably 50,000 ~ 150,000. When the weight average molecular weight of the resin (A) is within the above range, cracks are hardly generated after the film formation and the solubility in a specific solvent can be obtained.

It is preferable that 5 mol% or more of the monomer component constituting the resin (A) is a cycloolefin monomer from the viewpoints of high heat resistance (low thermally decomposable property and thermogravimetric property), and 10 mol% or more is a cycloolefin monomer , And more preferably 20 mol% or more. The upper limit is not particularly limited, but it is preferably 80 mol% or less from the viewpoints of solubility and stability with time in the solution, more preferably 70 mol% or less. When the other monomer contains a straight chain or branched chain alkene monomer, the content of the monomer component in the resin (A) is preferably from 10 to 90 mol%, from the viewpoint of solubility and flexibility, more preferably from 20 to 85 mol% , And particularly preferably from 30 to 80 mol%.

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

Examples of commercially available products that can be used as the resin (A) include "APEL (trade name)" manufactured by Mitsui Chemicals, "TOPAS (trade name)" manufactured by Polyplastics, "ZEONOR (trade name)" ZEONEX (trade name) "manufactured by JSR Corporation, and" ARTON (trade name) "manufactured by JSR.

The resin (B) is at least one resin selected from the group consisting of a terpene resin, a rosin resin and a petroleum resin as described above. Examples of the terpene resin include 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-based resin include an aliphatic or aromatic petroleum resin, a hydrogenated petroleum resin, a modified petroleum resin, an alicyclic petroleum resin, and a maroon-indene petroleum resin. 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 conversion value by GPC is 300 to 10,000, and more preferably 500 to 5,000. When the weight average molecular weight of the resin (B) is within the above range, cracks are hardly generated after the film formation and high heat resistance (resistance to thermal decomposition property and sublimation property) is obtained.

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, more preferably 60 parts by weight or more, based on the whole of the hydrocarbon resin. When the content of the resin (A) is 40 parts by weight or more based on the total weight of the hydrocarbon resin, flexibility and high heat resistance (low thermal decomposition resistance) can be exhibited.

(Elastomer)

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

In the present specification, the term " constituent unit " refers to a structure derived from one molecule of monomers in the structure constituting the polymer. In the present specification, the "styrene unit" is a styrene-derived structural unit contained in the polymer when styrene is polymerized, and the "styrene unit" may have a substituent. Examples of the substituent include an alkyl group of 1 to 5 carbon atoms, an alkoxy group of 1 to 5 carbon atoms, an alkoxyalkyl group of 1 to 5 carbon atoms, an acetoxy group, and a carboxyl group.

When the content of the styrene unit is in the range of 14 wt% to 50 wt%, and the weight average molecular weight of the elastomer is in the range of 10,000 to 200,000, it is easily dissolved in the hydrocarbon solvent described later, can do. Further, since the content of the styrene unit and the weight average molecular weight are in the above-mentioned ranges, resist solvents (for example, PGMEA, PGME, etc.) exposed when the wafer is provided to the resist lithography process, acids (hydrofluoric acid, etc.) TMAH and the like).

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

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

As the elastomer, the content of the styrene unit is in the range of 14 wt% to 50 wt%. When the weight average molecular weight of the elastomer is in the range of 10,000 to 200,000, various elastomers can be used. Styrene block copolymers (SIS), styrene-butadiene-styrene block copolymers (SBS), styrene-butadiene-butylene-styrene block copolymers Ethylene-butylene-styrene block copolymer (SEBS), styrene-ethylene-propylene-styrene block copolymer (styrene-isoprene-styrene block copolymer), styrene block copolymer (SBBS), ethylene propylene terpolymer (EPT) Styrene block copolymer (SEPS), a styrene-ethylene-ethylene-propylene-styrene block copolymer (SEEPS), a styrene block copolymer of styrene-ethylene-ethylene-propylene-styrene block copolymer (Septon V9461 ), A styrene-ethylene-butylene-styrene block copolymer having a reactive crosslinked styrene block (Septon V9827 having a reactive polystyrene-based hard block (Kuraray Co., Ltd.)), Those having an average molecular weight in the above-mentioned range can be used.

Among the elastomers, hydrous materials are more preferable. If it is a water-soluble additive, the stability against heat is improved, and deterioration such as decomposition or polymerization is hardly caused. It is more preferable from the viewpoints of solubility in hydrocarbon solvents and resistance to resist solvents.

Further, among the elastomers, styrene block polymers at both ends are more preferable. This is because styrene having high heat stability is blocked at both ends to exhibit higher heat resistance.

More specifically, it is more preferable to be a hydrogenated product of a block copolymer of styrene and a conjugated diene. The stability against heat is improved, and deterioration such as decomposition or polymerization is hardly caused. Further, styrene having high thermal stability is blocked at both ends to exhibit higher heat resistance. Further, from the viewpoints of solubility in a hydrocarbon solvent and resistance to a resist solvent, it is more preferable.

Examples of commercially available products that can be used as the elastomer contained in the adhesive composition according to the present invention include "Septon (trade name)" manufactured by Kuraray Co., Ltd., "Hiabra (trade name)" manufactured by Kuraray Co., (Trade name) manufactured by JSR Corporation, and Dynalon (trade name) manufactured by JSR Corporation.

The content of the elastomer contained in the adhesive composition according to the present invention is 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, based on 100 parts by weight of the total amount of the adhesive composition desirable.

The elastomer may be mixed with a plurality of kinds. That is, the adhesive composition according to the present invention may contain a plurality of kinds of elastomers. At least one of the plurality of kinds of elastomers contains a styrene unit as a constituent unit of the main chain, the content of the styrene unit is in a range of 14% by weight or more and 50% by weight or less, a weight average molecular weight of 10,000 or more and 200,000 or less Is a category of the present invention. In the adhesive composition according to the present invention, when a plurality of kinds of elastomers are contained, they may be prepared so that the content of the styrene unit is within the above range. For example, when Septon 8007 (trade name), which is a trade name of Kuraray Co., Ltd., having a styrene unit content of 30% by weight, and Septon 2063 (trade name), which has a styrene unit content of 13% by weight, are mixed at a weight ratio of 1: 1, The content of styrene relative to the total amount of the elastomer contained is 21 to 22% by weight, and is 14% by weight or more. For example, when the styrene unit is 10 wt% and 60 wt% is mixed in a one-to-one ratio, it becomes 35 wt%, which is within the above range. The present invention may be of such a form. It is most preferable that the plurality of kinds of elastomers included in the adhesive composition according to the present invention contain styrene units in the above-mentioned range, and the weight average molecular weight in the above range is the most preferable.

(solvent)

The adhesive composition according to the present invention preferably contains a solvent for dissolving a hydrocarbon resin or an elastomer. As such a solvent, for example, non-polar hydrocarbon solvents, polar and non-polar petroleum solvents, and the like can be used.

Preferably, the solvent may comprise condensed polycyclic hydrocarbons. By including the condensed polycyclic hydrocarbon in the solvent, clouding that can occur when the adhesive composition is stored in a liquid form (particularly at low temperature) can be avoided and the product stability can be improved.

Examples of the hydrocarbon-based solvent include linear, branched or cyclic hydrocarbons. For example, straight chain hydrocarbons such as hexane, heptane, octane, nonane, methyloctane, decane, undecane, dodecane and tridecane, branched hydrocarbons having 3 to 15 carbon atoms, p-menthane, o-menthane, m Beta-terpinene, beta -terpinene, gamma -terpinene, 1,4-terpine, 1,8-terpine, borane, norbonane, Pinene, thujane,? -Tujone,? -Tuzon, caran, longifolene, and the like.

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

The condensed polycyclic hydrocarbon is preferably a hydrocarbon formed by condensation of two monocyclic rings, which is a condensed ring hydrocarbon formed by feeding at least two monocyclic rings adjacent to the respective rings to each other.

Such hydrocarbons include a combination of a five-membered ring and a six-membered ring, or a combination of two six-membered rings. Examples of hydrocarbons in which a 5-membered ring and a 6-membered ring are combined include indene, pentane, indane, and tetrahydroindene. Examples of the hydrocarbon having two 6-membered rings include naphthalene, tetrahydronaphth Talline (tetralin) and decahydronaphthalene (decalin).

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 saturated aliphatic hydrocarbons. In this case, the content of the condensed polycyclic hydrocarbon is preferably at least 40 parts by weight, more preferably at least 60 parts by weight, based on the whole hydrocarbon solvent. When the content of the condensed polycyclic hydrocarbon is 40 parts by weight or more based on the total amount of the hydrocarbon-based solvent, high solubility in the resin can be exhibited. If the mixing ratio of the condensed polycyclic hydrocarbon and the saturated aliphatic hydrocarbon is within the above range, the odor of the condensed polycyclic hydrocarbon can be alleviated.

Examples of the saturated aliphatic hydrocarbon include straight chain hydrocarbons such as hexane, heptane, octane, nonane, methyloctane, decane, undecane, dodecane and tridecane, branched hydrocarbons having 3 to 15 carbon atoms, , o-menthane, m-menthane, diphenylmethane, 1,4-terpine, 1,8-terpine, borane, norbornane, pyrazane, tozan, caran and longpolyene.

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

(Thermal polymerization inhibitor)

The adhesive composition according to the present invention may contain a thermal polymerization inhibitor. The thermal polymerization inhibitor has a function of preventing radical polymerization reaction by heat. Specifically, since the thermal polymerization inhibitor exhibits high reactivity to the radical, it reacts preferentially to the monomer to inhibit the polymerization of the monomer. The adhesive composition containing such a thermal polymerization inhibitor is inhibited from polymerization under a high temperature environment (particularly 250 ° C to 350 ° C).

For example, in a semiconductor manufacturing process, there is a case that a high temperature process for heating a wafer to which a support is adhered at 250 DEG C for one hour is included. At this time, if the polymerization of the adhesive composition occurs at a high temperature, the solubility of the release plate for separating the support plate (support plate) from the wafer after the high temperature process deteriorates, and the support plate can not be satisfactorily peeled off from the wafer. However, in the adhesive composition of the present invention containing a thermal polymerization inhibitor, since the oxidation by heat and the polymerization reaction are suppressed, the support plate can be easily peeled off even after a high-temperature process, can do.

The thermal polymerization inhibitor is not particularly limited as long as it is effective in preventing radical polymerization by heat, but a thermal polymerization inhibitor having phenol is preferable. As a result, good solubility can be ensured even after the high temperature treatment in the atmosphere. As the thermal polymerization inhibitor, a hindered phenol-based antioxidant can be used. Examples of the heat-polymerization inhibitor include hindered phenol-based antioxidants such as pyrrole, benzoquinone, hydroquinone, methylene blue, tert- butylcatechol, monobenzyl ether, methylhydroquinone, , Amyl oxyhydroquinone, n-butyl phenol, phenol, hydroquinone monopropyl ether, 4,4'- (1-methylethylidene) bis (2-methylphenol), 4,4 ' ) Bis (2,6-dimethylphenol), 4,4 '- [1- [4- (1- (4- hydroxyphenyl) 4, 4 "-ethylenedendrisol phenol, 1,1,3-tris (2,5-dimethyl-4-hydroxyphenyl) -3 (4-methyl-6-tert-butylphenol), 4,4'-butylidenebis (3-tert-butylphenyl) (3-methyl-6-tert-butylphenol), 4,4'-thiobis -Hydroxy-5-methylphenyl) -propionyloxy) -1,1- Dimethylethyl] -2,4,8,10-tetraoxaspiro (5,5) undecane, triethylene glycol-bis-3- (3-tert- butyl-4-hydroxy-5-methylphenyl) propionate (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, pentaerythrityl tetrakis [3- (3,5-di-tert-butylhydroxybenzyl) isocyanurate, thiodiethylenebis [3- (3,5-di -tert-butyl-4-hydroxyphenyl) propionate]. The thermal polymerization inhibitor may be used alone or in combination of two or more.

The content of the thermal polymerization inhibitor may be appropriately determined according to the kind of the hydrocarbon resin or elastomer, the use of the adhesive composition, and the use environment. For example, when the amount of the hydrocarbon resin or elastomer is 100 parts by weight, , And 10 parts by weight or less. When the content of the thermal polymerization inhibitor is within the above range, the effect of inhibiting polymerization by heat is excellently exerted, and the deterioration of the solubility in the peeling liquid of the adhesive composition can be further suppressed after the high temperature process.

The adhesive composition according to the present invention may contain a heat polymerization inhibitor dissolved therein and an additive solvent having a different composition from the solvent for dissolving the hydrocarbon resin or elastomer. The additive is not particularly limited, but an organic solvent capable of dissolving the components contained in the adhesive composition can be used.

As the organic solvent, for example, the components of the adhesive composition may be dissolved to form a homogeneous solution, and any one kind or a combination of two or more kinds thereof may be used.

Specific examples of the organic solvent include, for example, a terpene solvent having an oxygen atom, a carbonyl group or an acetoxy group as a polar group, and examples thereof include geraniol, nerol, linalol, citral, But are not limited to, menthol, isomenthol, neomenthol,? -Terpineol,? -Terpineol,? -Terpineol, terpinene-1-ol, terpinene-4-ol, dihydrotaphenylacetate, Cineol, 1,8-cineol, borneol, carbone, ionone, thujone, camphor. Also, lactones such as? -Butyrolactone; ketones such as acetone, methyl ethyl ketone, cyclohexanone (CH 3), methyl-n-pentyl ketone, methyl isopentyl ketone and 2-heptanone; Polyhydric alcohols such as glycol, propylene glycol and dipropylene glycol; compounds having an ester bond such as ethylene glycol monoacetate, diethylene glycol monoacetate, propylene glycol monoacetate or dipropylene glycol monoacetate; A compound having an ether bond such as a monoalkyl ether of monoethyl ether, monoethyl ether, monopropyl ether, monobutyl ether, or monophenyl ether of a compound having a bond (among these, a derivative of a polyhydric alcohol such as propylene glycol mono Methyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME) A cyclic ether such as dioxane or an ester such as methyl lactate, ethyl lactate (EL), methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate and ethyl ethoxypropionate Aromatic organic solvents such as anisole, ethyl benzyl ether, cresyl methyl ether, diphenyl ether, dibenzyl ether, phenetole, butyl phenyl ether and the like.

The content of the additive solvent may be appropriately determined depending on the kind of the thermal polymerization inhibitor and is preferably from 1 part by weight to 50 parts by weight based on 1 part by weight of the thermal polymerization inhibitor, More preferably 1 to 15 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 components)

The adhesive composition according to the present invention may further contain other miscible materials insofar as the essential characteristics of the present invention are not impaired. For example, various additives commonly used such as an additive resin for improving the performance of the adhesive, a plasticizer, an adhesion assisting agent, a stabilizer, a colorant, and a surfactant can be further used.

(Method of preparing adhesive composition)

The method for preparing the adhesive composition before adjusting the content of the antistatic agent is not particularly limited and a known method may be used. For example, a method in which a hydrocarbon resin or an elastomer is dissolved in a solvent, By stirring the composition, an adhesive composition can be obtained.

When a heat polymerization inhibitor is added to the adhesive composition, it is preferable to add a heat polymerization inhibitor dissolved in an additive solvent for dissolving the heat polymerization inhibitor in advance.

The adhesive composition thus prepared can be subjected to a purification step in a method for producing an adhesive composition according to the present invention to be described later to obtain an adhesive composition according to the present invention. Further, even if the method other than the method for producing the adhesive composition according to the present invention described later is used, the adhesive composition according to the present invention can be produced as long as the method can remove the antireflection agent.

(Antistatic agent)

In the refining step, the antiglare agent to be removed from the adhesive composition is also referred to as an activator, and is contained in the resin when the resin (hydrocarbon resin, elastomer) used in the adhesive composition is molded into pellets. As a result, when the adhesive composition is prepared using the resin, an antireflection agent is finally contained in the adhesive composition. Because many commercially available resins are supplied on pellets, many adhesive compositions contain antiglare agents.

As examples of the antiglare agent, G., Talc _{(Mg 3 Si 4 O 10 (} OH) 2), hydro talc _{(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), lead stearate, zinc stearate, calcium stearate, stearates such as magnesium stearate, liquid paraffin, paraffin wax And fatty acid amides such as paraffins such as stearic acid, stearic acid amide, oleic acid amide, methylene bisstearic acid amide, ethylene bisstearic acid amide and erucic acid amide.

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

The adhesive composition according to the present invention has a content of a metal component derived from an anti-static agent of 10 ppb or more and 2 ppm or less based on the total solid weight of the adhesive composition.

If the content of the metal component derived from the antiglare agent contained in the adhesive composition is 2 ppm or less based on the total solid weight of the adhesive composition, residues are generated on the wafer even after the wafer and the support are bonded and dissolved using this adhesive composition and washed It is preferable. Although the lower limit value of the content of the metal component derived from the antiglare agent contained in the adhesive composition is preferably " 0 ", the detection limit value of the metal component (generally 10 ppb) may be used. Therefore, the lower limit of the content of the metal component derived from the antiglare agent contained in the adhesive composition is 10 ppb with respect to the total solid weight of the adhesive composition.

The content of the metal component derived from the antiglare agent contained in the adhesive composition can be determined by quantifying the metal component in the adhesive composition by, for example, ICP-MS (Dielectric Bonded 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 the value based on the total solid weight of the adhesive composition, and the concentration of the metal component in the adhesive composition The content of the metal component derived from the antiglare agent can be calculated.

In the adhesive composition according to the present invention, the content of the metal component most contained in the metal component derived from the antistatic agent contained in the adhesive composition may be 10 ppb or more and 2 ppm or less with respect to the total solid weight of the adhesive composition.

(Use of Adhesive Composition)

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

The support is bonded to the wafer by the adhesive composition according to the present invention, for example, by fulfilling the role of supporting the wafer in the step of thinning the wafer. In one embodiment, the support is formed of, for example, glass or silicon having a thickness of 500 to 1000 占 퐉.

In one embodiment, the support body is provided with a hole penetrating the support body in the thickness direction. And the support and the substrate can be easily separated from each other by pouring a solvent which dissolves the adhesive composition through the hole between the support and the wafer.

In another embodiment, a reaction layer may be interposed between the support and the wafer in addition to the adhesive layer. The reaction layer is altered by absorbing the light emitted through the support, and the support and the wafer can be easily separated from each other by modifying the reaction layer by irradiating the reaction layer with light or the like. In this case, it is preferable to use a support having no hole penetrating in the thickness direction.

The light to be irradiated to the reaction layer may be a solid laser such as a YAG laser, a laser beam, a glass laser, a YVO ₄ laser, an LD laser or a fiber laser, a liquid laser such as a dye laser , Gas lasers such as CO ₂ lasers, excimer lasers, Ar lasers, and He-Ne lasers, laser lasers such as semiconductor lasers, free electron lasers, or non-laser lasers. The wavelength of the light to be absorbed into the reaction layer is not limited to this, but may be, for example, a light having a wavelength of 600 nm or less.

The reaction layer may contain, for example, a light absorbent decomposed by light or the like. Examples of the light absorbing agent include graphite powder, fine metal powder such as iron, aluminum, copper, nickel, cobalt, manganese, chrome, zinc and terlue, metal oxide powder such as black titanium oxide, carbon black, A dyestuff or pigment such as a metal complex, an aliphatic diamine metal complex, an aromatic dithiol metal complex, a mercapto phenol metal complex, a squalinium compound, a cyanine dye, a methine dye, a naphthoquinone dye or an anthraquinone dye Can be used. Such a reaction layer can be formed, for example, by mixing with a binder resin and coating on a support. It is also possible to use a resin having a light absorber.

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

The adhesive composition according to the present invention is suitably used for adhesion between a wafer and a support provided in a thinning process after bonding with a support. As described above, this support maintains the strength of the wafer when the wafer is thinned. The adhesive composition according to the present invention is suitably used for adhesion between such a wafer and a support.

In addition, the adhesive composition according to the present invention is suitably used for adhesion between a wafer and a support provided in an electrode forming step after bonding with a support.

If the adhesive composition contains an antistatic agent, the metal component derived from the antiglare agent remains on the wafer, which adversely affects the electrical characteristics of the wafer on which the electrode is formed. On the other hand, the adhesive composition according to the present invention does not cause residues on the wafer after bonding and dissolution of the wafer and the support are washed, since the antireflection agent is removed. Therefore, when the adhesive composition according to the present invention is used for bonding a wafer and a support, electrical characteristics, particularly connection properties, of a wafer provided with an electric element such as an electrode are good.

According to the adhesive composition of the present invention, it is possible to prevent the residue from being formed on the wafer when it is dissolved in a solvent and washed after it is used for bonding the wafer and the support of the wafer.

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

In the case of removing the adhesive layer after separating the wafer and the support adhered by the adhesive composition according to the present invention by altering the reaction layer or the like, it is possible to easily dissolve and remove the adhesive layer by using a solvent dissolving the adhesive composition have. Further, by supplying the solvent directly to the adhesive layer in a state in which the wafer and the support are adhered without using the reaction layer and the like, the adhesive layer can be easily dissolved and the adhesive layer can be easily removed to separate the wafer and the support . In this case, it is more preferable that a hole penetrating the support body is provided in order to increase the supply efficiency of the solvent to the adhesive layer.

[Method of producing adhesive composition]

The method for producing an adhesive composition for adhering a wafer according to the present invention to a support of the wafer includes a purification step for removing an anticaking agent contained in the adhesive composition. In the method for producing an adhesive composition according to the present invention, it is preferable that the content of the metal component derived from the antiglare agent contained in the adhesive composition in the purification step is 2 ppm or less with respect to the total solid weight of the adhesive composition. Although the lower limit value of the content of the metal component derived from the antiglare agent contained in the adhesive composition is preferably " 0 ", the detection limit value of the metal component (generally 10 ppb) may be used.

(Purification process)

As a method for removing the antiglare agent contained in the adhesive composition in the purification process, specifically, (1) a method of filtering the adhesive composition to remove the antiglare agent may be mentioned.

In the method of filtering an adhesive composition to remove an antiglare agent, the adhesive composition is first passed through a filter having a pore diameter of 0.01 to 10 μm (preferably 0.1 to 10 μm) to remove the anticaking agent from the solution. The hole diameter of the filter can be appropriately selected depending on the kind of the antiglare agent contained in the adhesive composition. That is, the filter may have a hole diameter capable of filtering the anti-cracking agent.

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

In the pretreatment step (2) of the purification step (1), a resin solution in which a resin used in an adhesive composition is dissolved in a solvent is dropped into water or alcohol which is a poor solvent for the resin solution, May be reprecipitated (precipitated). Such alcohols are preferably alcohols having 1 to 4 carbon atoms, and examples thereof include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol and 2-butanol. Examples of the solvent for dissolving the resin include terpene solvents such as the above-mentioned p-menthane, petroleum solvents such as cyclohexane and decahydronaphthalene described above. Then, the precipitated resin is removed from the solution in which the anti-crossing agent is dispersed to remove the anti-cracking agent from the resin. Thus, an adhesive composition is prepared using a resin from which an anti-cracking agent has been removed. Further, by further purifying the adhesive composition by the purification step (1), the adhesive composition from which the anti-cracking agent has been removed can be produced.

The resin precipitated in the solution can be removed from the solution by a method such as filtration, supernatant removal (decantation), centrifugation, or reprecipitation of the resin.

As the pretreatment step (2) of the purification step (1), the pellet-shaped resin may be washed to remove the antiglare agent. First, the pellet-shaped resin is washed with stirring in a poor solvent such as water or an alcohol (preferably an alcohol having 1 to 4 carbon atoms) or the like to remove the antiglare agent adhering to the surface of the pellet-shaped resin. Then, the solution in which the pellets are dispersed is filtered by a mesh filter having a coarse mesh such as a pore diameter of 10 to 200 mu m to remove the antiglare agent desorbed from the resin. Thus, an adhesive composition is prepared using a resin from which an anti-cracking agent has been removed. Further, by further purifying the adhesive composition by the purification step (1), the adhesive composition from which the anti-cracking agent has been removed can be produced.

In the same manner as in the above-described cleaning with water or alcohol, the pellet-shaped resin may be immersed in an acid such as hydrofluoric acid to dissolve and remove the antireflection agent by a method of cleaning with an acid to dissolve and remove the antireflection agent.

Alternatively, the antistatic agent may be removed from the resin by collecting a relatively lightweight antistatic agent by a wind force using a wind separator (jet separator) and recovering only relatively heavy pellets.

As the pretreatment step (2) of the purification step (1), the antireflection agent may be removed by ultrasonically cleaning the resin immersed in the solution. The solution for immersing the resin is a poor solvent. Examples of the poor solvent include propylene glycol monomethyl ether acetate as a glycol ether, propylene glycol monomethyl ether, methanol as a lower alcohol having 1 to 5 carbon atoms, ethanol, propanol, and the like. By using these poor solvents, it is possible to remove the anti-cracking agent by swelling the resin, although the resin itself does not substantially dissolve. The temperature at which the resin is dipped in the solution is preferably not less than 20 degrees and not more than 50 degrees. The ultrasonic cleaning time is preferably 5 minutes or more and 60 minutes or less. Thus, an adhesive composition is prepared using a resin from which an anti-cracking agent has been removed. Further, by further purifying the adhesive composition by the purification step (1), the adhesive composition from which the anti-cracking agent has been removed can be produced.

When the resin is immersed in a solution and ultrasonically cleaned, a known ultrasonic cleaner may be used.

The method for removing the antiglare agent contained in the adhesive composition as described above may be performed individually or in combination of a plurality of methods. That is, the adhesive composition in which the antireflection agent contained in the resin is removed by the method of precipitating and removing the antireflection agent may be further subjected to filtration to provide a method for removing the antireflection agent.

When the above-mentioned resin is reprecipitated (or precipitated) or when the resin is cleaned, the resin is filtered by a mesh filter having a uniform shape of snow. Then, a terpene solvent such as p-menthane, a petroleum solvent such as cyclohexane and decahydronaphthalene The resin may be recovered by dissolving in a solvent. When the adhesive composition is filtered to remove the anti-cracking agent, the solution obtained by filtration is used as an adhesive composition.

According to the method for producing an adhesive composition according to the present invention, since the antiglare agent contained in the adhesive composition is removed by the purification step, it is possible to remove the residue on the wafer when it is used for adhesion between the wafer and the support, Can be produced. In addition, it is possible to provide an adhesive composition which is used for adhesion between a wafer and a support of the wafer, and which prevents the occurrence of residues on the wafer when it is dissolved and cleaned with a solvent.

Further, a method for producing a laminated body in which a wafer and a support are adhered to each other by using an adhesive composition to be an object from which an anti-static agent is to be removed by the method for producing an adhesive composition according to the present invention and an adhesive composition according to the present invention, A method of forming an electrode for forming an electrode on a wafer, a peeling method for peeling a support from a wafer of the above laminate, and a cleaning method for cleaning a wafer on which a support is peeled are also a category of the present invention.

[Adhesive film]

The adhesive composition according to the present invention may be used in various forms depending on the application. For example, it is possible to use a method in which the adhesive layer is formed on a workpiece such as a semiconductor wafer while being in a liquid state, or the adhesive layer according to the present invention, that is, (Adhesive film method) in which the adhesive layer containing the adhesive composition of the present invention is formed and dried, and the film (adhesive film) is affixed to the workpiece for use.

As described above, the adhesive film of the present invention has an adhesive layer containing any one of the above adhesive compositions on a film.

The adhesive film may be used by further coating a protective film on the adhesive layer. In this case, the protective film on the adhesive layer is peeled off, the adhesive layer exposed on the workpiece is covered, and the film is peeled off from the adhesive layer, whereby the adhesive layer can be easily provided on the workpiece.

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

The above-mentioned film used in the production of the adhesive film is not limited as long as the adhesive layer formed on the film can be peeled off from the film and the release layer can be transferred onto a protective substrate or a wafer. For example, a flexible film made of a synthetic resin film such as polyethylene terephthalate, polyethylene, polypropylene, polycarbonate, and polyvinyl chloride having a thickness of 15 to 125 탆 can be used. It is preferable that the film is subjected to a release treatment so as to facilitate the transfer if necessary.

As a method of forming the adhesive layer on the film, a known method such as a method of applying a film thickness of 10 to 1000 mu m to the adhesive layer on the film is carried out according to the thickness and uniformity of the desired adhesive layer And a method of applying an adhesive composition.

When a protective film is used, the protective film is not limited as long as it can be peeled off from the adhesive layer. For example, a polyethylene terephthalate film, a polypropylene film and a polyethylene film are preferable. It is preferable that each protective film is coated with silicon or baked. This is because peeling from the adhesive layer is facilitated. The thickness of the protective film is not particularly limited, but is preferably 15 to 125 占 퐉. This is because the flexibility of the adhesive film having the protective film can be secured.

The method of using the adhesive film is not particularly limited. For example, when a protective film is used, the adhesive film is peeled off. Then, the adhesive layer exposed on the object to be processed is overlaid and the film is peeled from the back surface And a method in which the adhesive layer is thermally pressed on the surface of the workpiece by moving the heating roller. At this time, the protective film peeled off from the adhesive film can be stored and reused after being rolled up in roll form by a roller such as a winding roller in turn.

Example

[Preparation of adhesive composition]

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

Mw = 95,000, Mw / Mn = 1.9, m: n = 35: 65 (molar ratio) " (hereinafter referred to as COC A) manufactured by Mitsui Chemicals, Inc. and TOPAS (trade name) 8007X10 manufactured by Polyplastics Co., Mw = 100,000, Mw / Mn = 2.1, m: n = 80: 20 (molar ratio) "(hereinafter referred to as COC1) was used as the APEL (trade name) 8008T COC.

As the elastomer, HG252 (SEEPS-OH: polystyrene-poly (ethylene-ethylene / propylene) block-polystyrene terminal hydroxyl group denaturation), HG253 and Septon 8007 (SEBS: polystyrene- H1051 (SEBS, hydrogenated styrenic thermoplastic elastomer) and H1053 (SEBS, hydrogenated styrenic thermoplastic elastomer), which are available from Asahi Chemical Industry Co., Ltd., were used. In the present embodiment, "hydrogenation" means a polymer obtained by hydrogenating a double bond of a block copolymer of styrene and butadiene.

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

As the thermal polymerization inhibitor, "IRGANOX (trade name) 1010" manufactured by BASF was used. As the main solvent, decahydronaphthalene represented by the following formula (I) was used. In addition, butyl acetate was used as an addition 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. Next, a butyl acetate solution containing a thermal polymerization inhibitor was added to 100 parts by weight of the elastomer such that 1 part by weight of the thermal polymerization inhibitor and 45 parts by weight of butyl acetate were added. The thus obtained adhesive composition was filtered using a PTFE filter (manufactured by PALL) having a pore diameter of 1 mu m. The content (metal content) of the metal component derived from the antiglare agent in the obtained adhesive composition was measured by ICP-MS (product name: 7500cs, manufactured by Ajinut Technology Co., Ltd.).

Further, the effect of removing the anti-cracking agent was confirmed by measuring the turbidity of the adhesive composition. Turbidity was measured using SHIMADZU UV-3600.

The content of the metal component in the adhesive composition was expressed as the content of the metal component contained most in the adhesive composition among the ten elements of sodium, magnesium, aluminum, potassium, calcium, chromium, manganese, iron, nickel and copper. The metal content in the adhesive composition is shown in Table 2. The adhesive compositions were also obtained in the same manner as in Examples 2 to 4 and 6. In Examples 5 and 7, the removal of the antiglare agent was carried out by agitating and cleaning the adhesive resin component at 23 占 폚 with methanol in a state of being immersed in methanol, followed by filtration in the same manner. In Example 8, Except that decahydronaphthalene solution (concentration of 10w%) of an adhesive resin component was added dropwise to water / methanol (weight ratio 2/8) as a poor solvent to reprecipitate the adhesive resin component and filtration was carried out in the same manner 1, an adhesive composition was obtained. In Example 9, the removal of the antiglare agent was carried out in the same manner as in Example 1 except that the antireflection agent was collected from the adhesive resin component using a wind separator (jet separator (Jet Separator CFS) manufactured by ACO) An adhesive composition was obtained by the same procedure.

For Example 10, the adhesive resin component was immersed in propylene glycol monomethyl ether acetate at 35 占 폚 in an ultrasonic cleaner (manufactured by Aiwa Chemical Industry Co., Ltd., product number: AU-70C, oscillation output: 100 W, frequency: 28 kHz) , And the same procedure as in Example 1 was followed to obtain an adhesive composition.

After the above-mentioned predetermined treatment was applied to the resins of Examples 5 and 7 to 10, an adhesive composition was prepared using the resin after the treatment. Here, in Examples 5, 7, 9 and 10, the pellets were treated as they were. In Example 8, the pellets were dissolved once to perform reprecipitation treatment.

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

For Comparative Examples 1 to 4, an adhesive composition was obtained in the same manner as in Example 1 except that the adhesive composition was filtered to measure the metal content.

[Formation of adhesive layer]

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

On one support, a reaction layer for peeling the support and the wafer was prepared by next irradiating the laser with the laser. A fluorocarbon film (1 탆) was coated on a support plate (12-inch glass, thickness: 20 탆) by a CVD method using C ₄ F ₈ as a reaction gas under the conditions of a flow rate of 400 sccm, a pressure of 700 mTorr, a high frequency power of 2500 W, 700 mu m).

[Thinning treatment of laminate]

Thinning and photolithography of the wafer were performed using a laminate of a wafer and a support.

[Cleansing of adhesive layer]

A wafer and a support were separated by irradiating a 532 nm laser. The wafer with the support removed was spray-rinsed with p-menthol to remove the adhesive layer. The surface of the wafer after removing the adhesive layer was observed under a microscope to confirm the occurrence of the residue. The results are shown in Table 2. The results indicated by " o " in Table 2 indicate that the residue was not confirmed, the result indicated by " DELTA " indicates that a small or small amount of residue was identified, Is confirmed.

As shown in Table 2, no residues were formed on the wafer after cleaning in Examples, but in Comparative Example, residues of crystal products of 1 to 100 탆 were confirmed on the surface of the wafer after cleaning. In the comparative example, the turbidity of the adhesive composition also exceeded 5%.

The present invention is not limited to the above-described embodiments, but various modifications may be made within the scope of the claims, and embodiments in which the technical means disclosed in the embodiments are appropriately combined are also included in the technical scope of the present invention.

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

Claims (12)

And a purification step of removing an anti-sticking agent containing a metal component contained in the adhesive composition,
In the purification step, the solution containing the adhesive composition is filtered,
The deadlock agent is talc _{(Mg 3 Si 4 O 10 (} OH) 2), and dihydro talc _{(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); Wherein the adhesive composition comprises at least one selected from the group consisting of lead stearate, zinc stearate, calcium stearate, and stearate including magnesium stearate. ≪ / RTI > The method according to claim 1,
Characterized in that the content of the metal component derived from the antiglare agent contained in the adhesive composition in the refining step is 2 ppm or less based on the total solid weight of the adhesive composition. Gt; The method according to claim 1 or 2,
Characterized in that the adhesive composition contains a resin taken out from the resin solution after the resin is reprecipitated in a resin solution containing a resin forming the adhesive composition before the purification step, And adhering the support of the wafer. The method according to claim 1 or 2,
Characterized in that before the purification step, the resin forming the adhesive composition is washed in a solution, and then the resin taken out from the solution containing the resin is contained in the adhesive composition. ≪ / RTI > The method according to claim 1 or 2,
A method for manufacturing an adhesive composition for bonding a wafer and a support of the wafer, comprising collecting the antigelling agent contained in the adhesive composition by wind power selection before the purification step. The method according to claim 1 or 2,
Characterized in that before the purification step, the resin forming the adhesive composition is ultrasonically washed in a state immersed in a solution, and then the resin taken out from the solution containing the resin is contained in the adhesive composition. A method for manufacturing an adhesive composition for bonding a support of a wafer. The antisticking agent according to any one of claims 1 to 3, wherein the antistatic agent comprises only an antistatic agent containing a metal component, the content of the metal component derived from the antistatic agent is 10 ppb or more and 2 ppm or less,
The deadlock agent is talc _{(Mg 3 Si 4 O 10 (} OH) 2), and dihydro talc _{(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); Wherein the adhesive composition comprises at least one selected from the group consisting of lead stearate, zinc stearate, calcium stearate, and stearate including magnesium stearate. . The method of claim 7,
Wherein the wafer is provided in an electrode forming process after being bonded to the support. The method according to claim 7 or 8,
The adhesive composition for bonding a wafer and a support of the wafer, which comprises a hydrocarbon resin. The method according to claim 7 or 8,
An adhesive composition for bonding a wafer and a support of the wafer, comprising an elastomer. Characterized in that an adhesive layer composed of an adhesive composition for bonding the wafer of claim 7 or claim 8 to the support of the wafer is formed on the film. delete