KR20170066582A - Method for manufacturing temporary adhesive film, temporary adhesive film, layered body, layered body provided with device wafer, and temporary adhesive composition - Google Patents

Abstract

The present invention also provides a method for manufacturing an adhesion film which is excellent in peelability and can control the peeling interface, a adhesion film, a laminate, a laminate with a device wafer, and a composition for adhesion.
A method for producing an adherent film comprising a step of applying a layer of an adhesive composition on a support in a layer form and drying the adherend film, wherein the adherend composition comprises a compound having a fluorine atom, In the presence of fluorine atoms on the surface of the adhesive film by the X-ray photoelectron spectroscopy, the ratio A of the presence of fluorine atoms on the surface a of the adherent film opposite to the support and the ratio A of the fluorine atoms on the surface of the support film Wherein the atomic ratio B of the atom satisfies the relationship of the formula (1) and the atomic ratio A of the atom is 5 to 40%.
Equation (1); A / B? 1.3

Description

FIELD OF THE INVENTION The present invention relates to a composition for adhering an adhesive layer, a laminate for a device wafer, a laminate for a device wafer, a composition for adhering a device wafer,

The present invention relates to a method for producing an adhesive film, an adhesive film, a laminate, a laminate with a device wafer, and a composition for adhesion. More particularly, the present invention relates to a method for producing an adherent film, an adherent film, a laminate, a device wafer laminate, and a composition for adhering, which can be preferably used for manufacturing semiconductor devices and the like.

In a manufacturing process of a semiconductor device such as an IC (integrated circuit) or an LSI (large-scale integrated circuit), a plurality of IC chips are formed on a device wafer and are diced into individual pieces.

Further miniaturization and high integration of IC chips mounted on electronic devices are required due to the demand for further miniaturization and high performance of electronic devices, but the integration of integrated circuits in the plane direction of device wafers is approaching the limit.

Conventionally, a wire bonding method is widely known as an electrical connection method from an integrated circuit in an IC chip to an external terminal of an IC chip. In order to miniaturize the IC chip, a through hole is recently formed in the device wafer (A method of forming a so-called silicon through electrode (TSV)) is known in which a metal plug as an external terminal is connected to an integrated circuit so as to pass through the through hole. However, the method of forming the silicon penetrating electrode alone can not sufficiently cope with the recent demand for higher integration of the IC chip.

In view of the above, there is known a technique for improving the degree of integration per unit area of a device wafer by making the integrated circuit in the IC chip multilayered. However, since the thickness of the IC chip is increased in the multilayered structure of the integrated circuit, it is necessary to reduce the thickness of the member constituting the IC chip. As for such thinning of the member, for example, the thinning of the device wafer has been studied, leading to the miniaturization of the IC chip, and the manufacturing process of the through-hole of the device wafer in manufacturing the silicon through- In terms of being able, it is becoming promising. In addition, in semiconductor devices such as power devices and image sensors, thinning has been attempted from the viewpoints of improvement of the degree of integration and freedom of device structure.

As device wafers, those having a thickness of about 700 to 900 mu m are widely known. In recent years, attempts have been made to thin device wafer thicknesses to 200 mu m or less for the purpose of miniaturization of IC chips and the like.

However, a device wafer having a thickness of 200 m or less is extremely thin, and since a member for manufacturing a semiconductor device using such a substrate is very thin, additional processing is performed on such a member, It is difficult to stably support the member without damaging it.

In order to solve the above problems, there is a technique of temporarily fixing (adhering) a device wafer and a carrier substrate before thinning by an adhesive, grinding the back surface of the device wafer to make it thin and then removing the carrier substrate from the device wafer Is known.

Patent Document 1 discloses an adhesive sheet for semiconductor device production which comprises a base material and an adhesive layer containing a resin provided on one surface of the base material and which is adhered to a lead frame or a wiring board of a semiconductor device so as to be releasable, , And a fluorine-containing additive which is liquid at 25 占 폚.

Patent Document 2 discloses a resin composition comprising a cycloolefin polymer and a structure having at least one of a silicone structure, a fluorinated alkyl group structure, an alkenyl fluoride structure and an alkyl structure having at least 8 carbon atoms, a structure having a polyoxyalkylene structure, , The support and the substrate are tentatively fixed via a temporary fixing material comprising a compound having at least one structure out of the structure having at least one structure selected from the group consisting of

Patent Document 3 discloses that a device wafer and a support are adhered to each other by using an adhesive composition comprising an elastomer containing a styrene unit as a constituent unit of a main chain and a wax.

Patent Document 1: JP-A-2013-201403 Patent Document 2: JP-A-2013-241568 Patent Document 3: JP-A-2014-34632

When the device wafer and the carrier substrate are adhered to each other, there is a demand for a property that the device wafer and the carrier substrate can easily be released from the adhesion state.

Whether the adhesive film peels off at the interface between the device wafer and the adhesive film or peels off from the interface between the carrier substrate and the adhesive film is not constant when releasing the adhesive state between the device wafer and the carrier substrate, When the device wafer is peeled from the interface between the adhesive film and the device wafer or peeled off from the interface between the carrier substrate and the adhesive film, it is necessary to change the removal process of the adhesive film from the device wafer or the carrier substrate every time, . In addition, if the device wafer and the carrier substrate can control the peeling interface between the device wafer and the adhesive film, for example, the adhesive film is left on the side where the adhesive film is easily removed, and the adhesive state between the device wafer and the carrier substrate is released It is possible to efficiently remove the adhesive film from the device wafer or the carrier substrate after the adhesion is released.

In order to improve the peelability of the adhesive film from the device wafer or the carrier substrate, studies have been made to form a releasing layer by applying a releasing agent to the surface of the adherent film. However, in this method, Since the number of processes increases, the number of processes increases, and it is a problem to improve the throughput.

In addition, as described in Patent Documents 1 and 2, studies have also been made on compounding a fluorine atom-containing compound or the like in the adhesive composition.

However, in Patent Documents 1 and 2, there is no description or suggestion of controlling the peeling interface between the device wafer and the carrier substrate and the peeling-off film when releasing the adhesion state between the device wafer and the carrier substrate.

In addition, in the invention disclosed in Patent Document 3, the peelability was insufficient. Patent Document 3 discloses a technique in which a carrier base material provided with a plurality of holes penetrating in the thickness direction is used for the purpose of easily separating the device wafer and the carrier base material, or by absorbing light between the carrier base material and the device wafer (Reaction layer) having a property of being altered is interposed, but in this method, it is necessary to use a special carrier substrate.

SUMMARY OF THE INVENTION The present invention has been made in consideration of the above background, and provides a method for manufacturing an adhesive film which is excellent in peeling property and can control a peeling interface, an adhesive film, a laminate, a device wafer laminate, .

DISCLOSURE OF THE INVENTION The present inventors have intensively studied in order to solve the above problems and found that the above object can be achieved by adjusting the ratio of fluorine atoms present on the surface of the adhesive film. The present invention provides the following.

<1> A method for producing an adhesion film comprising a step of coating a support composition on a support in the form of a layer and drying the composition,

Wherein the adhesive composition comprises a compound having a fluorine atom,

The adhering film was evaluated by X-ray photoelectron spectroscopy of the surface of the adherent film, which was measured by irradiating a monochromated AlK? Line at 25 W to an analysis area range of 1400 m x 700 m on the surface of the adherent film, The presence ratio A of the fluorine atoms on the surface of the adherent film opposite to the support and the ratio B of the presence of the fluorine atoms on the surface of the adhesive film on the support side satisfy the following formula ), And the presence ratio A of fluorine atoms is 5 to 40%;

A / B? 1.3 ... (1)

A is the ratio A of the presence of fluorine atoms on the surface of the adhesive film opposite to the support,

B is the presence ratio B of fluorine atoms on the surface of the adhesive film on the support side.

<2> The adhesive film according to <1>, wherein the presence ratio A of the fluorine atom and the presence ratio B of the fluorine atom satisfy the relationship represented by the following formula (2) and the fluorine atom content ratio A is 10 to 30% A method for producing an adherent film described in Japanese Patent Application Laid-

A / B? 1.5 (2)

A is the ratio A of the presence of fluorine atoms on the surface of the adhesive film opposite to the support,

B is the presence ratio B of fluorine atoms on the surface of the adhesive film on the support side.

&Lt; 3 > The method for producing an adherent film according to < 1 > or < 2 >, wherein the compound having a fluorine atom has a hydrophilic group.

<4> The method for producing an adhesion film as described in any one of <1> to <3>, wherein the adhesive composition comprises at least one selected from a binder and a radical polymerizable compound.

&Lt; 5 > The method for producing an adherent film according to < 4 >, wherein the binder is a block copolymer.

&Lt; 6 > The method for producing an adhesion film as described in <4> or <5>, wherein the binder is a styrene block copolymer having one end or both ends of the styrene block.

&Lt; 7 > The method for producing a tackifier film according to any one of < 4 > to < 6 >, wherein the binder is a hydrogenation product of a block copolymer.

&Lt; 8 > The method for producing a tackifier film according to < 4 >, wherein the binder is an elastomer.

<9> The method for producing an adherent film according to <8>, wherein the elastomer comprises a repeating unit derived from styrene.

&Lt; 10 > A process for producing an adhesion film as described in <8> or <9>, wherein the elastomer is a hydrogenation product.

<11> The process for producing an adherent film according to any one of <8> to <10>, wherein the elastomer is a styrene block copolymer having one end or both ends of the styrene block.

<12> The elastomer comprises an elastomer A containing repeating units derived from styrene in a proportion of 10% by mass or more and 50% by mass or less based on the total repeating units and an elastomer A containing 50% by mass or more of repeating units derived from styrene , And the elastomer (B) contains, in a proportion of not more than 95 mass%, the elastomer (B).

&Lt; 13 > A process for producing an adherent film according to < 12 >, wherein a mass ratio of elastomer A and elastomer B is 5: 95 to 95: 5.

&Lt; 14 > The method for producing an adherent film according to < 4 >, wherein the radically polymerizable compound is a compound having two or more radically polymerizable groups.

<15> A process for producing an adherent film according to <4> or <14>, wherein the radical polymerizing compound has at least one partial structure represented by the following (P-1) to (P-4). However, * in the equation is a connecting hand.

[Chemical Formula 1]

Wherein the radical polymerizing compound is at least one compound selected from the group consisting of trimethylolpropolay (meth) acrylate, isocyanuric acid ethyleneoxide modified di (meth) acrylate, isocyanuric acid ethyleneoxide modified tri (meth) acrylate (Meth) acrylate, pentaerythritol tetra (meth) acrylate, dimethylol propane tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate The pressure-sensitive adhesive composition according to any one of <4>, <14> and <15>, wherein the pressure-sensitive adhesive layer is at least one selected from the group consisting of dipentaerythritol hexa (meth) acrylate and tetramethylolmethane tetra Gt;

<17> The adhesive composition according to any one of <1> to <16>, wherein the adhesive composition contains 0.03% by mass or more and less than 0.5% by mass of a fluorine atom-containing compound in the total solid content of the adhesive composition. (2).

<18> The method for producing an adhesion film according to any one of <1> to <17>, wherein the average film thickness of the adhesion film is 0.1 to 500 μm.

<19> An adhesion film comprising a compound having a fluorine atom,

The adhesive film is a single-layer film,

Was subjected to X-ray photoelectron spectroscopy on the surface of the adhesive film, which was measured by irradiating a monochromatic AlK? Line at 25 W to an analysis area of 1400 m x 700 m on the surface of the adhesive film, The abundance ratio is defined as the ratio of the presence A1 of the fluorine atoms on the one surface a of the adhesive film to the presence ratio B1 of the fluorine atoms on the surface b of the adhesive film opposite to the surface a, 11), and the presence ratio A1 of the fluorine atoms is 5 to 40%;

A1 / B1? 1.3  (11)

A1 is the ratio A1 of the presence of fluorine atoms on the surface a of the adhesive film,

B1 is the presence ratio B1 of fluorine atoms on the surface b of the adhesive film.

<20> The adhesive film according to <19>, wherein the presence ratio A1 of the fluorine atom and the presence ratio B1 of the fluorine atom satisfy the relation of the following formula (12) and the presence ratio A1 of the fluorine atom is 10 to 30% A tacky adhesive film described in Japanese Patent Laid-

A1 / B1≥1.5 ... (12)

A1 is the ratio A1 of the presence of fluorine atoms on the surface a of the adhesive film,

B1 is the presence ratio B1 of fluorine atoms on the surface b of the adhesive film.

<21> The adhesion film according to <19> or <20>, wherein the fluorine atom-containing compound has a hydrophilic group.

<22> The adhesive film according to any one of <19> to <21>, wherein the adhesive film comprises at least one selected from a binder and a radical polymerizable compound.

<23> The adhesion film according to any one of <19> to <22>, wherein the adhesion film contains a compound having a fluorine atom in a ratio of 0.03 mass% or more to less than 0.5 mass% in the total solid content of the adhesion film.

<24> An adhesive film obtained by the production method according to any one of <1> to <18> or an adhesive film described in any one of <19> to <23> &Lt; / RTI &gt;

<25> An adhesion film obtained by a manufacturing method described in any one of <1> to <18> or an adhesion film described in any one of <19> to <23> is provided between a carrier substrate and a device wafer, Wherein one surface of the adhesive film is in contact with the device surface of the device wafer and the other surface is in contact with the surface of the carrier substrate.

<26> The device wafer laminate according to <25>, wherein the area of the film surface of the adhesive film is smaller than the area of the substrate surface of the carrier substrate.

(C-200)? T? D when the diameter of the substrate surface of the carrier substrate is C m, the diameter of the substrate surface of the device wafer is D m, and the diameter of the film surface of the adhesive film is T m &Lt; / RTI >

The diameter of the substrate surface of the carrier substrate is _C m, the diameter of the substrate surface of the device wafer is _D m, the diameter of the film surface of the adhesive film on the side in contact with the carrier substrate is T _C m, Satisfies (C-200)? T _C > T _D ? _D when the diameter of the film surface of the device wafer is T _D μm.

<29> A composition for adhesion comprising a compound having a fluorine atom,

Wherein the fluorine atom-containing compound is contained in an amount of 0.03 mass% or more and less than 0.5 mass% in the total solid content of the adhesive composition.

<30> The adhesive composition according to <29>, wherein the compound having a fluorine atom has a hydrophilic group.

<31> The adhesive composition according to <29>, further comprising at least one selected from a binder and a radical polymerizable compound.

<32> The adhesive composition according to <31>, wherein the binder is an elastomer.

According to the present invention, it is made possible to provide a method for producing an adhesive layer, an adhesive layer, a laminate having a device wafer, and a composition for adhering the adhesive layer, which is excellent in peeling property and can control the peeling interface.

BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic view of an adherent film of the present invention. Fig.
2 is a schematic view of a first embodiment showing a manufacturing method of a semiconductor device.
3 is a schematic view of a second embodiment showing a manufacturing method of a semiconductor device.

Hereinafter, embodiments of the present invention will be described in detail.

In the notation of the group (atomic group) in the present specification, the notation in which substitution and non-substitution are not described includes those having a substituent and having a substituent. For example, the "alkyl group" includes not only an alkyl group having no substituent (an unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).

The term &quot; active ray &quot; or &quot; radiation &quot; in this specification includes, for example, visible light, ultraviolet light, far ultraviolet light, electron beam, X-ray and the like.

In the present specification, the term &quot; light &quot; means an actinic ray or radiation.

As used herein, the term &quot; exposure &quot; means not only exposure by deep ultraviolet rays such as mercury lamps, ultraviolet rays, and excimer lasers, X-rays, EUV light, etc., but also drawing by particle beams such as electron beams and ion beams It means.

In the present specification, the total solid content refers to the total mass of components excluding the solvent from the total composition of the composition.

As used herein, "(meth) acrylate" refers to acrylate and methacrylate, "(meth) acrylic" refers to acrylic and methacrylic, "(meth) acryloyl" Quot; and &quot; methacryloyl &quot;.

In the present specification, the weight average molecular weight and the number average molecular weight are defined as polystyrene reduced values by Gel Permeation Chromatography (GPC) measurement. In the present specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are measured by using, for example, HLC-8220 (manufactured by TOSOH CORPORATION) and using TSK Gel Super AWM-H 6.0 mm (inner diameter) × 15.0 cm) of 10 mmol / L lithium bromide NMP (N-methylpyrrolidinone) solution as an eluent.

In the present specification, the term "hydrophilic group" means a functional group not containing a hydrophilic group. The term &quot; hydrophilic group &quot; means a functional group exhibiting affinity with water.

In the embodiments described below, the members described in the drawings already referred to are denoted by the same reference numerals or signs in the drawings, thereby simplifying or omitting the description.

In the present specification, the viscosity can be measured using a B-type viscometer. As a method for measuring the viscosity, a value obtained by measuring the viscosity using a B-type viscometer (Visco Reid Advance, manufactured by FUN JAPAN) is used.

&Lt; Process for producing adhesive film &

A method for producing an adherent film of the present invention is a method for producing an adherent film including a step of applying a layer of an adhesive composition on a support in a layer form and drying,

Wherein the adhesive composition comprises a compound having a fluorine atom,

The adhesive film was evaluated by X-ray photoelectron spectroscopy of the surface of the adhesive film, which was measured by irradiating monochromated AlK? Line at 25 W to an analysis area of 1400 m x 700 m on the surface of the adhesive film, The presence ratio A of the fluorine atoms on the surface of the adhesive film opposite to the support and the presence ratio B of the fluorine atoms on the surface of the adhesive film on the support side satisfy the relation of the following formula (1) And the presence ratio A of fluorine atoms is 5 to 40%.

A / B? 1.3 (1)

A is the ratio A of the presence of fluorine atoms on the surface of the adhesive film opposite to the support,

B is the presence ratio B of fluorine atoms on the surface of the adhesive film on the support side.

In the present invention, the measurement conditions in the X-ray photoelectron spectroscopy are a temperature of 20 to 25 ° C and a pressure of 10 ^-8 Pa or less.

As a device of X-ray photoelectron spectroscopy, PHI Quantera SXM (manufactured by ULVAC, PA) can be used.

In the present invention, as a composition for adhesion, an adhesive film containing a fluorine atom-containing compound is prepared. The fluorine atom-containing compound generally has a property that it is difficult to exist in the inside of a film such as an adherent film or the like and is prone to deviate on both surfaces of the film. The inventors of the present invention have also found that a fluorine atom-containing compound has a property of being easily localized on the surface having a high hydrophobicity, and can be used as a layered composition containing a compound having a fluorine atom on a support It was thought that the fluorine atom-containing compound was localized on the surface of the adhesive film opposite to the support (hereinafter also referred to as the air-side interface), which is a surface with high hydrophobicity.

Therefore, according to the present invention, it is possible to obtain a fluorine-containing compound having a fluorine atom-containing ratio A and a fluorine atom-present ratio B, by simply applying a layer- It is possible to produce an adhesive film which satisfies the relationship of the above formula (1) and has a fluorine atom content ratio A of 10 to 40%.

Since the present adhesive film of the present invention satisfies the relationship of the presence ratio A of the fluorine atom and the presence ratio B of the fluorine atom in the formula (1), the adhesion between the carrier substrate and the device wafer Can be peeled off.

In addition, since the presence ratio A of the fluorine atoms at the air-side interface of the adhesive film is 10 to 40%, the carrier base and the device wafer can be peeled off with a small peeling force.

As described above, the fluorine atom-containing compound is less likely to be present in the inside of the film, has a tendency to be unevenly distributed on both surfaces of the film, and particularly has a property that it is prone to localization on the surface with high hydrophobicity. As a result, when the adhesive composition is applied onto the support, the fluorine atom-containing compound tends to be largely unevenly distributed on the air-side interface, which is a surface with high hydrophobicity. On the other hand, if the proportion of the fluorine atom-containing compound in the air-side interface increases, the hydrophobicity at the air-side interface decreases, and the fluorine atom-containing compound tends to be unevenly distributed on the surface of the support. It has been found that by adjusting the content of the fluorine-containing compound, the compound having fluorine atoms at the air-side interface of the adhesive film can be more easily localized. For example, by using a composition for adhesion which contains 0.03% by mass or more and less than 0.5% by mass of a fluorine atom-containing compound in the total solid content of the adhesive composition for bonding, fluorine atoms It is possible to make the compound having the urethane prepolymer more easily.

Hereinafter, the present invention will be described.

<< Composition for adhesion >>

<<< Compounds Containing Fluorine Atoms >>

The adhesive composition of the present invention includes a compound having a fluorine atom (also referred to as a fluorine compound).

The fluorine-containing compound is preferably contained in a proportion of 0.03 mass% or more and less than 0.5 mass% in the total solid content of the adhesive composition. The lower limit is more preferably 0.03 mass% or more, still more preferably 0.04 mass% or more, and still more preferably 0.05 mass% or more. The upper limit is more preferably less than 0.5 mass%, more preferably 0.4 mass% or less, and further preferably 0.2 mass% or less.

The fluorinated compound may contain a plurality of kinds, and in this case, it is preferable that the total amount satisfies the above range.

As described above, when the content of the fluorine compound is within the above range, it is possible to make the fluorine compound more easily localized on the air interface side of the adhesive film, and the presence ratio A of the fluorine atom and the ratio B of the fluorine atom, It is easy to manufacture an adhesive film satisfying the relationship of the above formula (1) and having a fluorine atom content ratio A of 10 to 40%.

As the fluorine compound, a liquid compound is preferable.

In the present invention, the liquid phase means a compound having fluidity at 25 캜, for example, a compound having a viscosity of 1 to 100,000 mPa 에서 at 25 캜.

The viscosity of the fluorine compound at 25 占 폚 is more preferably 10 to 20,000 mPa 占 퐏, and more preferably 100 to 15,000 mPa 占 퐏. If the viscosity of the fluorine compound is within the above range, the fluorine compound tends to be unevenly distributed on the surface of the adhesive layer.

In the present invention, the fluorinated compound may be any of oligomer and polymer compounds. It may also be a mixture of an oligomer and a polymer. Such a mixture may further contain a monomer. The fluorinated compound may be a monomer.

The fluorinated compound is preferably an oligomer, a polymer, and a mixture thereof from the viewpoint of heat resistance and the like. Examples of the oligomer and polymer include a radical polymer, a cationic polymer, and an anionic polymer, and any of them can be preferably used. Vinyl polymers are particularly preferred.

The weight average molecular weight of the fluorine compound is preferably 500 to 100000, more preferably 1000 to 50000, and still more preferably 2000 to 20,000.

In the present invention, the fluorinated compound is preferably a compound which does not denature at the time of the treatment of the substrate provided for adhesion. For example, a compound which can be present as a liquid phase even after heating at 250 DEG C or higher or after treating the substrate with various chemical solutions is preferable. As a specific example, it is preferable that the viscosity at 25 ° C after heating from 250 ° C to 25 ° C at a temperature elevation condition of 10 ° C / min from 25 ° C and then at 25 ° C is 1 to 100,000 mPa · s, mPa · s is more preferable, and 100 to 15,000 mPa · s is more preferable.

As the fluorine compound having such characteristics, it is preferable that it is a non-thermosetting compound having no reactive group. The term "reactive group" as used herein refers to the whole group which reacts at a heating temperature of 250 ° C., and includes a polymerizable group and a hydrolyzable group. Specific examples thereof include a metha (acryl) group, an epoxy group, and an isocyanate group.

As the non-thermosetting compound, a polymer compound having a non-polymerizable fluorine atom is preferable. As the polymer compound having a non-polymerizable fluorine atom, a polymer composed of one kind or two or more kinds of fluorine monofunctional monomers can be preferably used. More specifically, there may be mentioned tetrafluoroethylene, hexafluoropropene, tetrafluoroethylene oxide, hexafluoropropene oxide, perfluoroalkyl vinyl ether, chlorotrifluoroethylene, vinylidene fluoride, purple (Meth) acrylic acid ester containing at least one fluoroalkyl group, a fluoroalkyl group-containing (meth) acrylic acid ester, and a fluoroalkyl group-containing (meth) acrylate ester, or copolymers of these monomers, , At least one fluorinated resin selected from a copolymer of one or more fluorinated monofunctional monomers and chlorotrifluoroethylene, and the like.

The polymer compound having a non-polymerizable fluorine atom is preferably a (meth) acrylic resin containing a perfluoroalkyl group, which can be synthesized from a perfluoroalkyl group-containing (meth) acrylic acid ester.

The (meth) acrylic resin containing a perfluoroalkyl group may optionally be selected from copolymerized components in addition to the (meth) acrylic acid ester containing a perfluoroalkyl group, in view of releasability. Examples of the radical polymerizable compound capable of forming a copolymerization component include acrylic acid esters, methacrylic acid esters, N, N-2 substituted acrylamides, N, N-2 substituted methacrylamides, styrene, Acrylonitrile, acrylonitrile, methacrylonitrile, and the like.

More specifically, acrylic acid esters such as alkyl acrylates (preferably having 1 to 20 carbon atoms in the alkyl group) (e.g., methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, amyl acrylate , Ethylhexyl acrylate, octyl acrylate, t-octyl acrylate, chloroethyl acrylate, 2,2-dimethylhydroxypropyl acrylate, 5-hydroxypentyl acrylate, trimethylolpropane monoacrylate, (For example, phenyl acrylate), alkyl (meth) acrylates such as methyl acrylate, ethyl acrylate, butyl acrylate, Methacrylic acid esters such as methacrylate (the alkyl group preferably has 1 to 20 carbon atoms) (e.g., methyl methacrylate Acrylates such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, amyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, chlorobenzyl methacrylate, octyl methacrylate, 4-hydroxybutyl methacrylate, 5-hydroxypentyl methacrylate, 2,2-dimethyl-3-hydroxypropyl methacrylate, trimethylolpropane monomethacrylate, pentaerythritol monomethacrylate (Methacrylic acid, methacrylic acid, methacrylic acid, methacrylic acid, methacrylic acid, methacrylic acid and the like), glycidyl methacrylate, furfuryl methacrylate, tetrahydrofurfuryl methacrylate and the like), aryl methacrylate Etc.), styrenes such as styrene and alkylstyrene (e.g., methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, , Diethylstyrene, isopropylstyrene, butylstyrene, hexylstyrene, cyclohexylstyrene, decylstyrene, benzylstyrene, chloromethylstyrene, trifluoromethylstyrene, ethoxymethylstyrene, Acetoxymethylstyrene, etc.), alkoxystyrene (e.g., methoxystyrene, 4-methoxy-3-methylstyrene, dimethoxystyrene, etc.), halogensilane But are not limited to, styrene, styrene, dichlorostyrene, trichlorostyrene, tetrachlorostyrene, pentachlorostyrene, bromostyrene, dibromostyrene, iodostyrene, fluorostyrene, -Bromo-4-trifluoromethylstyrene, 4-fluoro-3-trifluoromethylstyrene, etc.), acrylonitrile, methacrylonitrile acrylic acid, and carboxylic acid Water (such as acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, p-carboxylstyrene, and metal salts and ammonium salt compounds of these acid groups). (Meth) acrylic acid esters having a hydrocarbon group of 1 to 24 carbon atoms are particularly preferred from the viewpoint of releasability, and examples thereof include methyl, butyl, 2-ethylhexyl, lauryl, stearyl, glycidyl And (meth) acrylates of higher alcohols such as 2-ethylhexyl, lauryl, stearyl and the like, especially acrylates, are preferred.

In the present invention, the fluorine compound preferably has a 10% thermal mass reduction temperature at 25 ° C or higher at 20 ° C / min, preferably 250 ° C or higher, more preferably 280 ° C or higher. The upper limit value is not particularly limited, but is preferably 1000 占 폚 or lower, for example, and more preferably 800 占 폚 or lower. According to this embodiment, it is easy to form an adhesion film having excellent heat resistance. The 10% thermal mass reduction temperature is a temperature at which a 10% reduction in the weight before measurement is measured by the thermogravimetric system under the above-mentioned elevated temperature condition under a nitrogen gas stream.

In the present invention, the fluorinated compound is preferably a compound containing a hydrophilic group and a fluorine atom. Examples of the hydrophilic group include an alkyl group and an aromatic group.

The alkyl group includes a straight chain alkyl group, a branched alkyl group and a cyclic alkyl group.

The number of carbon atoms of the straight chain alkyl group is preferably from 2 to 30, more preferably from 4 to 30, still more preferably from 6 to 30, and particularly preferably from 12 to 20.

The number of carbon atoms of the branched alkyl group is preferably from 3 to 30, more preferably from 4 to 30, still more preferably from 6 to 30, and particularly preferably from 12 to 20.

The cyclic alkyl group may be monocyclic or polycyclic. The number of carbon atoms of the cyclic alkyl group is preferably from 3 to 30, more preferably from 4 to 30, still more preferably from 6 to 30, and most preferably from 12 to 20.

Specific examples of the straight chain or branched alkyl group include straight or branched chain alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, An isopropyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a 1-ethylpentyl group and a 2-ethylhexyl group.

Specific examples of the cyclic alkyl group include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl, adamantyl, norbornyl, , A tricyclodecanyl group, a tetracyclodecanyl group, a camphoryl group, a dicyclohexyl group, and a pinenyl group.

The alkyl group may have a substituent. Examples of the substituent include a halogen atom, an alkoxy group, and an aromatic group.

Examples of the halogen atom include a chlorine atom, a fluorine atom, a bromine atom, and an iodine atom, and a fluorine atom is preferable.

The carbon number of the alkoxy group is preferably from 1 to 30, more preferably from 1 to 20, and even more preferably from 1 to 10. The alkoxy group is preferably straight-chain or branched.

The aromatic group may be monocyclic or polycyclic. The carbon number of the aromatic group is preferably from 6 to 20, more preferably from 6 to 14, and most preferably from 6 to 10.

The aromatic group may be monocyclic or polycyclic. The carbon number of the aromatic group is preferably from 6 to 20, more preferably from 6 to 14, and most preferably from 6 to 10. It is preferable that the aromatic group does not contain a hetero atom (for example, a nitrogen atom, an oxygen atom, a sulfur atom, etc.) in the element constituting the ring. Specific examples of the aromatic group include a benzene ring, a naphthalene ring, a pentane ring, an indene ring, an azuren ring, a heptane ring, an indene ring, a perylene ring, a pentacene ring, an acenaphthalene ring, a phenanthrene ring, an anthracene ring, a naphthacene ring, A thiophene ring, a fluorene ring, a biphenyl ring, a pyrrole ring, a furan ring, a thiophen ring, an imidazole ring, an oxazole ring, a thiazole ring, a pyridine ring, a pyrazine ring, a pyrimidine ring, , Indole ring, benzofuran ring, benzothiophen ring, isobenzofuran ring, quinoline ring, quinoline ring, phthalazine ring, naphthyridine ring, quinoxaline ring, quinoxazoline ring, isoquinoline ring, carbazole ring, phenan Triazine ring, acridine ring, phenanthroline ring, thianthrene ring, cromene ring, zanthen ring, phenoxathiine ring, phenothiazine ring, and phenanthrene ring.

The aromatic group may have the substituent described above.

The fluorine-containing compound may be a compound containing only one oil-soluble group, or may contain two or more species. The organic group may contain a fluorine atom. That is, the fluorinated compound may be a compound in which only the oil-containing group contains a fluorine atom. Further, in addition to a hydrophilic group, a compound having a fluorine atom-containing group (also referred to as a fluorine group) may be used. Preferably, it is a compound containing a mineral oil and a fluorine group.

When the fluorine compound is a compound having a hydrophilic group and a fluorine group, the hydrophilic group may or may not contain a fluorine atom, but it is preferable that the hydrophilic group does not contain a fluorine atom.

The fluorine-containing compound preferably has 2 or more, more preferably 6 to 80, groups having at least one lipophilic group in one molecule.

As the fluorine group, a known fluorine group can be used. For example, fluorinated alkyl groups, fluorinated alkylene groups and the like. Among the fluorine groups, those functioning as a lipophilic group are assumed to be included in lipophilic groups.

The carbon number of the fluorinated alkyl group is preferably from 1 to 30, more preferably from 1 to 20, and still more preferably from 1 to 15. The fluorine alkyl group may be linear, branched or cyclic. It may also have an ether bond. The fluorinated alkyl group may also be a perfluoroalkyl group in which all of the hydrogen atoms are substituted with fluorine atoms.

The fluorine-containing alkylene group preferably has 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, and more preferably 2 to 15 carbon atoms. The fluorine-containing alkylene group may be linear, branched or cyclic. It may also have an ether bond. The fluorinated alkylene group may be a perfluoroalkylene group in which all of the hydrogen atoms are substituted with fluorine atoms.

The fluorine compound preferably has a fluorine atom content of 1 to 90 mass%, more preferably 2 to 80 mass%, and still more preferably 5 to 70 mass%. When the fluorine content is in the above range, the releasability is excellent.

The content of fluorine atoms is defined as "{(the number of fluorine atoms in one molecule x the mass of fluorine atoms) / the mass of all atoms in one molecule} x 100".

Commercially available products may also be used as fluorine compounds. As the non-thermosetting compound, Teflon (registered trademark) (DuPont), Teflon (DuPont), Fluon (Asahi Glass Co.), Hyler (Solvay Solexis) Fluorine resins such as Hyalur (Solvay Solexis), Lumipro (Asahi Glass Co.), Arplus (Asahi Glass Co.), Sephrase Soft (Central Glass Co.), and Cefalcoat (Central Glass Co.) (Du Pont), Pombulin (Daitoku Tech), Demnum (Daikin Kogei), etc., which are trade names of SIFEL (Shinetsuga Kagaku Kogyo Co., Ltd.) Various fluorine oils including perfluoropolyether oils such as Surflon (for example, Surfron S243, AGC Seiyam Chemical Co., Ltd.), Dyepref FB Series such as Dyepref FB962 (Daikin Kogyo Co., Ltd.) Fluorine-containing mold release agents such as Megapak series (DIC) and the like.

F-251, F-471, F-553, F-554, F-555, and F-551 of Megapark series manufactured by DIC Co., F-566, F-567, F-568, F-571, R-40, R-41, F-556, F-557, F-558, F-559, F- R-43 and R-94, and 710F, 710FM, 710FS, 710FL, 730FL and 730LM of the Fotograph series manufactured by NEOS.

In the present invention, a fluorine-containing silane coupling agent may be used as the fluorine compound. As the fluorine-containing silane coupling agent, a non-halogeno-silane coupling agent is preferable, and a fluorine-containing alkoxysilane is particularly preferable. Commercially available products include OptuT DAC-HP and Optun DSX manufactured by Daikin Industries, Ltd.

<< Binder >>

The adhesive composition of the present invention preferably contains at least one kind selected from a binder and a radical polymerizable compound. The binder and the radical polymerizing compound may be used in combination, or may be used alone. First, the binder will be described.

In the present invention, any binder may be used.

The binder includes block copolymers, random copolymers and graft copolymers, and block copolymers are preferred. The block copolymer can suppress the flow of the adhesive composition during the heating process, so that adhesion can be maintained even during the heating process, and the effect that the peelability is not changed even after the heating process can be expected.

The type of the binder is not particularly limited and examples thereof include polystyrene copolymers, polyester copolymers, polyolefin copolymers, polyuretene copolymers, polyamide copolymers, polyacrylic copolymers, silicone copolymers, Based copolymer or the like can be used. In particular, a polystyrene-based copolymer, a polyester-based copolymer and a polyamide-based copolymer are preferable, and a polystyrene-based copolymer is more preferable from the viewpoint of heat resistance and releasability. Among them, the binder is preferably a block copolymer of styrene and other monomers, and a styrene block copolymer in which one terminal or both terminals is a styrene block is particularly preferable.

The binder is preferably a hydrogenated product of a block copolymer. If the binder is a hydrogenated material, the thermal stability and the storage stability are improved. Further, the peelability and the removability of the adhesive film after peeling can be improved. The hydrogenated product means a polymer in which a block copolymer is hydrogenated.

In the present invention, the binder is preferably an elastomer. By using an elastomer as the binder, it is possible to form an antistatic film with excellent adhesion by following the fine unevenness of the carrier substrate or the device wafer and by an appropriate anchoring effect. The elastomer may be used alone or in combination of two or more.

In the present specification, the elastomer refers to a polymer compound exhibiting elastic deformation. That is, when an external force is applied, it is defined as a polymer compound that has a property of being instantly deformed according to its external force and recovering its original shape in a short time when an external force is removed.

<<< Elastomer >>>

In the present invention, the weight average molecular weight of the elastomer is preferably 2,000 to 200,000, more preferably 10,000 to 200,000, and even more preferably 50,000 to 100,000. When the support substrate is in this range, even when the support substrate is peeled off from the device wafer and the residue of the elastomer remaining on the device wafer and / or the support substrate is removed, the solubility in the solvent is excellent, There is an advantage such as not leaving.

In the present invention, the elastomer is not particularly limited, and examples thereof include an elastomer (polystyrene elastomer) containing a repeating unit derived from styrene, a polyester elastomer, a polyolefin elastomer, a polyurethane elastomer, a polyamide elastomer, Acrylic elastomer, silicone-based elastomer, polyimide-based elastomer, and the like. In particular, a polystyrene-based elastomer, a polyester-based elastomer, and a polyamide-based elastomer are preferable, and a polystyrene-based elastomer is most preferable from the viewpoint of heat resistance and releasability.

In the present invention, the elastomer is preferably a hydrogenated product. Particularly, a hydrogenated product of a polystyrene type elastomer is preferable. When the elastomer is a hydrogenated material, thermal stability and storage stability are improved. Further, the peelability and the removability of the adhesive film after peeling can be improved. When the hydrogenated product of the polystyrenic elastomer is used, the above effect is remarkable. Further, the hydrogenated substance means a polymer in which the elastomer is hydrogenated.

In the present invention, the elastomer preferably has a 5% heat mass reduction temperature of 25 ° C or higher at 20 ° C / min of 250 ° C or higher, more preferably 300 ° C or higher, still more preferably 350 ° C or higher, And most preferably at least 400 ° C. The upper limit value is not particularly limited, but is preferably 1000 占 폚 or lower, for example, and more preferably 800 占 폚 or lower. According to this embodiment, it is easy to form an adhesion film having excellent heat resistance.

The elastomer of the present invention can be deformed up to 200% at a room temperature (20 ° C) with a small external force when the original size is set at 100%, and the elastomer can return to 130% or less in a short time when the external force is removed .

<<<< Polystyrene based elastomer >>>>

The polystyrene-based elastomer is not particularly limited and may be appropriately selected depending on the purpose. For example, styrene-butadiene-styrene block copolymer (SBS), styrene-isoprene-styrene block copolymer (SIS), styrene-ethylene-butylene-styrene block copolymer ), Styrene-butadiene-butylene-styrene copolymers (SBBS) and their hydrogenated products, styrene-ethylene-butylene styrene block copolymer (SEBS), styrene-ethylene-propylene-styrene Block copolymer (SEPS), styrene-ethylene-ethylene-propylene-styrene block copolymer, and the like.

The content of the styrene-derived repeating unit in the polystyrene-based elastomer is preferably from 10 to 90% by mass. From the viewpoint of releasability, the lower limit value is preferably 25% by mass or more, more preferably 51% by mass or more.

In the present invention, the polystyrene-based elastomer comprises an elastomer A containing repeating units derived from styrene in a proportion of 10% by mass or more and 50% by mass or less in the total repeating units and 50% by mass or less of styrene- It is also preferable to use a combination of the elastomer B containing more than 95% by mass and not more than 95% by mass. By using the elastomer A and the elastomer B in combination, the flatness of the polished surface of the base material (hereinafter also referred to as flat polishability) is good and the occurrence of warpage of the base material after polishing can be effectively suppressed, with excellent peelability. The mechanism by which such an effect can be obtained is presumed to be as follows.

That is, since elastomer A is a relatively soft material, it is easy to form an adhesion film having elasticity. Thus, when a laminate of a substrate and a support is produced using the adhesive composition of the present invention and the substrate is polished to form a thin film, even when the pressure at the time of polishing is locally applied, the adhesive film is elastically deformed, It is easy to return to the shape. As a result, excellent flat polishing performance can be obtained. Also, even if the laminated body after polishing is subjected to heat treatment and then cooled, the internal stress generated at the time of cooling can be alleviated by the adhesive film, and occurrence of warpage can be effectively suppressed.

Further, since the elastomer B is a relatively hard material, by including the elastomer B, it is possible to produce an adhesion film excellent in peelability.

The elastomer A preferably contains 13 to 45 mass%, more preferably 15 to 40 mass%, of the repeating units derived from styrene in the total repeating units. In this embodiment, more excellent flat polishing performance can be obtained. Further, occurrence of warping of the base material after polishing can be effectively suppressed.

The hardness of the elastomer A is preferably from 20 to 82, more preferably from 60 to 79. The hardness is a value measured with a Type A durometer according to the method of JIS K6253.

The elastomer B preferably contains 55 to 90 mass%, more preferably 60 to 80 mass%, of the styrene-derived repeating unit in the total repeating units. According to this embodiment, the peelability can be improved more effectively.

The hardness of the elastomer B is preferably 83 to 100, more preferably 90 to 99. [

The mass ratio of the elastomer A and the elastomer B is preferably 5:95 to 95: 5, more preferably 10:90 to 80:20, and more preferably 15:85 to 60:40 in terms of the mass ratio of the elastomer A and the elastomer B. And most preferably 25 to 75: 60 to 40. Within the above range, the above-mentioned effect can be obtained more effectively.

The polystyrene-based elastomer is preferably a block copolymer of styrene and other monomers, more preferably a block copolymer in which one terminal or both terminals are styrene blocks, and particularly preferably both terminals are styrene blocks. When both ends of the polystyrene-based elastomer are made of styrene block (repeating unit derived from styrene), the heat resistance tends to be further improved. This is because the repeating unit derived from styrene having high heat resistance is present at the terminal. Particularly, since the block portion of the repeating unit derived from styrene is a reactive polystyrene-based hard block, it is preferable because heat resistance and chemical resistance tend to be better. When these are used as a block copolymer, it is considered that phase separation is performed between the hard block and the soft block at 200 캜 or higher. It is considered that the shape of the phase separation contributes to suppression of the generation of irregularities on the surface of the device wafer. Further, such an elastomer is more preferable in terms of solubility in a solvent and resistance to a resist solvent.

In addition, if the polystyrene-based elastomer is a hydrogenated product, stability against heat is improved, and deterioration such as decomposition or polymerization is hardly caused. And is more preferable in view of solubility in solvents and resistance to resist solvents.

The amount of the unsaturated double bond of the polystyrene-based elastomer is preferably less than 15 mmol, more preferably less than 5 mmol, and most preferably less than 0.5 mmol, per 1 g of the polystyrene-based elastomer from the viewpoint of releasability. The amount of the unsaturated double bond referred to herein does not include an unsaturated double bond in the benzene ring derived from styrene. The amount of unsaturated double bonds can be calculated by NMR (nuclear magnetic resonance) measurement.

In the present specification, the "repeating unit derived from styrene" is a structural unit derived from styrene contained in the polymer when the styrene or styrene derivative is polymerized, and may have a substituent. Examples of the styrene derivative include? -Methylstyrene, 3-methylstyrene, 4-propylstyrene and 4-cyclohexylstyrene. 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.

Examples of commercially available polystyrene elastomers include toughprene A, toughprene 125, toughprene 126S, solfrene T, asaprene T-411, asaprene T-432, asaprene T-437, Toughtech H1052, Tuftec H1052, Tuftec M1943, Tuftec M1911, Tuftec H1041, Tuftec MP10, Tuftec M1913, Tuftec H1051, Tuftec H1053, Tuftec H1052, Elastomer AR-850C, elastomer AR-830C, elastomer AR860C, elastomer AR-875C, elastomer AR-885C, elastomer (trade name: Elastomer AR-SC-15, elastomer AR-SC-15, elastomer AR-SC-15, elastomer AR-SC-5, elastomer AR- -45, Elastomer AR-720, Elastomer AR-741, Elastomer AR-731, Elastomer AR-750, Elastomer AR- Elastomer AR-FL-85N, elastomer AR-FL-60N, elastomer AR-1050, elastomer AR-1060, elastomer AR-760, elastomer AR- 1040 (Aaron Gassée), Creighton D1111, Creighton D1113, Creighton D1114, Creighton D1117, Creighton D1119, Creighton D1124, Creighton D1126, Creayton D1161, Creayton D1162, Creayton D1163, Creighton D1164 , Kraton D1165, Kraton D1183, Kraton D1193, Kraton DX406, Kraton D4141, Kraton D4150, Kraton D4153, Kraton D4158, Kraton D4270, Kraton D4271, Kraton D4433, Kraton D1170, Kr Creighton D1171, Creighton D1173, Creighton D1153, Creayt D1152, Creighton D1153, Creighton D1124, Creighton D1101, Creighton D1102, Creayton D1116, Creayton D1118, Creayton D1133, Creayton D1152, , Creighton D1155, Creighton D1184, Creighton D1186, Creighton D1189, Creighton D1191, Creighton D1192, Creighton DX405, Creighton DX408, Creayton DX410, Creayton DX414, Creayton DX415, Creayton A1535, Creayton A1536, Creighton FG1901 , Kraton FG1924, Kraton G1640, Kraton G1641, Kraton G1642, Kraton G1643, Kraton G1645, Kraton G1633, Kraton G1650, Kraton G1651, Kraton G1652, Kraton G1654, Kraton G1657, Kr (Manufactured by Kraton), TR2000, TR2001, TR2003, TR2250, Kraton G1660, Kraton G1726, Kraton G1701, Kraton G1702, Kraton G1730, Kraton G1750, Kraton G1765, , TR2500, TR2601, TR2630, TR2787, TR2827, TR1086, TR1600, SIS5002, SIS5200, SIS5250, SIS5405, SIS5505, Dynaron 6100P, Dynaron 4600P, Dynaron 6200P, Dynaron 4630P, Dynaron 8601P, Dynaron 8630P, Ron 8600P, Dynalon 8903P, DENARON 1320P, DYNARON 1320P, DYNARON 2324P, DYNARON 9901P (manufactured by JSR Corporation), Denka STR series (manufactured by Denki Kagaku Kogyo K.K.), Quintex 3520, Quintex 3433N, Quintax 3421, (Manufactured by Sumitomo Chemical Co., Ltd.), Lavalon series (manufactured by Mitsubishi Kagaku K.K.), Septon 1001, Septon 8004, Septon 4033, Nippon Kasei Kogyo Co., The following examples are provided to illustrate the present invention. Examples of the present invention include, but are not limited to, Septon 2104, Septon 8007, Septon 2007, Septon 2004, Septon 2063, Septon HG 252, Septon 8076, Septon 2002, Septon 1020, Septon 8104, Septon 2005, Septon 2006, Septon 4055, Septon 4044, Septon 4077, (Manufactured by Sumitomo Bakelite Co., Ltd.), Rheostomer (manufactured by Sumitomo Bakelite Co., Ltd.), Acromic acid (manufactured by Sumitomo Bakelite Co., Ltd.), Sephadex V9461, Septon V9475, Septon V9827, HiBra 7311, HiBra 7125, HiBra 5127, HiBra 5125 Manufactured by Riken Vinyl Corporation), and the like.

<<<< Polyester elastomer >>>>

The polyester-based elastomer is not particularly limited and may be appropriately selected depending on the purpose. For example, those obtained by polycondensation of a dicarboxylic acid or a derivative thereof with a diol compound or a derivative thereof.

Examples of the dicarboxylic acid include aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid and naphthalenedicarboxylic acid, aromatic dicarboxylic acids in which the hydrogen atoms of the aromatic nuclei are substituted with methyl, ethyl, phenyl and the like, adipic acid, Aliphatic dicarboxylic acids having 2 to 20 carbon atoms such as dicarboxylic acid, and alicyclic dicarboxylic acids such as cyclohexane dicarboxylic acid. These may be used alone or in combination of two or more.

Examples of the diol compounds include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,10-decanediol, , Alicyclic diols such as 4-cyclohexane diol, alicyclic diols, and divalent phenols represented by the following structural formula.

(2)

^Wherein Y ^DO represents any one of an alkylene group of 1 to 10 carbon atoms, a cycloalkylene group of 4 to 8 carbon atoms, -O-, -S-, and -SO ₂ - Represents a direct bond (single bond) between rings. R ^DO1 and R ^DO2 each independently represent a halogen atom or an alkyl group having 1 to 12 carbon atoms. p ^do1 and p ^do2 each independently represent an integer of 0 to 4, and n ^do1 represents 0 or 1;

Specific examples of the polyester elastomer include bisphenol A, bis- (4-hydroxyphenyl) methane, bis- (4-hydroxy-3-methylphenyl) propane and resorcin. These may be used alone or in combination of two or more.

As the polyester elastomer, an aromatic polyester (e.g., polybutylene terephthalate) portion as a hard segment component and an aliphatic polyester (e.g., a polytetramethylene glycol) portion as a soft segment component One multi-block copolymer may be used. As the multi-block copolymer, various grades may be cited depending on the kind, ratio, and molecular weight of the hard segment and the soft segment. Specific examples thereof include Hytrel (manufactured by Du Pont-Toray Co., Ltd.), Pelprene (manufactured by Toyobo Co., Ltd.), Primaloy (manufactured by Mitsubishi Kagaku), Nuberan Manufactured by Hitachi Kasei Kogyo Co., Ltd.).

<<<< Polyolefinic Elastomer >>>>

The polyolefin elastomer is not particularly limited and may be appropriately selected depending on the purpose. Examples of the copolymer include copolymers of C2-C20? -Olefins such as ethylene, propylene, 1-butene, 1-hexene and 4-methyl-pentene. Examples thereof include ethylene-propylene copolymer (EPR), ethylene-propylene-diene copolymer (EPDM) and the like. The non-conjugated dienes having 2 to 20 carbon atoms such as dicyclopentadiene, 1,4-hexadiene, cyclooctadiene, methylene norbornene, ethylidene norbornene, butadiene, and isoprene, Olefin copolymers, and the like. Further, carboxy modified nitrile rubber obtained by copolymerizing methacrylic acid with a butadiene-acrylonitrile copolymer may be mentioned. Specific examples include ethylene /? - olefin copolymer rubber, ethylene /? - olefin / non-conjugated diene copolymer rubber, propylene /? - olefin copolymer rubber, and butene /? - olefin copolymer rubber.

(Manufactured by Mitsui Chemicals, Inc.), Thermolun (Mitsubishi Kagaku Co., Ltd.), EXACT (Exxugagucu), ENGAGE (manufactured by Dow Chemical), S-pollex (manufactured by Sumitomo Chemical Co., Sarlink (Toyo Bosje), Newcorn (Nippon Polypropylene), EXCELINK (manufactured by JSR), and the like.

<<<< Polyurethane-based elastomer >>>>

The polyurethane-based elastomer is not particularly limited and may be appropriately selected according to the purpose. For example, an elastomer containing a structural unit of a soft segment composed of a hard segment composed of low molecular weight glycol and diisocyanate and a polymer (long chain) diol and diisocyanate, and the like can be given.

Examples of the polymer (long chain) diol include polypropylene glycol, polytetramethylene oxide, poly (1,4-butylene adipate), poly (ethylene 1,4-butylene adipate), polycaprolactone, poly (1,6-hexylene carbonate), and poly (1,6-hexylene-neopentylene adipate). The number average molecular weight of the polymer (long chain) diol is preferably from 500 to 10,000.

As a low molecular weight glycol, short chain diols such as ethylene glycol, propylene glycol, 1,4-butanediol, and bisphenol A can be used. The number-average molecular weight of the short-chain diol is preferably 48 to 500.

Examples of commercially available products of the polyurethane-based elastomer include PANDEX T-2185, T-2983N (manufactured by DIC Corporation), Miractoran (manufactured by Nippon Miraclast), ELASTOLAN (manufactured by BASF) (Manufactured by Dainichiseika Chemical Co., Ltd.), Peltan (manufactured by Dow Chemical Co.), iron rubber (manufactured by NOK Corporation), and Mobil Lon (manufactured by Nisshinbo Chemical Co., Ltd.).

<<<< Polyamide elastomer >>>>

The polyamide-based elastomer is not particularly limited and may be appropriately selected depending on the purpose. For example, a polyamide such as polyamide-6, 11, 12 or the like may be used for a hard segment and a polyether and / or polyester such as polyoxyethylene, polyoxypropylene, and polytetramethylene glycol may be used as a soft segment And the like. This elastomer is roughly classified into two types, a polyether block amide type and a polyetherester block amide type.

As a commercial product, UBE polyamide elastomer, UBESTA XPA (manufactured by Ube Gosan Co., Ltd.), diamide (manufactured by Daicel Ebonic Co., Ltd.), PEBAX (manufactured by ARKEMA) PAA-200, PA-201, TPAE-12, TPAE-12, and PAA-200 are commercially available from Mitsubishi Chemical Co., 32, polyester amide TPAE-617, and TPAE-617C (manufactured by T & K TOKA).

<<<< Polyacrylic elastomer >>>>

The polyacrylic elastomer is not particularly limited and may be appropriately selected depending on the purpose. For example, acrylic acid esters such as ethyl acrylate, butyl acrylate, methoxyethyl acrylate, and ethoxyethyl acrylate as main components, acrylic esters such as glycidyl methacrylate, allyl glycidyl ether, etc. . And those obtained by copolymerizing acrylonitrile and crosslinking point monomers such as ethylene. Specific examples include acrylonitrile-butyl acrylate copolymer, acrylonitrile-butyl acrylate-ethyl acrylate copolymer, acrylonitrile-butyl acrylate-glycidyl methacrylate copolymer, and the like. .

<<<< Silicone Elastomer >>>>

The silicone-based elastomer is not particularly limited and may be appropriately selected depending on the purpose. Examples thereof include polydimethylsiloxane-based, polymethylphenylsiloxane-based, and polydiphenylsiloxane, which are mainly composed of organopolysiloxane. Specific examples of commercially available products include KE series (manufactured by Shin-Etsu Chemical Co., Ltd.), SE series, CY series, and SH series (manufactured by Toray Dow Corning Silicone Co., Ltd.).

<<<< Other elastomers >>>>

In the present invention, a rubber-modified epoxy resin (epoxy-based elastomer) can be used as the elastomer. Examples of the epoxy-based elastomer include epoxy resins of a part or all of bisphenol F type epoxy resin, bisphenol A type epoxy resin, salicylaldehyde type epoxy resin, phenol novolak type epoxy resin or cresol novolak type epoxy resin, Carboxylic acid modified form, butadiene-acrylonitrile rubber, and terminal amino-modified silicone rubber.

<<< Other Polymer Compound >>>

In the present invention, as the binder, a polymer compound other than the above-described elastomer (also referred to as another polymer compound) can be used. The other polymer compound may be used alone or in combination of two or more.

Specific examples of other polymer compounds include hydrocarbon resins, novolac resins, phenol resins, epoxy resins, melamine resins, urea resins, unsaturated polyester resins, alkyd resins, polyamide resins, polyimide resins, polyamideimide resins , Polybenzimidazole resin, polybenzoxazole resin, polyvinyl chloride resin, polyvinyl acetate resin, polyacetal resin, polycarbonate resin, polyphenylene ether resin, polystyrene terephthalate resin, polyethylene terephthalate resin, Polyphenylene sulfide resin, polysulfone resin, polyethersulfone resin, polyarylate resin, polyetheretherketone resin, and the like. Among them, a hydrocarbon resin, a polyimide resin, and a polycarbonate resin are preferable, and a hydrocarbon resin is more preferable.

In the present invention, those containing a fluorine atom can be used as the binder, but it is preferable that a binder containing a fluorine atom (hereinafter also referred to as a fluorine-based binder) is substantially not included. In the case where the fluorine-based binder is not substantially contained, the content of the fluorine-based binder is preferably 0.1% by mass or less, more preferably 0.05% by mass or less, relative to the total mass of the binder, .

<<<< Hydrocarbon resin >>>>

In the present invention, any hydrocarbon resin may be used.

A hydrocarbon resin basically means a resin composed only of carbon atoms and hydrogen atoms. However, if the basic skeleton is a hydrocarbon resin, it may contain other atoms as side chains. That is, when a functional group other than a hydrocarbon group is directly bonded to a main chain such as an acrylic resin, a polyvinyl alcohol resin, a polyvinyl acetal resin, and a polyvinyl pyrrolidone resin to a hydrocarbon resin composed only of carbon atoms and hydrogen atoms In this case, the content of the repeating unit in which the hydrocarbon group is directly bonded to the main chain is preferably 30 mol% or more with respect to the total repeating units of the resin.

Examples of hydrocarbon resins conforming to the above conditions include terpene resins, terpene phenol resins, modified terpene resins, hydrogenated terpene resins, hydrogenated terpenephenol resins, rosins, rosin esters, hydrogenated rosins, hydrogenated rosin esters, An aliphatic petroleum resin, an aromatic petroleum resin, a hydrogenated petroleum resin, a modified petroleum resin, an alicyclic petroleum resin, a coumarone petroleum resin, an indene petroleum resin, a polystyrene -Olefin polymers (e.g., methylpentene copolymers), and cycloolefin polymers (e.g., norbornene copolymers, dicyclopentadiene copolymers, tetracyclododecene copolymers) .

The hydrocarbon resin is preferably a terpene resin, a rosin, a petroleum resin, a hydrogenated rosin, a polymerized rosin, an olefin polymer, or a cycloolefin polymer, more preferably a terpene resin, a rosin, an olefin polymer, or a cycloolefin polymer More preferably a terpene resin, a rosin, an olefin polymer, or a cycloolefin polymer, more preferably a terpene resin, a rosin, a cycloolefin polymer, or an olefin polymer, particularly preferably a cycloolefin polymer.

Examples of the cycloolefin polymer include norbornene polymers, polymers of monocyclic cycloolefins, polymers of cyclic conjugated dienes, vinyl alicyclic hydrocarbon polymers, and hydrides of these polymers. Preferable examples of the cycloolefin polymer include an addition (co) polymer containing at least one repeating unit represented by the following general formula (II), and a copolymer comprising at least one repeating unit represented by the general formula (I) (Co) polymer. Another preferred example of the cycloolefin polymer is a ring-opening (co) polymer containing at least one cyclic repeating unit represented by the general formula (III).

(3)

In the formula, m represents an integer of 0 to 4. R ¹ to R ⁶ each represent a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms; X ¹ to X ³ and Y ¹ to Y ³ each represent a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, (CH ₂ ) n COOR ¹¹ , - (CH ₂ ) n OCOR ¹² , - (CH ₂ ) nNCO, - (CH ₂ ) nNO ₂ , - (CH _{2) nCN, - (CH 2} ) nCONR 13 R 14, - (CH 2) nNR 15 R 16, - (CH 2) nOZ, - (CH 2) nW, or X ¹ and Y ^1, X ² and Y ² , Or (-CO) ₂ O, (-CO) ₂ NR ¹⁷ composed of X ³ and Y ³ . Each of R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ and R ¹⁷ is a hydrogen atom or a hydrocarbon group (preferably a hydrocarbon group having 1 to 20 carbon atoms), Z is a hydrocarbon group W represents SiR ¹⁸ _p D _{3 -p} (R ¹⁸ represents a hydrocarbon group of 1 to 10 carbon atoms, D represents a halogen atom, -OCOR ¹⁸ or -OR ¹⁸ , and p represents an integer of 0 to 3). n represents an integer of 0 to 10;

The norbornene polymer is disclosed in, for example, Japanese Unexamined Patent Application Publication No. 10-7732, Japanese Unexamined Patent Publication No. 2002-504184, US2004 / 229157A1, and WO2004 / 070463A1. The norbornene polymer can be obtained by addition polymerization of norbornene polycyclic unsaturated compounds. If necessary, norbornene polycyclic unsaturated compounds and ethylene, propylene, butene; Conjugated dienes such as butadiene, isoprene; And non-conjugated dienes such as ethylidene norbornene may be addition polymerized. This norbornene polymer is commercially available from Mitsui Chemicals, Inc. under the trade name APELPEL and has a glass transition temperature (Tg) of, for example, APL8008T (Tg70 DEG C), APL6013T (Tg125 DEG C) or APL6015T Of grade. Pellets such as TOPAS 8007, 5013, 6013 and 6015 are commercially available from Polyplastics Co., Ltd. Also Appear3000 is being released from Ferrania.

The hydrides of the norbornene-based polymers are disclosed in JP-A-1-240517, JP-A-7-196736, JP-A-60-26024, JP-A-62-19801, As disclosed in, for example, Japanese Patent Application Laid-Open No. 2003-1159767 or Japanese Patent Application Laid-Open No. 2004-309979, by subjecting a polycyclic unsaturated compound to addition polymerization or metathesis ring-opening polymerization, followed by hydrogenation.

In the general formula (III), R ⁵ and R ⁶ are preferably a hydrogen atom or a methyl group, and X ³ and Y ³ are preferably a hydrogen atom, and other groups are appropriately selected. This norbornene polymer is commercially available under the trade name of Arton G or Aton F from JSR Corporation and Zeonor ZF14, ZF16, Zeonex 250, 280, and 480R, and they can be used.

<<<< Polyimide resin >>>>

As the polyimide resin, those obtained by condensation reaction of tetracarboxylic acid dianhydride and diamine by a known method can be used.

As a known method, for example, a method of dehydrating and cyclizing a polyamic acid obtained by mixing tetracarboxylic dianhydride and diamine in approximately equimolar mixing in an organic solvent at a reaction temperature of 80 ° C or lower, and the like can be given. Here, approximately equimolar means that the molar ratio of tetracarboxylic acid dianhydride to diamine is in the vicinity of 1: 1. If necessary, the composition ratio of the tetracarboxylic dianhydride and the diamine may be adjusted so that the total amount of the diamine is from 0.5 to 2.0 moles per 1.0 mole of the tetracarboxylic acid dianhydride. The weight average molecular weight of the polyimide resin can be adjusted by adjusting the composition ratio of tetracarboxylic dianhydride and diamine within the above range.

Examples of the tetracarboxylic acid dianhydride include, but are not limited to, pyromellitic dianhydride, 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, 2,2', 3,3'- Bis (2,3-dicarboxyphenyl) propane dianhydride, 1,1-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2- Bis (3,4-dicarboxyphenyl) ethane dianhydride, bis (2,3-dicarboxyphenyl) methane dianhydride, bis (3,4 (3,4-dicarboxyphenyl) sulfone dianhydride, 3,4,9,10-perylene tetracarboxylic acid dianhydride, bis (3,4-dicarboxyphenyl) ether Dianhydride, benzene-1,2,3,4-tetracarboxylic acid dianhydride, 3,4,3 ', 4'-benzophenone tetracarboxylic acid dianhydride, 2,3,2', 3'-benzophenone tetracarboxylic acid dianhydride Water, 2,3,3 ', 4'-benzophenone tetracarboxylic acid imine Water, 1,2,5,6-naphthalenetetracarboxylic acid dianhydride, 1,4,5,8-naphthalenetetracarboxylic acid dianhydride, 2,3,6,7-naphthalenetetracarboxylic acid dianhydride, 1,2,4- 5-naphthalenetetracarboxylic acid dianhydride, 2,6-dichloronaphthalene-1,4,5,8-tetracarboxylic acid dianhydride, 2,7-dichloronaphthalene-1,4,5,8-tetracarboxylic acid dianhydride, 2,3,6,7-tetrachloronaphthalene-1,4,5,8-tetracarboxylic acid dianhydride, phenanthrene-1,8,9,10-tetracarboxylic acid dianhydride, pyrazine-2,3,5,6 -Tetracarboxylic acid dianhydride, thiophene-2,3,5,6-tetracarboxylic acid dianhydride, 2,3,3 ', 4'-biphenyltetracarboxylic acid dianhydride, 3,4,3', 4'- (3,4-dicarboxyphenyl) dimethylsilane dianhydride, bis (3,4-dicarboxyphenyl) diisocyanate dianhydride, 2,3,4'- Methylphenylsilane dianhydride, bis (3,4-dicarboxyphenyl) diphenylsilane (3,4-dicarboxyphenyldimethylsilyl) benzene dianhydride, 1,3-bis (3,4-dicarboxyphenyl) -1,1,3,3-tetramethyl di Cyclohexane dianhydride, p-phenylene bis (trimellitate anhydride), ethylene tetracarboxylic acid dianhydride, 1,2,3,4-butane tetracarboxylic acid dianhydride, decahydronaphthalene-1,4,5,8 -Tetracarboxylic acid dianhydride, 4,8-dimethyl-1,2,3,5,6,7-hexahydronaphthalene-1,2,5,6-tetracarboxylic acid dianhydride, cyclopentane- Tetracarboxylic acid dianhydride, pyrrolidine-2,3,4,5-tetracarboxylic acid dianhydride, 1,2,3,4-cyclobutante tetracarboxylic acid dianhydride, bis (exo- bicyclo [2 , 2,1 heptane-2,3-dicarboxylic acid dianhydride, bicyclo- [2,2,2] -oct-7-ene-2,3,5,6-tetracarboxylic acid dianhydride, 2,2 Bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2, -bis [4- (3,4-dicarboxyphenyl) Phenyl] propane dianhydride, 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride, 2,2-bis [4- (3,4-dicarboxyphenoxy) diphenyl sulfide dianhydride, 1,4-bis (2-hydroxyhexafluoroisopropyl) benzene bis (trimellitic anhydride) (2-hydroxyhexafluoroisopropyl) benzene bis (trimellitic anhydride), 5- (2,5-dioxotetrahydrofuryl) -3-methyl- Hexene-1,2-dicarboxylic acid dianhydride, tetrahydrofuran-2,3,4,5-tetracarboxylic dianhydride, 4,4 ', -oxydiphthalic dianhydride, 1,2- (ethylene) bis (Trimellitate anhydride), 1,4- (tetramethylene) bis (trimellitate anhydride), 1,5- (pentamethylene) bis (trimellitate anhydride) radish Water), 1,6- (hexamethylene) bis (trimellitate anhydride) 1,7- (heptamethylene) bis (trimellitate anhydride) 1,8- (octamethylene) bis (trimellitate anhydride) , 1,12- (nonamethylene) bis (trimellitate anhydride), 1,10- (decamethylene) bis (trimellitate anhydride), 1,12- (Trimellitate anhydride), 1,18- (octadecamethylene) bis (trimellitate anhydride), and the like. These may be used singly or in combination of two or more kinds. . Among them, 3,4,3 ', 4'-benzophenonetetracarboxylic dianhydride, 2,3,2', 3'-benzophenonetetracarboxylic dianhydride, 2,3,3 ', 4'-benzophenonetetra Carboxylic acid dianhydride is preferable, and 3,4,3 ', 4'-benzophenonetracarboxylic acid dianhydride is more preferable.

The diamine is not particularly limited and examples thereof include o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 3,3'-diaminodiphenylether, 3,4'-di Aminodiphenylether, 4,4'-diaminodiphenylether, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, bis (4-amino- (4-amino-3,5-diisopropylphenyl) methane, 3,3'-diaminodiphenyldifluoromethane, 3,4'-diaminodiphenyl Diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfone, 4,4'-diamino Diphenyl sulfone, 3,3'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl ketone, 4'-diaminodiphenyl ketone, 4,4'- Aminodiphenyl ketone, 2,2'- (3-aminophenyl) propane, 2,2'- (3-aminophenyl) Bis (3-aminophenyl) hexafluoropropane, 2,2- (3-aminophenyl) propane, Bis (4-aminophenoxy) benzene, 1,4-bis (4-aminophenyl) (3-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 3,3 ' 2, 4 '- (1,4-phenylenebis (1-methylethylidene)) bisaniline, 4,4' Bis (4- (3-aminophenoxy) phenyl) hexafluoropropane, 2,2-bis (4- 4-aminophenoxy) phenyl) hexafluoropropane, bis (4- (3-aminoenoxy) phenyl) sulfide, Bis (4- (4-amino-enoxy) phenyl) sulfone, bis (4- Aromatic amines such as dihydroxy-4,4'-diaminobiphenyl and 3,5-diaminobenzoic acid, 1,3-bis (aminomethyl) cyclohexane, 2,2- Dioxadecane-1,12-diamine, 4,9,14-trioxaheptadecane-1,17-diamine, 1,2- Diaminoethane, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, Diaminodecane, 1,1-diaminododecane, 1,12-diaminododecane, 1,1-diaminododecane, 1,1-diaminododecane, Hexane, 1,3-bis (3-aminopropyl) tetramethyldisiloxane, and the like.

Among these diamines, it is preferable to use at least one selected from the group consisting of 3- (4-aminophenyl) -1,1,3-trimethyl-5-aminoindene, 1,3-bis (3-aminopropyl) tetramethyldisiloxane, Diamine, 1,6-diaminohexane, and 4,9,14-tri (4-aminophenoxyphenyl) propane, 4,9-dioxadecane- Oxaheptadecane-1,17-diamine, and more preferably at least one selected from the group consisting of 3- (4-aminophenyl) -1,1,3-trimethyl-5-aminoindene Do.

Examples of the solvent used in the reaction of the tetracarboxylic acid dianhydride with diamine include N, N-dimethylacetamide, N-methyl-2-pyrrolidone and N, N-dimethylformamide. In order to adjust the solubility of raw materials and the like, a nonpolar solvent (for example, toluene or xylene) may be used in combination.

The reaction temperature of the tetracarboxylic dianhydride and the diamine is preferably less than 100 占 폚, more preferably less than 90 占 폚. Imidization of polyamic acid is typically performed by heat treatment under an inert atmosphere (typically, a vacuum or a nitrogen atmosphere). The heat treatment temperature is preferably 150 占 폚 or higher, more preferably 180 to 450 占 폚.

The weight average molecular weight (Mw) of the polyimide resin is preferably 10,000 to 1,000,000, more preferably 20,000 to 100,000.

In the present invention, the polyimide resin is at least one selected from the group consisting of? -Butyrolactone, cyclopentanone, N-methylpyrrolidone, cyclohexanone, glycol ether, dimethylsulfoxide and tetramethylurea A polyimide resin having a solubility of 10 g / 100 g Solvent at 25 캜 for a solvent of a species is preferable.

The polyimide resin having such a solubility can be obtained, for example, by reacting 3,4,3 ', 4'-benzophenonetetracarboxylic dianhydride with 3- (4-aminophenyl) -1,1,3- And polyimide resins obtained by reacting a polyimide resin with an aminoindine. This polyimide resin is particularly excellent in heat resistance.

As the polyimide resin, a commercially available product may be used. S, SOXR-M, SOXR-U, SOXR-C (manufactured by Fuji Photo Film Co., Ltd.), GPT-LT (manufactured by Gunpo Aikagaku), Durimide (registered trademark) 200, 208A, (All manufactured by Nippon Kogyo Co., Ltd.), and the like.

<<< Polycarbonate Resin >>>

In the present invention, the polycarbonate resin preferably has a repeating unit represented by the following general formula (1).

[Chemical Formula 4]

In the general formula (1), Ar ¹ and Ar ² each independently represent an aromatic group, and L represents a single bond or a divalent linking group.

Ar ¹ and Ar ² in the general formula (1) each independently represent an aromatic group. Examples of the aromatic group include a benzene ring, a naphthalene ring, a pentane ring, an indene ring, an azole ring, a heptylene ring, an indene ring, a perylene ring, a pentacene ring, an acenaphthalene ring, a phenanthrene ring, an anthracene ring, a naphthacene ring, A thiophene ring, an imidazole ring, an oxazole ring, a thiazole ring, a pyridine ring, a pyrazine ring, a pyrimidine ring, a pyridazin ring, an indolizine ring, an indole ring A benzofuran ring, a benzothiophen ring, an isobenzofuran ring, a quinoline ring, a quinoline ring, a phthalazine ring, a naphthyridine ring, a quinoxaline ring, a quinoxazoline ring, an isoquinoline ring, a carbazole ring, a phenanthridine ring , An acridine ring, a phenanthroline ring, a thianthrene ring, a cromene ring, a zentylene ring, a phenoxathiine ring, a phenothiazine ring, and a phenanthrene ring. Among them, a benzene ring is preferable.

These aromatic groups may or may not have substituents.

Examples of the substituent which the aromatic group may have include a halogen atom, an alkyl group, an alkoxy group, and an aryl group.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

The alkyl group includes an alkyl group having 1 to 30 carbon atoms. The alkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms. The alkyl group may be linear or branched. Further, a part or all of the hydrogen atoms of the alkyl group may be substituted with a halogen atom. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a fluorine atom is preferable.

As the alkoxy group, an alkoxy group having 1 to 30 carbon atoms is preferable. The carbon number of the alkoxy group is more preferably from 1 to 20, and even more preferably from 1 to 10. The alkoxy group may be linear, branched or cyclic.

The aryl group is preferably an aryl group having 6 to 30 carbon atoms, and more preferably an aryl group having 6 to 20 carbon atoms.

The weight average molecular weight (Mw) of the polycarbonate resin is preferably 1,000 to 1,000,000, more preferably 10,000 to 80,000. Within the above range, the solubility in solvents and the heat resistance are good.

Examples of commercially available products of polycarbonate resins include PCZ-200, PCZ-300, PCZ-500, PCZ-800 (Mitsubishi Gas Gas Company), APEC 9379 (manufactured by Bayer), Panlite L-1225LM .

The adhesive composition of the present invention preferably contains the binder in an amount of 50.00 to 99.99% by mass, more preferably 70.00 to 99.99% by mass, and more preferably 88.00 to 99.99% by mass in the total solid content of the adhesive composition Particularly preferred. When the content of the binder is within the above range, the adhesive property and the peeling property are excellent.

When an elastomer is used as the binder, the elastomer is preferably contained in a proportion of 50.00 to 99.99 mass%, more preferably 70.00 to 99.99 mass%, and particularly preferably 88.00 to 99.99 mass% in the total solid content of the adhesive composition Do. When the content of the elastomer is within the above range, the adhesive property and the peelability are excellent. When two or more kinds of elastomers are used, the total amount is preferably in the above range.

When the elastomer is used as the binder, the content of the elastomer in the total mass of the binder is preferably 50 to 100% by mass, more preferably 70 to 100% by mass, still more preferably 80 to 100% To 100% by mass is more preferable. The binder may be substantially only an elastomer. The content of the elastomer in the total mass of the binder is preferably 99% by mass or more, more preferably 99.9% by mass or more, and more preferably only the elastomer.

In the adhesive composition of the present invention, the mass ratio of the fluorine compound and the binder is preferably 0.001: 99.999 to 10: 90.00, more preferably 0.001: 99.999 to 5:95.00, and more preferably 0.010 : 99.99 to 5: 95.00 is more preferable. By setting the mass ratio of the fluorine compound and the binder within the above range, it is easy to localize the fluorine compound more on the air interface side of the adhesive film.

<< Radical Polymerizable Compound >>

The adhesive composition of the present invention of the present invention preferably contains a radically polymerizable compound. The use of the adhesion-promoting composition containing a radical polymerizable compound makes it easy to suppress the flow deformation of the adherent film during heating. This makes it possible to suppress the flow deformation of the adherent film at the time of heating, for example, when heat treatment is applied to the laminate after polishing the substrate, for example, and the occurrence of warpage can be effectively suppressed. Further, since an adhesive film having a hardness can be formed, even if a pressure is locally applied at the time of polishing the substrate, the adhesive film is hardly deformed and the flat polishing property is excellent.

In the present invention, as the radically polymerizable compound, a compound having a radically polymerizable group, a known radically polymerizable compound capable of being polymerized by a radical can be used. Such compounds are widely known in the industrial field, and they can be used without any particular limitation in the present invention. These may be, for example, any of chemical forms such as monomers, prepolymers, oligomers or mixtures thereof and their multimers.

In the present invention, the monomer-type radical polymerizable compound (hereinafter also referred to as polymerizable monomer) is a compound different from the polymer compound. The polymerizable monomer is typically a low molecular compound, preferably a low molecular weight compound having a molecular weight of 2000 or less, more preferably a low molecular weight compound having a molecular weight of 1,500 or less, and still more preferably a low molecular weight compound having a molecular weight of 900 or less. The molecular weight of the polymerizable monomer is usually 100 or more.

The oligomer type radical polymerizable compound (hereinafter also referred to as polymerizable oligomer) is typically a polymer having a relatively low molecular weight, and is preferably a polymer having 10 to 100 polymerizable monomers bonded thereto. The molecular weight is preferably 2000 to 20,000, more preferably 2,000 to 15,000, and most preferably 2,000 to 10,000 in terms of polystyrene conversion by gel permeation chromatography (GPC).

The functional group number of the radical polymerizable compound in the present invention means the number of radical polymerizable groups in one molecule. The radical polymerizable group is a group capable of polymerization by the action of an actinic ray, radiation, or radical. Examples of the radical polymerizable group include groups having an ethylenic unsaturated bond. As the group having an ethylenically unsaturated bond, a styryl group, a (meth) acryloyl group and a (meth) allyl group are preferable, and a (meth) acryloyl group is more preferable. That is, the radical polymerizing compound used in the present invention is preferably a (meth) acrylate compound, more preferably an acrylate compound.

The radically polymerizable compound preferably contains at least one radically polymerizable compound having two or more radically polymerizable groups containing two or more radically polymerizable groups and preferably contains at least one radically polymerizable compound having three or more functional groups . The upper limit of the radically polymerizable group of the radical polymerizable compound is not particularly limited, but may be, for example, 15 or less, and may be 6 or less.

In addition, the radically polymerizable compound in the present invention preferably contains at least one radically polymerizable compound having three or more functional groups in view of improving the heat resistance by forming a three-dimensional crosslinked structure. A mixture of a radically polymerizable compound having two or less functional groups and a radically polymerizable compound having three or more functional groups may be used.

Specific examples of the radical polymerizing compound include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), esters thereof, amides, And is preferably an ester of an unsaturated carboxylic acid and a polyhydric alcohol compound, and an amide of an unsaturated carboxylic acid and a polyvalent amine compound, and a multimer thereof. Further, an addition reaction product of an unsaturated carboxylic acid ester or amide having a nucleophilic substituent such as a hydroxyl group, an amino group or a mercapto group with a monofunctional or multifunctional isocyanate or an epoxide, a monofunctional or polyfunctional A dehydration condensation reaction product with a carboxylic acid, and the like are suitably used. In addition, it is also possible to use an unsaturated carboxylic acid ester or amide having an electrophilic substituent such as an isocyanate group or an epoxy group, an addition reaction product of monofunctional or polyfunctional alcohols, amines, thiols, Unsaturated carboxylic acid esters or amides having a desilyl substituent group and mono- or polyfunctional alcohols, amines, and thioes are also suitable. As another example, in place of the above unsaturated carboxylic acid, it is also possible to use a compound group substituted with an unsaturated phosphonic acid, a vinylbenzene derivative such as styrene, a vinyl ether, an ally ether or the like.

As specific compounds thereof, the compounds described in paragraphs [0029] to [0037] of Japanese Laid-Open Patent Publication No. 2014-189696 can be suitably used in the present invention.

Also, a urethane-based addition polymerizable monomer prepared by the addition reaction of an isocyanate and a hydroxyl group is also suitable. Specific examples thereof include, for example, 1 in Japanese Patent Publication A polyisocyanate compound having two or more isocyanate groups in a molecule is produced by reacting a vinyl monomer containing two or more polymerizable vinyl groups in a molecule with a vinyl monomer containing a hydroxyl group represented by the following general formula (A) And the like.

CH ₂ = C (R ⁴ ) COOCH ₂ CH (R ⁵ ) OH (A)

(Provided that R ⁴ and R ⁵ represent H or CH ₃ )

In addition, the urethane acrylates described in JP-B-51-37193, JP-A-2-32293, JP-A-2-16765, JP-A-58-49860 Japanese Patent Publication No. 56-17654, Japanese Patent Publication No. 62-39417, and Japanese Patent Publication No. 62-39418, all of which are well known in the art, are also suitable.

As the radical polymerizing compound, the compounds described in paragraph [0095] to [0108] of Japanese Laid-Open Patent Publication No. 2009-288705 can be suitably used in the present invention.

As the radical polymerizing compound, a compound having at least one addition-polymerizable ethylene group and having a boiling point of 100 占 폚 or more at normal pressure is also preferable. As an example thereof, the compound described in Japanese Patent Application Laid-Open No. 2014-189696, paragraph No. 0040, can be suitably used in the present invention.

Also, as the compound having at least one addition-polymerizable ethylenic unsaturated group having a boiling point of 100 캜 or higher at normal pressure, the compounds described in paragraphs 0254 to 0257 of JP-A No. 2008-292970 are also suitable.

Radical polymerizable compounds represented by the following general formulas (MO-1) to (MO-5) may also be suitably used. In the formula, when T is an oxyalkylene group, the terminal on the carbon atom side is bonded to R.

[Chemical Formula 5]

[Chemical Formula 6]

In the general formula, n is an integer of 0 to 14, and m is an integer of 1 to 8. A plurality of R and T present in one molecule may be the same or different.

At least one of the plurality of Rs is -OC (= O) CH = CH ₂ or -OC (= O (O) ) C (CH ₃₎ represents a group represented by = CH _2.

Specific examples of the radical polymerizable compound represented by the above general formulas (MO-1) to (MO-5) include compounds described in paragraphs 0248 to 0251 of JP-A No. 2007-269779 Can be used.

Further, in JP-A 10-62986, it is also possible to add ethylene oxide or propylene oxide to a polyfunctional alcohol, which is described together with specific examples thereof as general formulas (1) and (2) The compound may also be used as a radical polymerizing compound.

Examples of the radical polymerizing compound include dipentaerythritol triacrylate (KAYARAD D-330 manufactured by Nippon Kayaku Kabushiki Kaisha) and dipentaerythritol tetraacrylate (commercially available as Kayarad D-320; Acrylate (commercially available as Kayarad D-310, manufactured by Nippon Kayaku K.K.), dipentaerythritol hexa (meth) acrylate (commercially available as Nippon Kayaku K.K.), dipentaerythritol penta (meth) KAYARAD DPHA, manufactured by Nippon Kayaku Co., Ltd.), and a structure in which the (meth) acryloyl group intervenes between ethylene glycol and propylene glycol moieties. These oligomer types can also be used.

The radically polymerizable compound may be a polyfunctional monomer having an acid group such as a carboxyl group, a sulfonic acid group or a phosphoric acid group. Examples of the polyfunctional monomer having an acid group include an aliphatic polyhydroxy compound and an ester of an unsaturated carboxylic acid, and a polyfunctional monomer having an acid group by reacting an unreacted hydroxyl group of the aliphatic polyhydroxy compound with a nonaromatic carboxylic acid anhydride . Especially preferably, in this ester, the aliphatic polyhydroxy compound is pentaerythritol and / or dipentaerythritol. Commercially available products include, for example, M-510 and M-520 as a polybasic acid-modified acrylic oligomer made by Toagosei Co., Ltd.

One kind of polyfunctional monomer having an acid group may be used alone, or two or more kinds thereof may be used in combination.

The preferable acid value of the polyfunctional monomer having an acid group is 0.1 to 40 mg KOH / g, particularly preferably 5 to 30 mg KOH / g. When the acid value of the polyfunctional monomer is within the above range, the preparation and handling properties are excellent.

As the radical polymerizing compound, a polyfunctional monomer having a caprolactone structure may also be used.

The polyfunctional monomer having a caprolactone structure is not particularly limited as long as it has a caprolactone structure in its molecule, and examples thereof include trimethylolethane, ditrimethylolethane, trimethylolpropane, ditrimethylolpropane (Meth) acrylic acid and? -Caprolactone obtained by esterifying polyhydric alcohols such as glycerin, diglycerol, trimethylolmelamine and the like with (meth) acrylic acid and? -Caprolactone, And polyfunctional (meth) acrylates. Among them, a polyfunctional monomer having a caprolactone structure represented by the following general formula (B) is preferable.

In general formula (B)

(7)

(Wherein all of the six Rs are groups represented by the following formula (C), or one to five of the six Rs are groups represented by the following formula (C) and the remainder is a group represented by the following formula It is an emerging period.)

In the general formula (C)

[Chemical Formula 8]

(Wherein R ¹ represents a hydrogen atom or a methyl group, m represents a number of 1 or 2, and "*" represents a bonding bond.)

In general formula (D)

[Chemical Formula 9]

(Wherein R ¹ represents a hydrogen atom or a methyl group, and "*" represents a bond.)

Such a polyfunctional monomer having a caprolactone structure is commercially available, for example, as a Kayarad DPCA series from Nippon Kayaku Co., and DPCA-20 (in the general formulas (B) to (D) , The number of groups represented by the general formula (C) = 2, and R1 are all hydrogen atoms), DPCA-30 (the same formula, m = 1, the number of groups represented by the formula (C) = 3, DPCA-120 (in the same formula: m = 2, a compound in which R1 is a hydrogen atom), DPCA-60 (the same formula, m = 1, the number of groups represented by the formula , The number of groups represented by the general formula (C) = 6, and R1 are all hydrogen atoms).

In the present invention, the polyfunctional monomer having a caprolactone structure may be used singly or in combination of two or more.

The radical polymerizing compound is preferably at least one selected from the group of compounds represented by the following general formula (i) or (ii).

[Chemical formula 10]

In the general formulas (i) and (ii), E independently represents - ((CH ₂ ) y CH ₂ O) - or - ((CH ₂ ) y CH (CH ₃ ) Independently represents an integer of 0 to 10, and each X independently represents a (meth) acryloyl group, a hydrogen atom, or a carboxyl group.

In the general formula (i), the sum of the (meth) acryloyl groups is 3 or 4, m is independently an integer of 0 to 10, and the sum of m is an integer of 0 to 40.

The total number of (meth) acryloyl groups in the general formula (ii) is 5 or 6, and each n independently represents an integer of 0 to 10, and the sum of n is an integer of 0 to 60.

In the general formula (i), m is preferably an integer of 0 to 6, more preferably an integer of 0 to 4.

The sum of m is preferably an integer of 2 to 40, more preferably an integer of 2 to 16, and an integer of 4 to 8 is particularly preferable.

In the general formula (ii), n is preferably an integer of 0 to 6, more preferably an integer of 0 to 4.

The sum of each n is preferably an integer of 3 to 60, more preferably an integer of 3 to 24, and particularly preferably an integer of 6 to 12.

The - ((CH ₂ ) _y CH ₂ O) - or - ((CH ₂ ) _y CH (CH ₃ ) O) - in the general formula (i) or the general formula X is preferable.

Particularly, in the general formula (ii), all of the six X's are preferably acryloyl groups.

The compound represented by the general formula (i) or (ii) can be produced by a process known in the art such as a step of binding an open-chain skeleton to pentaerythritol or dipentaerythritol by ring-opening addition reaction of ethylene oxide or propylene oxide, Can be synthesized from a step of introducing a (meth) acryloyl group by reacting a terminal hydroxyl group of the (meth) acryloyl chloride with, for example, (meth) acryloyl chloride. Each process is a well-known process, and one skilled in the art can easily synthesize the compound represented by the general formula (i) or (ii).

Among the compounds represented by the general formulas (i) and (ii), pentaerythritol derivatives and / or dipentaerythritol derivatives are more preferable.

(A), (b), (f), (f), (f) and (f) , (e) and (f) are preferable.

(11)

[Chemical Formula 12]

Examples of commercially available radically polymerizable compounds represented by the general formulas (i) and (ii) include SR-494, a tetrafunctional acrylate having four ethyleneoxy chains of Satomar, manufactured by Nippon Kayaku Co., DPCA-60, which is a hexafunctional acrylate having 6 pentyleneoxy chains, and TPA-330, which is a trifunctional acrylate having 3 isobutyleneoxy chains.

The radically polymerizable compounds are described in Japanese Patent Publication Nos. 48-41708, 51-37193, 2-32293, and 2-16765, Butene-containing acrylate, ethylene-vinyl acetate copolymer, ethylene-vinyl acetate copolymer, ethylene-vinyl acetate copolymer, Yutein compounds having an oxide-based skeleton are also suitable. Examples of the radical polymerizing compound include compounds having an amino structure or a sulfide structure in the molecule, such as those described in JP-A-63-277653, JP-A-63-260909 and JP-A-1-105238 Polymerizable monomers may also be used.

N-Ester M-4G, NK Ester A-9300, NK Ester M-9300 (manufactured by Sanyo Chemical Industries, Ltd.), Urethane oligomer UAS- NK Ester A-DPH, NK Ester A-BPE-4, UA-7200 (manufactured by Shin Nakamura Kagaku), DPHA-40H (manufactured by Nippon Kayaku), UA-306H, UA- UA-306I, AH-600, T-600, AI-600 (manufactured by Kyowa Chemical Industry Co., Ltd.) and Blemmer PME400 (manufactured by Nichiyu Corporation).

In the present invention, the radical polymerizing compound preferably has at least one kind of partial structure represented by the following (P-1) to (P-4) from the viewpoint of heat resistance, It is more preferable to have a partial structure. * In the equation is the connecting hand.

[Chemical Formula 13]

Specific examples of the radical polymerizable compound having the partial structure include trimethylolpropane tri (meth) acrylate, isocyanuric acid ethylene oxide modified di (meth) acrylate, isocyanuric acid ethylene oxide (Meth) acrylate, dipentaerythritol tetra (meth) acrylate, dimethylol propane tetra (meth) acrylate, dipentaerythritol tri (meth) acrylate, (Meth) acrylate, tetramethylolmethane tetra (meth) acrylate, and the like. In the present invention, these radically polymerizable compounds are particularly preferably used Can be used.

The content of the radically polymerizable compound in the adhesive composition of the present invention is preferably from 1 to 100 parts by weight based on the total solid content of the adhesive composition in terms of good adhesiveness and flat abrasion resistance, Is preferably 50 mass%, more preferably 1 mass% to 30 mass%, still more preferably 5 mass% to 30 mass%. The radical polymerizing compound may be used singly or in combination of two or more kinds.

When the binder and the radical polymerizing compound are used in combination, the mass ratio of the binder and the radical polymerizing compound is preferably 99.5: 0.5 to 90: 10, more preferably 99: 1 to 90:10, : 2 to 92: 8 is most preferable. When the mass ratio of the binder to the radical polymerizable compound is within the above range, an adhesion film excellent in adhesiveness, flat abrasion resistance, peelability and flexural restraint can be formed.

<<< Antioxidants >>>

The adhesive composition of the present invention may contain an antioxidant. As the antioxidant, phenol antioxidants, sulfur antioxidants, phosphorus antioxidants, quinone antioxidants, amine antioxidants and the like can be used.

Examples of the phenolic antioxidant include p-methoxyphenol, 2,6-di-tert-butyl-4-methylphenol, Irganox 1010, Irganox 1330 , "Irganox 3114", "Irganox 1035", "Sumilizer MDP-S", "Sumilizer GA-80" manufactured by Sumitomo Chemical Co., Ltd., and the like.

Examples of the sulfur-based antioxidant include 3,3'-thiodipropionate diastereomer, "Sumilizer TPM", "Sumilizer TPS", "Sumilizer TP-D", etc. manufactured by Sumitomo Chemical Co., .

Examples of the phosphorus antioxidant include tris (2,4-di-tert-butylphenyl) phosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, poly Irgafos 168 &quot;, &quot; Irgafos 38 &quot;, and the like, which are available from BASF Co., .

Examples of the quinone antioxidant include p-benzoquinone, 2-tert-butyl-1,4-benzoquinone, and the like.

Examples of the amine-based antioxidant include dimethyl aniline and phenothiazine.

The antioxidant is preferably IRGANOX 1010, Irganox 1330, 3,3'-thiodipropionate distearyl, and Sumilizer TP-D, preferably Irganox 1010, Irganox 1330, And Irganox 1010 is particularly preferable.

Among the above-mentioned antioxidants, phenol-based antioxidants and sulfur-based antioxidants or phosphorus-based antioxidants are preferably used in combination, and phenol-based antioxidants and sulfur-based antioxidants are most preferably used in combination. Particularly, when a polystyrene-based elastomer is used as the elastomer, it is preferable to use a phenolic antioxidant and a sulfur-based antioxidant in combination. By using such a combination, the effect of effectively suppressing the deterioration of the binder due to the oxidation reaction can be expected. When the phenolic antioxidant and the sulfur antioxidant are used in combination, the mass ratio of the phenol antioxidant to the sulfur antioxidant is preferably 95: 5 to 5:95, : 25 is more preferable.

As a combination of the antioxidants, Irganox 1010, Sumilizer TP-D, Irganox 1330 and Sumilizer TP-D, and Sumilizer GA-80 and Sumilizer TP-D are preferable, and Irganox 1010, Riser TP-D, Irganox 1330 and Sumilizer TP-D are more preferable, and Irganox 1010 and Smearizer TP-D are particularly preferable.

From the viewpoint of preventing sublimation during heating, the molecular weight of the antioxidant is preferably 400 or more, more preferably 600 or more, and particularly preferably 750 or more.

When the adhesive composition has an antioxidant, the content of the antioxidant is preferably 0.001 to 20.0% by mass, more preferably 0.005 to 10.0% by mass, based on the total solid content of the adhesive composition.

The antioxidant may be of one kind alone or in combination of two or more kinds. When the amount of the antioxidant is two or more, the total amount is preferably in the above range.

<< Solvent >>

The adhesive composition of the present invention preferably contains a solvent. As the solvent, any of known solvents can be used without limitation, and organic solvents are preferable.

Examples of the organic solvent include ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, butyl butyrate, butyl lactate, (For example, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.)), 3-oxypropionic acid alkyl esters such as methyl 3-oxypropionate and ethyl 3-oxypropionate (for example, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3- Ethyl ethoxypropionate, etc.)), 2-oxypropionic acid alkyl esters (e.g., methyl 2-oxypropionate, ethyl 2-oxypropionate, Propyl methoxypropionate, ethyl 2-ethoxypropionate), 2-oxy-2- (2-methoxypropionate, Methyl propionate and ethyl 2-oxy-2-methylpropionate (for example, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate and the like), methyl pyruvate, ethyl pyruvate, , Esters such as methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, and 1-methoxy-2-propyl acetate;

Diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol mono Diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether, Ethers such as acetate, propylene glycol monopropyl ether acetate;

Ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone, N-methyl-2-pyrrolidone and gamma butyrolactone;

Butylbenzene, isobutylbenzene, tert-butylbenzene, amylbenzene, isoamylbenzene, (2,2-dimethylbenzyl) benzene, toluene, xylene, anisole, mesitylene, ethylbenzene, propylbenzene, cumene, 1-phenyloctane, 1-phenylnonane, 1-phenyldecane, cyclopropylbenzene, cyclohexylbenzene, 2-ethyltoluene, 1 , 2-diethylbenzene, o-cymene, indene, 1,2,3,4-tetrahydronaphthalene, 3-ethyltoluene, m-cymene, 1,3-diisopropylbenzene, , 1,4-diethylbenzene, p-cymene, 1,4-diisopropylbenzene, 4-tert-butyltoluene, 1,4-di-tert-butylbenzene, , 2,3-trimethylbenzene, 1,2,4-trimethylbenzene, 4-tert-butyl-ozylene, 1,2,4-triethylbenzene, 1,3,5- 1,3,5-triisopropylbenzene, 5-tert-butyl-m-xylene, 3,5-di-tert-butyltoluene, 1,2,3,5-tetramethyl Zhen, 1,2,4,5-tetramethyl benzene, be an aromatic hydrocarbon such as benzene pentamethyl soryu;

And hydrocarbons such as limonene, p-mentine, nonene, decane, dodecane and decalin, and the like.

These solvents are also preferably mixed with two or more kinds in view of improving the application surface shape and the like. In this case, particularly preferable examples include mesitylene, tert-butylbenzene, 1,2,4-trimethylbenzene, p-mentine, gamma butyrolactone, anisole, methyl 3-ethoxypropionate, Ethyl propionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, ethylcarbitol acetate, butylcarbitol acetate , Propylene glycol methyl ether, and propylene glycol methyl ether acetate.

In the case where the adhesive composition has a solvent, the content of the solvent in the adhesive composition is preferably such that the total solid content concentration of the adhesive composition is 5 to 80 mass%, more preferably 5 to 70 mass% %, And particularly preferably from 10 to 60% by mass.

The solvent may be a single kind or two or more types. When two or more kinds of solvents are used, the total amount is preferably in the above range.

<< Surfactant >>

The adhesive composition used in the present invention preferably contains a surfactant.

As the surfactant, any of anionic, cationic, nonionic or amphoteric surfactants may be used, but preferred surfactants are nonionic surfactants.

Preferable examples of the nonionic surfactants include polyoxyethylene higher alkyl ethers, polyoxyethylene higher alkyl phenyl ethers, higher fatty acid diesters of polyoxyethylene glycol, and silicone surfactants.

The adhesive composition preferably contains a silicone surfactant as a surfactant from the viewpoint of coating properties. Generally, the use of a composition having a high viscosity for adhesion makes it difficult to apply the composition in a uniform thickness. However, since it is easy to coat the composition with a uniform thickness, the composition can be more preferably used because it contains a silicone surfactant.

As the silicone surfactants, there can be mentioned, for example, JP-A 62-36663, JP-A 61-226746, JP-A 61-226745, JP-A 62-170950, Japanese Patent Application Laid-Open No. 63-34540, Japanese Patent Application Laid-Open Nos. 7-230165, 8-62834, 9-54432, 9-5988, A surfactant described in each of Japanese Patent Application Laid-Open No. 2001-330953, or a commercially available surfactant may be used.

Examples of commercially available silicone surfactants include KP-301, KP-306, KP-109, KP-310, KP-310B, KP-323, KP-326, KP- KP-365, KP-365, KP-358, KP-358, KP-361, KP-361, KP-361, KP-369, KP-330, KP-650, KP-651, KP-390, KP-391 and KP-392 (manufactured by Shin-Etsu Chemical Co., Ltd.).

When the adhesive composition contains a surfactant, the content of the surfactant in the adhesive composition is preferably 0.001 to 5% by mass, more preferably 0.005 to 1% by mass, based on the total solid content of the adhesive composition, By mass, more preferably from 0.01 to 0.5% by mass. The surfactant may be one kind or two or more kinds. When two or more kinds of surfactants are used, the total amount is preferably in the above range.

<< Other additives >>

The adhesive composition of the present invention may contain various additives such as a curing agent, a curing catalyst, a silane coupling agent, a filler, an adhesion promoter, an ultraviolet absorber, an anti-aggregation agent, and the like insofar as the effect of the present invention is not impaired Can be blended. When these additives are compounded, the total amount of these additives is preferably 3% by mass or less based on the total solid content of the adhesive composition.

The adhesive composition of the present invention preferably does not contain impurities such as metals. The content of the impurities contained in these materials is preferably 1 ppm or less, more preferably 100 ppt or less, more preferably 10 ppt or less, and particularly preferably 10 to 100 ppt or less (particularly preferably less than the detection limit of the measuring apparatus).

Examples of the method for removing impurities such as metals from the adhesive composition include filtration using a filter. The filter hole diameter is preferably 10 nm or less in pore size, more preferably 5 nm or less, and further preferably 3 nm or less. As the material of the filter, a filter made of polytetrafluoroethylene, polyethylene or nylon is preferable. The filter may be previously washed with an organic solvent. In the filter filtering step, a plurality of types of filters may be connected in series or in parallel. When a plurality of types of filters are used, filters having different hole diameters and / or different materials may be used in combination. In addition, the various materials may be filtered a plurality of times, and the step of filtering a plurality of times may be a circulating filtration step.

As a method of reducing impurities such as metals contained in the adhesive composition, it is possible to select a raw material having a small metal content as a raw material constituting the adhesive composition or to filter the raw materials constituting the adhesive composition Or by lining the inside of the apparatus with polytetrafluoroethylene or the like and performing distillation under the condition that contemination is suppressed as much as possible. Is the same as the above-mentioned conditions in the filter filtration performed on the raw material constituting the adhesive composition.

In addition to filter filtration, impurities may be removed by the adsorbent, or a combination of filter filtration and adsorbent may be used. As the adsorbent, known adsorbents can be used. For example, inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon can be used.

<Preparation of Adhesive Composition>

The adhesive composition of the present invention can be prepared by mixing the respective components described above. The mixing of the respective components is usually carried out in the range of 0 ° C to 100 ° C. It is also preferable to mix the respective components and then filter them with a filter, for example. The filtration may be performed in multiple steps or repeated a plurality of times. In addition, the filtrate may be re-filtered.

The filter is not particularly limited as long as it is conventionally used for filtration and the like. For example, a fluororesin such as PTFE (polytetrafluoroethylene), a polyamide resin such as nylon-6 or nylon-6,6, a polyolefin resin such as polyethylene or polypropylene (PP) And the like). Of these materials, polypropylene (including high-density polypropylene) and nylon are preferred.

The pore diameter of the filter is suitably about 0.003 to 5.0 mu m, for example. By setting this range, it becomes possible to reliably remove fine foreign matters such as impurities and aggregates contained in the composition while suppressing filtration clogging.

When using a filter, other filters may be combined. At this time, the filtering by the first filter may be performed once, or may be performed twice or more. When filtering is performed two or more times in combination with other filters, it is preferable that the pore diameters of the second and subsequent pores are equal to or smaller than the pore diameters of the first filtering. The first filter having different pore diameters may be combined within the above-described range. The pore diameter here can refer to the nominal value of the filter manufacturer. As a commercially available filter, there may be selected, for example, various filters provided by Nippon Oil Corporation, Advantech Toyokawa Co., Ltd., Nippon Integrity Corporation (formerly Nihon Micro-Roller Corporation) or Kitsch Microfilter .

&Lt; Process for producing adhesive film &

Next, a method for manufacturing the adhesive film of the present invention will be described.

In the method for producing an adherent film of the present invention, the above-mentioned adherent composition is applied on a support in the form of a layer and dried to produce the following adherent film of <1>. Preferably, an adhesion film of the following <2> is produced.

<1> is a ratio of the presence of fluorine atoms on the surface of the adhesive film by the X-ray photoelectron spectroscopy, the ratio A of the presence of fluorine atoms on the surface of the adhesive film opposite to the support and the ratio A of the presence of fluorine atoms on the surface of the support film Wherein the fluorine atom existing ratio B satisfies the relationship of the following formula (1) and the fluorine atom present ratio A is 10 to 40%.

A / B? 1.3 ... (1)

A is the ratio A of the presence of fluorine atoms on the surface of the adhesive film opposite to the support,

B is the presence ratio B of fluorine atoms on the surface of the adhesive film on the support side.

&Lt; 2 > An adhesive film wherein the ratio A of the fluorine atom and the ratio B of the fluorine atom satisfy the relation of the following formula (2), and the fluorine atom present ratio A is 18 to 40%.

A / B? 1.5 ... (2)

A is the ratio A of the presence of fluorine atoms on the surface of the adhesive film opposite to the support,

B is the presence ratio B of fluorine atoms on the surface of the adhesive film on the support side.

A spin coating method, a spray coating method, a roller coating method, a flow coating method, a doctor coating method, a screen printing method, a dip coating method and the like can be given as a coating method of the adhesive composition. Alternatively, the adhesive composition may be extruded from a slit-shaped opening under pressure to apply the adhesive composition onto the support.

The application amount of the adhesive composition varies depending on the use, but is preferably, for example, a coating amount in which the average film thickness of the dried adhesive film becomes 0.1 to 500 mu m. The lower limit is preferably 1 m or more. The upper limit is preferably 200 mu m or less, more preferably 100 mu m or less.

In the present invention, the average film thickness of the adherent film is preferably in a range from the one end face to the other end face in five positions at regular intervals from one end face to the other end face Is defined as the average value of the values measured by the micrometer. In the present invention, the term &quot; cross-section along one direction of the adhesive film &quot; means a cross section perpendicular to the direction of the long side when the adhesive film has a polygonal shape. When the adhering adhesive film has a square shape, it is a cross section orthogonal to one of the sides. In the case where the adhesive film is circular or elliptical, it is a section passing through the center.

Examples of the support include drums and bands. As the support, a substrate such as a release film, a device wafer, or a carrier substrate may be used.

The carrier substrate is not particularly limited, and examples thereof include a silicon substrate, a glass substrate, a metal substrate, and a compound semiconductor substrate. Among them, a silicon substrate is preferable in view of the fact that it is difficult to contaminate a silicon substrate which is typically used as a substrate of a semiconductor device, and an electrostatic chuck generally used in a semiconductor device manufacturing process can be used.

The thickness of the carrier base material is not particularly limited, but is preferably 300 占 퐉 to 100 mm, more preferably 300 占 퐉 to 10 mm, for example.

The surface of the carrier substrate may have a release layer. As the release layer, a low surface energy layer containing a fluorine atom and / or a silicon atom is preferable, and it is preferable to have a material containing a fluorine atom and / or a silicon atom. The fluorine content of the release layer is preferably 30 to 80 mass%, more preferably 40 to 76 mass%, and particularly preferably 60 to 75 mass%.

As the device wafer, known ones can be used without limitation, and examples thereof include a silicon substrate and a compound semiconductor substrate. Specific examples of the compound semiconductor substrate include SiC substrate, SiGe substrate, ZnS substrate, ZnSe substrate, GaAs substrate, InP substrate, GaN substrate and the like.

A mechanical structure or a circuit may be formed on the surface of the device wafer. As a device wafer on which a mechanical structure or a circuit is formed, a device wafer such as MEMS (Micro Electro Mechanical Systems), a power device, an image sensor, a microsensor, a light emitting diode (LED), an optical device, an interposer, a buried device, .

The device wafer preferably has a structure such as a metal bank. According to the present invention, it is possible to stably adhere to a device wafer having a structure on the surface, and to easily release adhesion to the device wafer. The height of the structure is not particularly limited, but is preferably 1 to 150 mu m, more preferably 5 to 100 mu m.

A single adherent film (film) can be obtained by applying a layer of an adhesive composition on a support in a layer form, drying and solidifying the adherent film mechanically from the support.

The drying conditions depend on the kind of the adhesive composition and the film thickness of the adhesive film. For example, at 60 to 180 DEG C, 10 to 600 seconds are preferable. The drying temperature is more preferably 80 to 150 占 폚, and more preferably 100 to 120 占 폚. The drying time is preferably 30 to 300 seconds, more preferably 40 to 180 seconds.

Drying may be carried out by increasing the temperature stepwise by dividing into two steps.

In the case of using a release film as the support, the adhesion film may be left as it is without peeling from the support, and the adhesion of the release film may be made as an adhesive film (laminate).

By performing these treatments continuously, a roll-shaped long film can be obtained. The length of the long film is not particularly limited, but the lower limit is preferably 5000 mm or more, for example, and more preferably 1000 mm or more. The upper limit is preferably, for example, 500000 mm or less, and more preferably 200000 mm or less.

Alternatively, a release film (substrate) may be applied to both sides of the adhesive film to form a double-sided release film adhering film (laminate). It is possible to prevent troubles such as scratches on the surface of the adhesive film or sticking to the adhesive film during storage by adhering the release film to one side or both sides of the adhesive film. The release film can be peeled and removed in use.

Further, even when a device wafer or a carrier substrate is used as a support, the adhesion film may be left as it is without peeling from the support.

In the present invention, the presence ratio A of fluorine atoms in the adhesion film is more preferably 5.0 to 35%, and further preferably 10 to 30%. According to this embodiment, it is possible to provide an adhesion film excellent in peelability.

In the present invention, the presence ratio B of the fluorine atoms in the adhesion film is more preferably 1 to 20%, and further preferably 1 to 15%. According to this aspect, it is easy to control the peeling interface by the surface of the adhesive film opposite to the support.

<Adhesive film>

Next, the adhesive film of the present invention will be described with reference to Fig.

As shown in Fig. 1, the adhesion film of the present invention is an adhesion film comprising a compound having a fluorine atom,

The adhesive film 11 is a single layer film,

Of the surface of the adhesive film was irradiated with monochromatic AlK? Ray of 25W for an analysis area of 1400 占 퐉 占 700 占 퐉 of the surface of the adhesive film and was detected at an extraction angle of 45 占 and the presence ratio of fluorine atoms The ratio B1 of the presence of fluorine atoms on the one surface a of the adhesive film 11 and the ratio B1 of the presence of fluorine atoms on the surface b of the adhesive film on the opposite side to the surface a satisfy the following expression Satisfy the relationship of the formula (11), and the presence ratio A1 of fluorine atoms is 5 to 40%.

A1 / B1? 1.3 (11)

A1 is the ratio A1 of the presence of fluorine atoms on the surface a of the adhesive film,

B1 is the presence ratio B1 of fluorine atoms on the surface b of the adhesive film.

The adhesion film of the present invention can peel the carrier substrate and the device wafer from the surface a side of the adhesion film since the presence ratio A1 of the fluorine atoms and the presence ratio B1 of the fluorine atoms satisfy the relationship of the formula (11) .

Also, since the presence ratio A1 of the fluorine atoms on the surface a is 5 to 40%, the carrier base and the device wafer can be peeled off with a smaller peeling force.

The adhesive film of the present invention preferably has the fluorine atom abundance ratio A1 and the fluorine atom abundance ratio B1 satisfy the relation of the following formula (12) and the fluorine atom abundance ratio A1 of 10 to 30%.

A1 / B1≥1.5 ... (12)

A1 is the ratio A1 of the presence of fluorine atoms on the surface a of the adhesive film,

B1 is the presence ratio B1 of fluorine atoms on the surface b of the adhesive film.

In the present invention, the presence ratio A of the fluorine atoms in the adhesion film is more preferably 5 to 35%, and further preferably 10 to 30%. According to this embodiment, it is possible to provide an adhesion film excellent in peelability.

In the present invention, the presence ratio B of the fluorine atoms in the adhesion film is more preferably 1 to 20%, and further preferably 1 to 15%. According to this aspect, it is easy to control the peeling interface by the surface of the adhesive film opposite to the support.

The adhesion film of the present invention can be produced by the above-described production method of the adhesion film of the present invention.

The adhesive film of the present invention preferably has an average film thickness of 0.1 to 500 mu m. The lower limit is preferably 1 m or more. The upper limit is preferably 200 mu m or less, more preferably 100 mu m or less.

In the adhesion film of the present invention, the compound having a fluorine atom is preferably a compound having a hydrophilic group and a fluorine atom. Details of the compound having a fluorine atom can be cited as the adhesive composition, and the preferable range is also the same.

The adhesive film of the present invention preferably contains the fluorine atom-containing compound in a proportion of 0.03 mass% or more and less than 0.5 mass%, more preferably 0.04 to 0.4 mass%, and more preferably 0.05 to 0.2 mass%, based on the total solid content of the adhesive film. More preferably,% by mass.

In the adhesion film of the present invention, the adhesion film preferably includes at least one kind selected from a binder and a radical polymerizable compound. It is more preferable that the binder includes an elastomer. As for the details of the binder, there may be mentioned those described as the adhesive composition, and the preferred range is also the same.

When the adhesive film of the present invention comprises a binder, the binder is preferably contained in a proportion of 50.00 to 99.99 mass%, more preferably 70.00 to 99.99 mass%, and more preferably 88.00 to 99.99 mass%, based on the total solid content of the adhesive film. Is particularly preferable.

When an elastomer is used as the binder, the elastomer is preferably contained in a proportion of 50.00 to 99.99 mass%, more preferably 70.00 to 99.99 mass%, and particularly preferably 88.00 to 99.99 mass% in the total solid content of the adhesive film Do.

When the adhesive film of the present invention contains a radical polymerizing compound, the radical polymerizing compound is preferably contained in a proportion of 1 to 50 mass% in the total solid content of the adhesive film, more preferably 1 to 30 mass% , And particularly preferably from 5 to 30 mass%.

The adhesive film of the present invention may further include other additives such as an antioxidant. The details of these can be cited as examples of the adhesive composition, and the preferable range is also the same.

<Laminate>

Next, the laminate of the present invention will be described.

The laminate of the present invention has the adhesive film obtained by the production method of the present invention described above, or the above-described adhesive film and a substrate on one side or both sides of the adhesive film.

Examples of the substrate include a release film, a device wafer, and a carrier substrate.

For example, by using a release film as a base material, adhesion of the release film can be used as an adhesive film. The adhesive film with the releasing film can be produced by the above-described method of manufacturing the adhesive film of the present invention. Further, it can be produced by attaching a release film to one side or both sides of the adhesive film of the present invention described above.

Also, by using a carrier base material or a device wafer as the base material, an adhesive base material can be used. The adhesive base material can be produced by using the above-described production method of the adhesive film of the present invention. It is also possible to form the above-described adhesive film of the present invention by laminating on a substrate. For example, an adhesive film is set on a vacuum laminator, the adhesive film is placed on a substrate in the apparatus, the adhesive film is contacted with the substrate under vacuum, and the adhesive film is fixed on the substrate And a method of laminating them). The adhesive film fixed on the substrate may be cut into a desired shape such as a circular shape.

&Lt; Device Wafer Laminate >

Next, the device wafer laminate of the present invention will be described.

The device wafer stacking laminate of the present invention has the above-described adhesive film of the present invention between the carrier substrate and the device wafer, wherein one surface of the adhesive film is in contact with the device surface of the device wafer, And is in contact with the surface of the substrate. As described above, the adhesion film is a single-layer film, and does not have a release layer or the like. This can improve the throughput of the laminate formation.

The carrier substrate and the device wafer may be those described above.

The thickness of the device wafer before mechanical or chemical treatment is preferably 500 탆 or more, more preferably 600 탆 or more, and more preferably 700 탆 or more. The upper limit is preferably, for example, 2000 占 퐉 or less, more preferably 1500 占 퐉 or less.

The thickness of the device wafer after thinning by mechanical or chemical treatment is preferably, for example, less than 500 mu m, more preferably 400 mu m or less, and further preferably 300 mu m or less. The lower limit is preferably 1 m or more, for example, and more preferably 5 m or more.

The device wafer laminate of the present invention can be produced by heat-pressing a surface of the above-mentioned adhesive base material on which the adhesive film is formed and a device wafer or a carrier base material. The pressure bonding conditions are, for example, a temperature of 100 to 200 DEG C, a pressure of 0.01 to 1 MPa, and a time of 1 to 15 minutes.

It is also possible to arrange the above-described adhesive film of the present invention between the carrier substrate and the device wafer, followed by hot-pressing.

<Method of Manufacturing Semiconductor Device>

&Lt; First Embodiment &gt;

Hereinafter, one embodiment of a method of manufacturing a semiconductor device will be described with reference to FIG. The present invention is not limited to the following embodiments.

2 (A) to 2 (E) are schematic cross-sectional views (Figs. 2A and 2B) for explaining adherence between a carrier substrate and a device wafer, a state in which a device wafer adhered to a carrier substrate is thinned (FIG. 2 (C)), a state in which the carrier substrate and the device wafer are separated (FIG. 2 (D)), and a state after the adhesive film is removed from the device wafer (FIG.

As shown in Fig. 2 (A), an adhesive base material 100 having the adhesive film 11 of the present invention is prepared on a carrier base material 12. In this embodiment, the surface a of the above-mentioned adhesion film is disposed on the carrier base material 12 side. The adhesive base material (100) can be produced by arranging a film-like adherent film on a carrier substrate so as to place the surface (a) of the adhesive film on the carrier base material (12) side and laminating it.

The device wafer 60 is formed by providing a plurality of device chips 62 on the surface 61a of the silicon substrate 61. [

The thickness of the silicon substrate 61 is preferably 200 to 1200 占 퐉, for example. The device chip 62 is preferably, for example, a metal structure, and the height is preferably 10 to 100 mu m.

A step of cleaning the back surface of the carrier substrate 12 or the device wafer 60 with a solvent may be provided in the process of forming the adhesive film 11. [ Concretely, it is possible to prevent the apparatus from being contaminated by removing the residue of the adhesive film adhering to the end faces and back faces of the carrier substrate 12 and the device wafer 60 using a solvent in which the adhesive film is dissolved, The total thickness variation (TTV) of the device wafer can be lowered. As the solvent used in the step of cleaning the back surface of the carrier substrate 12 or the device wafer 60 with a solvent, a solvent included in the above-mentioned adhesive bonding composition may be used.

Subsequently, as shown in Fig. 2 (B), the adhesive base material 100 and the device wafer 60 are pressed together to bond the carrier base material 12 and the device wafer 60 together.

It is preferable that the adhesive film 11 completely covers the device chip 62. When the height of the device chip is X m and the thickness of the adhesive film is Y m, the relationship of &quot; X + 100 & .

The reason why the adhesive film 11 completely covers the device chip 62 is that the TTV (Total Thickness Variation) of the thin device wafer is further lowered (that is, ).

That is, when the device wafer is thinned, the plurality of device chips 62 are protected by the adhesive film 11, thereby making it possible to substantially eliminate the irregularities on the contact surface with the carrier substrate 12. [ Therefore, even if the substrate is thinned in such a supported state, the possibility that the shape derived from the plurality of device chips 62 is transferred to the back surface 61b1 of the thin device wafer is reduced, and as a result, Can be lowered.

Then, as shown in Fig. 2 (C), the surface 61b of the silicon substrate 61 is subjected to mechanical or chemical treatment (though not particularly limited, for example, thinning such as grinding or chemical mechanical polishing Treatment with high temperature and vacuum such as chemical vapor deposition (CVD) or physical vapor deposition (PVD), treatment with chemicals such as organic solvents, acidic treatment solution or basic treatment solution, plating treatment, irradiation with active rays, heating (For example, the average thickness is preferably less than 500 탆 and more preferably 1 to 200 탆), as shown in Fig. 2 (C) To obtain a thin device wafer 60a.

A step of cleaning the adherent film protruding outward beyond the area of the substrate surface of the device wafer with a solvent may be provided at a stage before the processing of the device wafer is made at a high temperature and under vacuum. Specifically, after the device wafer is thinned, the protruding adherent film is removed by using a solvent in which the adherent film is dissolved, whereby the deformation and alteration of the adherent film caused by the direct treatment under high temperature and vacuum . As the solvent used in the step of cleaning the adherent film protruding outward beyond the area of the substrate surface of the carrier substrate or the area of the substrate surface of the device wafer with a solvent, a solvent included in the adhesive composition may be used.

That is, in the present invention, the area of the film surface of the adhesive film is preferably smaller than the area of the substrate surface of the carrier substrate. (C-200)? T? D where D is the diameter of the substrate surface of the carrier substrate, D is the diameter of the substrate surface of the device wafer, and T is the diameter of the film surface of the adhesive film. Is more preferable. The diameter of the substrate surface of the carrier substrate is _C m, the diameter of the substrate surface of the device wafer is _D m, the diameter of the film surface of the adhesive film on the side in contact with the carrier substrate is T _C m, when the diameter of a T _D μm, preferably satisfies _{(C-200) ≥T C>} T D ≥D. With this structure, it is possible to further suppress the deformation and the deterioration of the adhered film caused by the direct application of the treatment under high temperature and vacuum to the adhered film.

The area of the film surface of the adhesive film refers to the area when viewed in a direction perpendicular to the carrier substrate, and the surface irregularities are not considered. The same applies to the substrate surface of the device wafer. That is, the substrate surface of the device wafer referred to herein corresponds to, for example, the 61a surface of FIG. The same applies to the diameter of the film surface of the adhesive film or the like.

The diameter T of the film surface of the adherent film is defined as T _C μm and the diameter of the film surface on the side of the adherent film in contact with the carrier substrate is T _D μm, T = (T _C + T _D ) / 2. The diameter of the substrate surface of the carrier substrate and the diameter of the substrate surface of the device wafer refer to the diameter of the surface on the side in contact with the adhesive film.

Further, although the carrier base material is defined as &quot; diameter &quot;, it is not essential that the carrier base material and the like have a circular shape (mathematical sense), and it may be substantially circular. In the case of not a garden, the diameter when converted into a garden having the same area is defined as the above diameter.

As a mechanical or chemical treatment, a through hole (not shown) that penetrates the silicon substrate from the back surface 61b1 of the thin device wafer 60a is formed after the thinning process, and a silicon penetration electrode (Not shown) may be formed.

After the carrier base material 12 and the device wafer 60 are adhered to each other, the heat treatment may be performed until peeling off. As an example of the heat treatment, a heat treatment is performed in a mechanical or chemical treatment.

The maximum attained temperature in the heat treatment is preferably 80 to 400 占 폚, more preferably 130 to 400 占 폚, and more preferably 180 to 350 占 폚. The maximum attained temperature in the heat treatment is preferably lower than the decomposition temperature of the adhesive film. The heat treatment is preferably heating for 30 seconds to 30 minutes at the maximum attained temperature, and more preferably for 1 minute to 10 minutes at the maximum attained temperature.

Subsequently, as shown in Fig. 2 (D), the carrier substrate 12 is removed from the thin device wafer 60a. Although the method of desorbing is not particularly limited, it is preferable to pull up the end portion of the thin device wafer 60a in the vertical direction with respect to the thin device wafer 60a and peel it off without any treatment.

In this embodiment, since the surface a of the above-mentioned adhesive film is disposed on the carrier substrate 12 side, peeling occurs at the interface between the carrier substrate 12 and the adhesive film 11 as shown in Fig. 2 (D) do.

In the case of using the adhesive base material on the side of the carrier substrate 12 on which the surface b of the above-mentioned adhesive film is disposed, it is preferable that the distance between the thin device wafer 60a and the adherent film 11, Peeled.

A thin film device wafer 60a is slid with respect to the carrier substrate 12 and then the thin film device wafer 60a is removed from the end of the thin device wafer 60a, It can be pulled up in the vertical direction to peel off.

<Release liquid>

Hereinafter, the release liquid will be described in detail.

As the peeling solution, water and a solvent (organic solvent) can be used.

As the removing solution, an organic solvent which dissolves the adhesive film 11 is preferable. Examples of the organic solvent include aliphatic hydrocarbons such as aliphatic hydrocarbons (such as hexane, heptane, isophora E, H, G (manufactured by Esso Kagaku), limonene, p-menthane, nonane, decane, dodecane , Decalin, etc.), aromatic hydrocarbons (toluene, xylene, anisole, mesitylene, ethylbenzene, propylbenzene, cumene, n-butylbenzene, sec-butylbenzene, isobutylbenzene, tert- , Isoamylbenzene, (2,2-dimethylpropyl) benzene, 1-phenylhexane, 1-phenylheptane, 1-phenyloctane, 1-phenylnonane, 1-phenyldecane, cyclopropylbenzene, Cyclohexylbenzene, 2-ethyltoluene, 1,2-diethylbenzene, o-cymene, indene, 1,2,3,4-tetrahydronaphthalene, 3-ethyltoluene, m- Diisopropylbenzene, 4-ethyltoluene, 1,4-diethylbenzene, p-cymene, 1,4-diisopropylbenzene, 4-tert-butyltoluene, 1,4- , 1,3-diethylbenzene, 1,2,3-trimethylbenzene, 1 , 2,4-trimethylbenzene, 4-tert-butyl-ozylene, 1,2,4-triethylbenzene, 1,3,5-triethylbenzene, 1,3,5-triisopropylbenzene Tert-butyl-m-xylene, 3,5-di-tert-butyltoluene, 1,2,3,5-tetramethylbenzene, 1,2,4,5-tetramethylbenzene, Etc.), halogenated hydrocarbons (e.g., methylene dichloride, ethylene dichloride, trichlorethylene, and monochlorobenzene), and polar solvents. Examples of the polar solvent include alcohols (such as methanol, ethanol, propanol, isopropanol, 1-butanol, 1-pentanol, 1-hexanol, 1-heptanol, But are not limited to, 1-hexanol, 1-nonanol, 1-decanol, benzyl alcohol, ethylene glycol monomethyl ether, 2-ethoxy ethanol, diethylene glycol monoethyl ether, diethylene glycol monohexyl Ether, triethylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether, polyethylene glycol monomethyl ether, polypropylene glycol, tetraethylene glycol Ethylene glycol monobutyl ether, ethylene glycol monophenyl ether, propylene glycol monophenyl ether, methylphenyl carbinol, n-amyl alcohol, methyl amyl alcohol Etc.), ketones (acetone, methyl ethyl ketone, ethyl butyl ketone, methyl isobutyl ketone, cyclohexanone, etc.) And examples thereof include esters (such as ethyl acetate, propyl acetate, butyl acetate, amyl acetate, benzyl acetate, methyl lactate, butyl lactate, ethylene glycol monobutyl acetate, propylene glycol monomethyl ether acetate, diethylene glycol acetate, N-phenyldiethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, 4-ethyldiethanolamine, 4-ethylhexylamine, - (2-hydroxyethyl) morpholine, N, N-dimethylacetamide, N-methylpyrrolidone, etc.).

From the viewpoint of releasability, the release liquid may contain an alkali, an acid, and a surfactant. When these components are blended, the blending amount is preferably 0.1 to 5.0 mass% of the peeling solution.

From the viewpoint of releasability, a mode of mixing two or more kinds of organic solvents and water, two or more kinds of alkali, acid and surfactant is also preferable.

The alkali includes, for example, sodium tertiary phosphate, potassium tertiary phosphate, ammonium tertiary phosphate, sodium secondary phosphate, potassium secondary phosphate, ammonium secondary phosphate, sodium carbonate, potassium carbonate, ammonium carbonate, sodium hydrogen carbonate, An inorganic alkali agent such as potassium hydrogen carbonate, ammonium hydrogen carbonate, sodium borate, potassium borate, ammonium borate, sodium hydroxide, ammonium hydroxide, potassium hydroxide and lithium hydroxide, and organic alkali agents such as monomethylamine, dimethylamine, trimethylamine, But are not limited to, ethylamine, triethylamine, monoisopropylamine, diisopropylamine, triisopropylamine, n-butylamine, monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, ethyleneimine , Ethylenediamine, pyridine, tetramethylammonium hydroxide and the like can be used. These alkaline agents may be used alone or in combination of two or more.

Examples of the acid include inorganic acids such as hydrogen halide, sulfuric acid, nitric acid, phosphoric acid and boric acid, and organic acids such as methanesulfonic acid, ethanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, trifluoromethanesulfonic acid, acetic acid, , Gluconic acid, lactic acid, oxalic acid, and tartaric acid.

As the surfactant, anionic, cationic, nonionic or amphoteric surfactants can be used. In this case, the content of the surfactant is preferably 1 to 20% by mass, more preferably 1 to 10% by mass with respect to the total amount of the alkali aqueous solution.

By setting the content of the surfactant within the above-described range, the peeling property of the adhesive film 11 and the thin device wafer 60a can be further improved.

Examples of the anionic surfactant include, but are not limited to, fatty acid salts, abietic acid salts, hydroxyalkane sulfonic acid salts, alkane sulfonic acid salts, dialkyl sulfosuccinic acid salts, straight chain alkylbenzene sulfonic acid salts, Benzene sulfonic acid salts, alkyl naphthalene sulfonic acid salts, alkyl diphenyl ether (di) sulfonic acid salts, alkylphenoxy polyoxyethylene alkyl sulfonic acid salts, polyoxyethylene alkyl sulfophenyl ether salts, N-alkyl- Sodium oleyl taurate, disodium salt of N-alkylsulfosuccinic acid monoamide, petroleum sulfonic acid salts, sulfated castor oil, sulfuric acid waxy oil, sulfuric acid ester salts of fatty acid alkyl ester, alkyl sulfate ester salts, polyoxyethylene alkyl Ether sulfuric acid ester salts, fatty acid monoglyceride sulfuric acid ester salts, polyoxyethylene alkylphenyl ether sulfuric acid ester salts, polyoxyethylene styrylphenyl ether sulfuric acid ester salts, Polyoxyethylene alkyl ether phosphate ester salts, polyoxyethylene alkyl phenyl ether phosphate ester salts, partially saponified products of styrene-maleic anhydride copolymer, partially saponified products of olefin-maleic anhydride copolymer, naphthalene Sulfonate phomalin condensates, and the like. Among them, alkylbenzenesulfonic acid salts, alkylnaphthalenesulfonic acid salts and alkyldiphenylether (di) sulfonic acid salts are particularly preferably used.

The cationic surfactant is not particularly limited, but conventionally known ones can be used. Examples thereof include alkylamine salts, quaternary ammonium salts, alkylimidazolinium salts, polyoxyethylene alkylamine salts, and polyethylene polyamine derivatives.

Examples of nonionic surfactants include, but are not particularly limited to, polyethylene glycol type higher alcohol ethylene oxide adducts, alkylphenol ethylene oxide adducts, alkylnaphthol ethylene oxide adducts, phenol ethylene oxide adducts, naphthol ethylene oxide adducts, Fatty acid ethylen oxide adducts, fatty acid ethylene oxide adducts, polyhydric alcohol fatty acid ester ethylene oxide adducts, high alkylamine ethylene oxide adducts, fatty acid amide ethylene oxide adducts, ethylene oxide adducts of oils, polypropylene glycol ethylene oxide adducts, Ethylene oxide block copolymer, dimethylsiloxane- (propylene oxide-ethylene oxide) block copolymer, fatty acid esters of polyhydric alcohol type glycerol, fatty acid esters of pentaerythritol, fatty acid esters of sorbitol and sorbitol, sucrose Of fatty acids , Polyol and the like can be given to the emitter of an alkyl alcohol, fatty acid amides of alkanol amines. Of these, those having an aromatic ring and an ethylene oxide chain are preferable, and alkyl-substituted or unsubstituted phenol ethylene oxide adducts or alkyl-substituted or unsubstituted naphthol ethylene oxide adducts are more preferable.

Examples of the amphoteric surfactant include, but are not limited to, amine oxides such as alkyl dimethyl amine oxide, betaine based ones such as alkyl betaine, and amino acid based ones such as alkylamino fatty acid sodium. In particular, alkyldimethylamine oxide which may have a substituent, alkylcarboxybetaine which may have a substituent, and alkylsulfobetaine which may have a substituent are preferably used. Specifically, the compound represented by the formula (2) in paragraph [0256] of Japanese Laid-Open Patent Publication No. 2008-203359, the compound represented by the formula (I), the formula (II) Compounds represented by the formula (VI) and compounds represented by the paragraphs [0022] to [0029] of JP-A No. 2009-47927 can be used.

If necessary, additives such as antifoaming agents and water softening agents may be contained.

2 (E), a thin device wafer can be obtained by removing the adhesion film 11 from the thin device wafer 60a.

The method of removing the adhesive film 11 is, for example, a method of peeling off (peeling) the adhesive film with the film form (mechanical peeling), a method of peeling off the adhesive film after the adhesive film is swollen with the peeling solution, A method in which the adhesive film is dissolved and removed in a peeling solution, and a method in which the adhesive film is decomposed and vaporized by irradiation with actinic rays, radiation or heat, and the like. A method in which the adhesive film is peeled off and removed while remaining in a film form, and a method of dissolving and removing the adhesive film in an aqueous solution or an organic solvent can be preferably used. As the organic solvent, the organic solvent described above for the exfoliation liquid can be used. From the viewpoint of reducing the amount of the solvent used, it is preferable to remove the film in the form of a film. From the viewpoint of damage reduction on the surface of the device wafer, dissolution and removal are preferable.

It is preferable that the peel strength B of the device wafer surface 61a and the peeling adhesion film 11 satisfy the following formula (2).

B? 4 N / cm ... (2)

When the peel strength of the interface between the carrier substrate 12 and the adherent film 11 is A and the peel strength of the adhesive film 11 is B on the device wafer surface 61a, It is possible to pull up the carrier substrate 12 from the end of the thin device wafer 60a in a direction perpendicular to the device wafer and peel it off without any treatment at the time of peeling off the carrier substrate 12 from the thin device wafer 60a, The adhesive film 11 on the device wafer surface 61a can be removed in the form of a film.

After the carrier substrate 12 is removed from the thin device wafer 60a, various known processes are performed on the thin device wafer 60a as necessary to manufacture a semiconductor device having the thin device wafer 60a do.

When the residue of the adhesive film is adhered to the carrier substrate, the carrier substrate can be regenerated by removing the residue. Examples of the method for removing the residue include a method of physically removing the residue by spraying a brush, an ultrasonic wave, an ice particle, or an aerosol, a method of dissolving and removing it by dissolving in an aqueous solution or an organic solvent, and decomposing and vaporizing by irradiation of an actinic ray, And the like. However, depending on the carrier substrate, conventionally known cleaning methods can be used.

For example, when a silicon substrate is used as the carrier substrate, conventionally known cleaning methods for silicon wafers can be used. For example, aqueous solutions or organic solvents that can be used for chemical removal include strong acids, strong bases, strong oxidizing agents And specific examples thereof include acids such as sulfuric acid, hydrochloric acid, hydrofluoric acid, nitric acid and organic acids, bases such as tetramethylammonium, ammonia and organic bases, oxidizing agents such as hydrogen peroxide, A mixture of hydrochloric acid and hydrogen peroxide, a mixture of sulfuric acid and hydrogen peroxide, a mixture of hydrofluoric acid and hydrogen peroxide, a mixture of hydrofluoric acid and ammonium fluoride, and the like.

From the viewpoint of adhesiveness when a recycled carrier substrate is used, it is preferable to use a cleaning liquid.

It is preferable that the cleaning liquid contains an acid (strong acid) having a pKa of less than 0 and hydrogen peroxide. The acid having a pKa of less than 0 is selected from an inorganic acid such as hydrogen iodide, perchloric acid, hydrogen bromide, hydrogen chloride, nitric acid, sulfuric acid, or an organic acid such as alkylsulfonic acid or arylsulfonic acid. From the viewpoint of the cleaning property of the adhesion film on the carrier substrate, it is preferably an inorganic acid, and sulfuric acid is most preferable.

As the hydrogen peroxide, 30 mass% of hydrogen peroxide can be preferably used. The mixing ratio of the strong acid to the 30 mass% aqueous hydrogen peroxide is preferably 0.1: 1 to 100: 1, more preferably 1: 1 to 10: 1, most preferably 3: 1 to 5: 1 in terms of the mass ratio.

&Lt; Embodiment 2 &gt;

A second embodiment of a method of manufacturing a semiconductor through a process of manufacturing a laminate will be described with reference to FIG. The same portions as those of the first embodiment described above are denoted by the same reference numerals, and a description thereof will be omitted.

3 (A) to 3 (E) are schematic cross-sectional views (Figs. 3A and 3B) for explaining adhesion between a carrier substrate and a device wafer, a state in which a device wafer adhered to a carrier substrate is thinned (Fig. 3 (C)), a state in which the carrier substrate and the device wafer are separated (Fig. 3 (D)), and a state after the adhesive film is removed from the device wafer (Fig.

In this embodiment, as shown in Fig. 3A, the adhesive film 11a is formed on the surface 61a of the device wafer, which is different from the first embodiment. In this embodiment, the surface b of the above-mentioned adhesive film is disposed on the device wafer 60 side. As a method of forming the adhesion film 11a on the surface 61a of the device wafer so that the surface b of the adhesion film is placed on the device wafer 60 side, A method in which the adhesive composition is applied in a layer form and dried to form an adhesive film. It is also possible to arrange a film-like adhesion film on the device wafer so that the surface b of the adhesion film is disposed on the side of the device wafer 60 and laminating it.

Subsequently, as shown in Fig. 3 (B), the carrier base material 12 and the device wafer 60 are pressed together to bond the carrier base material 12 and the device wafer 60 together. Subsequently, as shown in Fig. 3 (C), the back surface 61b of the silicon substrate 61 is mechanically or chemically treated to thin the silicon substrate 61 to form a thin device wafer 60a. . Subsequently, as shown in Fig. 3 (D), the carrier substrate 12 is removed from the thin device wafer 60a.

In this embodiment, since the surface a of the above-mentioned adhesion film is disposed on the carrier substrate 12 side, the adhesion between the carrier substrate 12 and the adhesion film 11 is peeled off as shown in Fig. 3 (D) do.

Then, as shown in Fig. 3 (E), by removing the adhering film 11 from the thin device wafer 60a, a thin device wafer can be obtained.

Example

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to the following examples unless the scope of the present invention is exceeded. Unless otherwise specified, &quot; part &quot; and &quot;% &quot; are based on mass.

[Test Example 1]

<Preparation of Adhesive Composition>

The following components were mixed to prepare an adhesive composition.

&Lt; - &gt; Fluorine atom-containing compound:

Binder: The binder of the type shown in Table 1,

Irganox 1010 (manufactured by BASF Corporation): 5 parts by mass

Sumilizer TP-D (manufactured by Sumitomo Chemical Co., Ltd.): 5 parts by mass

Solvent: The solvent shown in Table 1 was added to the mass part

[Table 1]

The compounds shown in Table 1 are as follows.

[Compound having fluorine atom]

(Viscosity in the range of 1 to 100,000 mPa 占 퐏 at 25 占 폚), 10% thermal mass reduction temperature = 247 占 폚, Mw = 0.2 to less than 2.0, manufactured by DIC)

(Viscosity at 25 占 폚 in the range of 1 to 100,000 mPa 占 퐏), 10% thermal mass reduction temperature = 267 占 폚, Mw = 0.2 to less than 2.0 million, manufactured by DIC)

(Viscosity in the range of 1 to 100,000 mPa 25 at 25 캜), 10% thermal mass reduction temperature = 277 캜, Mw = 0.2 to less than 2.0, manufactured by DIC)

(Viscosity in the range of 1 to 100,000 mPa 占 퐏 at 25 占 폚), 10% thermal mass reduction temperature = 299 占 폚, Mw = 0.2 to less than 2.0, manufactured by DIC)

(Viscosity in the range of 1 to 100,000 mPa 占 퐏 at 25 占 폚), 10% thermal mass reduction temperature = 286 占 폚, Mw = 2.0 to less than 5.0 million, manufactured by DIC)

(A-6): Fotogen 710 FL (fluorine group, hydrophilic group, lipophilic group-containing oligomer, liquid phase compound (viscosity at 25 ° C in the range of 1 to 100,000 mPa · s)

(Viscosity at 25 캜 of from 1 to 100,000 mPa)), Neos) (A-7): Fotogen 730LM (fluorine group, hydrophilic group, oligomer-containing oligomer, liquid phase compound

(A-8) Surflon S243 (fluorine-containing ethylene oxide adduct, lipophilic liquid-phase compound, manufactured by AGC Seiyam Chemical Co., Ltd.)

[bookbinder]

(B-1): Septon 2002 (hydrogenated polystyrene elastomer, styrene content = 30 mass%, unsaturated double bond amount = less than 0.5 mmol / g, Less than 50,000 and less than 100,000, hardness (type A durometer) = 80, manufactured by Kuraray Co., Ltd.)

(B-2): Septon 2104 (hydrogenated polystyrene elastomer having a styrene content of 65% by weight, an unsaturated double bond content of less than 0.5 mmol / g, a thermal mass reduction temperature of not less than 400 ° C and less than 450 ° C, Less than 50,000 and less than 100,000, hardness (type A durometer) = 98, manufactured by Kuraray Co., Ltd.)

(B-3): Tuftec P2000 (hydrogenated polystyrene elastomer, styrene content = 67 mass%, unsaturated double bond amount = 0.5 mmol / g or more and less than 5 mmol / g, ° C, Mw = 50,000 or more and less than 100,000, hardness (type A durometer) = 90 or more, manufactured by Asahi Kasei Corporation)

(B-4): Duraimide (registered trademark) 284 (polyimide manufactured by Fuji Film)

(B-5): Zeonex 480R (cycloolefin-based polymer manufactured by Zeon)

(B-6): PCZ300 (polycarbonate manufactured by Mitsubishi Gas Chemical)

The amount of the unsaturated double bond is a value calculated by NMR (nuclear magnetic resonance) measurement.

The mass reduction temperature is a value measured by a thermogravimetric analyzer under the condition that the temperature is raised from 25 占 폚 to 20 占 폚 / min under a nitrogen stream.

&Lt; Preparation of test piece &

The above-mentioned adhesive composition was spin-coated on a silicon wafer (first substrate), dried at 110 ° C for 2 minutes and further at 190 ° C for 4 minutes to obtain a silicon wafer (first substrate) A laminate having an adhesive film was produced. Hereinafter, the surface (air side surface) opposite to the first substrate of the adhesive film is also referred to as the A side. The surface of the adhesive film on the first base side is also referred to as the B side.

The surface of the laminate on which the adhesion film was formed and the silicon wafer (second substrate) were pressed under vacuum at 190 캜 under a pressure of 0.11 MPa for 3 minutes to prepare a test piece.

<< Measurement of the Presence Rate of Fluorine Atoms in the Adhesive Film >>

The first base material of the obtained test piece, the adhesion film and the second base material were separated, and the ratio of the presence of fluorine atoms on the A- and B-surfaces of the adhesion film was measured by X-ray photoelectron spectroscopy. A monochromatized AlKa line was irradiated with 25 W for an analysis area of 1400 m x 700 mu m of the adhesive film using PHI Quanta SXM (manufactured by ULVAC, Pa.), And the film was detected at an extraction angle of 45 deg. The existence ratio of fluorine atoms on the face and the B face was measured. The measurement temperature was room temperature (20 to 25 ° C), and the measurement pressure was 10 ^-8 Pa or less.

<< Evaluation of peelability >>

The test pieces prepared under the conditions shown in the following table were pulled in the vertical direction of the adherent film under the condition of 250 mm / min to confirm the peelability.

A: The maximum peeling force was less than 15 N,

B: Peeling force of 15N or more and less than 25N could be peeled at the maximum

C: Peeling force of 25N or more and less than 40N could be peeled

D: Maximum peel force is 50N or more or the wafer is broken

<< Evaluation of peeling interface >>

The peeling test was performed ten times to measure the number of peeling on the A-plane and the number of peeling on the B-plane.

[Table 2]

From the above results, Examples 1 to 16 were excellent in peelability. In addition, it was possible to peel off from the side A of the adhesive film, and the peeling interface was stable.

On the other hand, Comparative Examples 1 and 2 were poor in peelability. In Comparative Examples 3 to 5, peeling was observed on the A side of the adhesive film or on the B side, and the peeling interface was not stable.

[Test Example 2]

<Preparation of Adhesive Composition>

The following components were mixed to prepare an adhesive composition.

&Lt; tb &gt; &lt; TABLE &gt; Columns = 3 &lt; tb &gt;

Binder: The binder of the type shown in Table 3,

Irganox 1010 (manufactured by BASF Corporation): 5 parts by mass

Sumilizer TP-D (manufactured by Sumitomo Chemical Co., Ltd.): 5 parts by mass

Solvent: The solvent shown in Table 3 was added to the mass parts shown in Table 3

[Table 3]

The compounds listed in the table are as follows.

[Compound having fluorine atom]

(A-4): same as (A-4) described in Table 1

[bookbinder]

(B-1) to (B-3) described in Table 1:

(B-7): Septon 4033 (hydrogenated polystyrene elastomer, styrene content = 30 mass%, unsaturated double bond amount = less than 0.5 mmol / g, Type A durometer) = 76, manufactured by Kuraray Co., Ltd.)

(B-8): Septon 4044 (hydrogenated polystyrene elastomer, styrene content = 30 mass%, unsaturated double bond amount = less than 0.5 mmol / g, (subject)

(B-9): Kraton G1650 (hydrogenated polystyrene elastomer, content of styrene = 30 mass%, amount of unsaturated double bond = less than 0.5 mmol / g, (Type A durometer) = 70, manufactured by Kraton)

(B-10): Septon 8104 (hydrogenated polystyrene elastomer, styrene content = 60 mass%, unsaturated double bond amount = less than 0.5 mmol / g, Type A durometer) = 98, manufactured by Kuraray Co., Ltd.)

(B-11): Kraton A1535 (hydrogenated polystyrene elastomer, content of styrene = 58 mass%, amount of unsaturated double bond = less than 0.5 mmol / g, (Type A durometer) = 83, manufactured by Kraton)

&Lt; Preparation of test piece &

The above-mentioned adhesive composition was spin-coated on a silicon wafer (first substrate) having a diameter of 100 mm and a thickness of 525 탆, and dried at 110 캜 for 2 minutes and further at 190 캜 for 4 minutes to form a silicon wafer ) Having a thickness of 60 mu m. Hereinafter, the surface (air side surface) opposite to the first substrate of the adhesive film is also referred to as the A side. The surface of the adhesive film on the first base side is also referred to as the B side.

A silicon wafer (second substrate) having a diameter of 100 mm and a thickness of 525 m was pressed on the side of the laminate on which the adhesion film was formed and under vacuum at 190 DEG C and 0.11 MPa for 3 minutes to prepare test pieces.

<< Measurement of the Presence Rate of Fluorine Atoms in the Adhesive Film >>

The first base material of the obtained test piece, the adhesion film and the second base material were separated, and the ratio of the presence of fluorine atoms on the A- and B-surfaces of the adhesion film was measured by X-ray photoelectron spectroscopy. A monochromatized AlKa line was irradiated with 25 W for an analysis area of 1400 m x 700 mu m of the adhesive film using PHI Quanta SXM (manufactured by ULVAC, Pa.), And the film was detected at an extraction angle of 45 deg. The existence ratio of fluorine atoms on the face and the B face was measured. The measurement temperature was room temperature (20 to 25 ° C), and the measurement pressure was 10 ^-8 Pa or less.

<< Evaluation of peelability >>

The test pieces prepared under the conditions shown in the following table were pulled in the vertical direction of the adherent film under the condition of 250 mm / min to confirm the peelability.

A: The maximum peeling force was less than 15 N,

B: Peeling force of 15N or more and less than 25N could be peeled at the maximum

C: Peeling force of 25N or more and less than 40N could be peeled

D: Maximum peel force is 50N or more or the wafer is broken

<< Evaluation of peeling interface >>

The peeling test was performed ten times to measure the number of peeling on the A-plane and the number of peeling on the B-plane.

<Flat abrasive property>

The first base material of the prepared test piece was polished until the thickness became 35 탆. The abraded first substrate was visually inspected to confirm whether or not a concave portion having a diameter of 1 mm or more was present.

A: No indentation at all

B: The concave part is slightly generated, but it is acceptable.

C: The concave portion is generated in a large amount and can not be accepted.

&Lt; Wafer bending >

The first base material of the prepared test piece was polished until the thickness became 35 mu m and then the heating rate and the cooling rate were set at 10 DEG C / min using FLX-2320 manufactured by KLA-Tencor, After heating up to 200 DEG C, the temperature was cooled to room temperature and Bow value was measured.

A: Bow value is 40μm or less

B: Bow value exceeding 40 탆 and less than 80 탆

C: Bow value of 80μm or more

[Table 4]

From the above results, Examples 17 to 30 were excellent in peelability. In addition, it was possible to peel off from the side A of the adhesive film, and the peeling interface was stable.

Further, the flat polishing property was good and the warpage of the wafer was suppressed.

In Examples 17 to 26 in which the elastomer A and the elastomer B were used in combination as the elastomer, the flat abrasion resistance was particularly good.

[Test Example 3]

<Preparation of Adhesive Composition>

The following components were mixed to prepare an adhesive composition.

(Composition of Adhesive Composition)

&Lt; - &gt; Fluorine atom-containing compounds:

Binder: The kind shown in Table 5, the mass part shown in Table 5

Radical Polymerizable Compound: The radical polymerizable compound of the type shown in Table 5,

Irgainox 1010 (manufactured by BASF Corporation): 0.9 parts by mass

Sumilizer TP-D (manufactured by Sumitomo Chemical Co., Ltd.): 0.9 parts by mass

Solvent: The solvent shown in Table 5 was added to the mass part

[Table 5]

The compounds shown in Table 5 are as follows.

[Compound having fluorine atom]

(A-1): same as (A-1) in Table 1

[bookbinder]

(B-2): same as (B-2) in Table 1

(Type A durometer) = 78, Gurare (Note) (B-12) Septon V9827 (hydrogenated polystyrene elastomer, styrene content = 30 mass% )My)

[Radical Polymerizable Compound]

(C-1) NK Ester M-40G (monohydric methacrylate structure of Shin Nakamura Kagaku Kogyo Co., Ltd.)

[Chemical Formula 14]

(C-2) NK Ester 4G (Shin-Nakamura Kagaku Kogyo Kabushiki Kaisha, second functional methacrylate structure below)

[Chemical Formula 15]

(C-3) NK Ester A-9300 (the following structure of a tertiary acrylate of Shin Nakamura Kagaku Kogyo Co., Ltd.)

[Chemical Formula 16]

(C-4) triallyl isocyanurate (trifunctional allyl compound manufactured by Tokyo Kasei Kogyo Co., Ltd.)

[Chemical Formula 17]

(C-5) NK Ester A-TMMT (manufactured by Shin Nakamura Kagaku Kogyo Co., Ltd., tetrafunctional acrylate)

[Chemical Formula 18]

(C-6) NK Ester A-DPH (manufactured by Shin Nakamura Kagaku Kogyo Co., Ltd., hexafunctional acrylate)

[Chemical Formula 19]

(C-7) NK Ester A-BPE-4 (bifunctional acrylate, manufactured by Shin Nakamura Kagaku Kogyo Co., Ltd.)

[Chemical Formula 20]

&Lt; Preparation of test piece &

The above-mentioned adhesive composition was spin-coated on a silicon wafer (first substrate) having a diameter of 100 mm and a thickness of 525 m and dried at 110 ° C for 2 minutes and further at 150 ° C for 4 minutes to obtain a silicon wafer ) Having a thickness of 60 mu m. Hereinafter, the surface (air side surface) opposite to the first substrate of the adhesive film is also referred to as the A side. The surface of the adhesive film on the first base side is also referred to as the B side.

A silicon wafer (second substrate) having a diameter of 100 mm and a thickness of 525 m was pressed on the side of the laminate on which the adhesion film was formed for 3 minutes under a vacuum of 220 DEG C and a pressure of 0.11 MPa to prepare a test piece.

<< Measurement of the Presence Rate of Fluorine Atoms in the Adhesive Film >>

The first base material, the adhesion film and the second base material of the obtained test piece were separated, and the presence ratio of fluorine atoms on the A-plane and B-plane of the adhesion film was measured by X-ray photoelectron spectroscopy. A monochromatized AlKa line was irradiated with 25 W for an analysis area of 1400 m x 700 mu m of the adhesive film using PHI Quanta SXM (manufactured by ULVAC, Pa.), And the film was detected at an extraction angle of 45 deg. The existence ratio of fluorine atoms on the face and the B face was measured. The measurement temperature was room temperature (20 to 25 ° C), and the measurement pressure was 10 ^-8 Pa or less.

<< Evaluation of peelability >>

The test pieces prepared under the conditions shown in the following table were pulled in the vertical direction of the adherent film under the condition of 250 mm / min to confirm the peelability.

A: The maximum peeling force was less than 15 N,

B: Peeling force of 15N or more and less than 25N could be peeled at the maximum

C: Peeling force of 25N or more and less than 40N could be peeled

D: Maximum peel force is 50N or more or the wafer is broken

<< Evaluation of peeling interface >>

The peeling test was performed ten times to measure the number of peeling on the A-plane and the number of peeling on the B-plane.

<Flat abrasive property>

The first base material of the prepared test piece was polished until the thickness became 35 탆. The abraded first substrate was visually inspected to confirm whether or not a concave portion having a diameter of 1 mm or more was present.

A: No indentation at all

B: The concave part is slightly generated, but it is acceptable.

C: The concave portion is generated in a large amount and can not be accepted.

&Lt; Wafer bending >

The first base material of the prepared test piece was polished until the thickness became 35 μm, and then the heating rate and the cooling rate were set at 10 ° C./minute by using FLX-2320 manufactured by KLA-Tencor Co., After heating, it was cooled to room temperature, and Bow value was measured.

A: Bow value is 40μm or less

B: Bow value exceeding 40 탆 and less than 80 탆

C: Bow value of 80μm or more

[Table 6]

From the above results, the examples were excellent in peelability. In addition, the peeling interface was stable.

Further, the flat polishing property was good and the warpage of the wafer was suppressed.

[Test Example 4]

&Lt; Preparation of test piece &

The adhesive composition used in Examples 1 to 40 was applied onto the surface of a 12-inch diameter silicon wafer (1 inch is 2.54 cm) subjected to edge trimming treatment with a width of 500 탆 and a depth of 100 탆 provided with a plurality of bumps, (Synapse V, manufactured by Tokyo Electron, Co., Ltd.) while rotating at 50 rpm. The rotation number was raised to 600 rpm and held for 30 seconds. Then, mesitylene was supplied to the outer periphery of the silicon wafer and the backside of the silicon wafer for 40 seconds while rotating the silicon wafer to clean the adhesion composition adhered to the outer periphery of the silicon wafer and the back surface of the silicon wafer did. An adhesive film was formed on the surface of the silicon wafer by heating at 110 DEG C for 3 minutes using a hot plate and further heating at 190 DEG C for 3 minutes.

Then, another 12-inch silicon wafer (carrier substrate) was vacuum-bonded to the surface of the side on which the adhesion film was formed by a wafer bonding apparatus (Synapse V manufactured by Tokyo Electron) at 190 ° C and 0.11 MPa At a pressure of 5 MPa for 3 minutes to obtain a laminate. The thickness of the adhesive film at this time was 40 占 퐉.

Next, the silicon wafer side of the above-mentioned laminate was polished down to a thickness of 35 mu m using a back grinder DFG8540 (Disco) to obtain a thin laminated body.

The diameter of the thinned silicon wafer of the laminate was 299 mm.

<End face treatment after thinning>

The thinned laminate was immersed in a 15 mL (10 mL) solution of mesitylene at 20 mm from the end of the silicon wafer for 10 seconds while rotating the carrier at 300 rpm by using a wafer bonding apparatus (Synex V, manufactured by Tokyo Electron) And added. Then, the number of revolutions was increased to 1000 rpm and 45 mL of mesitylene was added dropwise for 30 seconds. Thereafter, the surface of the silicon wafer was dried by rotating for 20 seconds while maintaining the rotation speed at 1000 rpm.

The obtained laminate was observed with an optical microscope from a direction perpendicular to a 12-inch diameter silicon wafer provided with a plurality of bumps. As a result, it was confirmed that the diameter of the substrate surface of the adhesive film was smaller than the diameter of the substrate surface of the carrier substrate by 250 占 퐉 or more there was. The diameter of the film surface of the adherent film on the side in contact with the carrier substrate was larger than the diameter of the film surface on the side in contact with the device wafer.

11, 11a:
12: carrier substrate
60: device wafer
60a: thin device wafer
61: silicon substrate
62: Device chip
100: Adhesive substrate

Claims (32)

A process for producing an adhesion film comprising a step of coating a support composition with a composition for adhesion in a layer form and drying,
Wherein the adhesive composition comprises a compound having a fluorine atom,
The above-mentioned adherent film was subjected to X-ray photoelectron spectroscopy of the surface of the adherent film, which was measured by irradiating a monochromatic AlK? Line at 25 W to an analysis area range of 1400 μm × 700 μm on the surface of the adherent film, Wherein a ratio A of the presence of fluorine atoms on the surface of the adhesion film opposite to the support and a ratio B of the presence of fluorine atoms on the surface of the adhesion film on the support side, , And satisfying the relationship of the following formula (1) and the presence ratio A of the fluorine atom is 5 to 40%;
A / B? 1.3 (1)
A is the ratio A of the presence of fluorine atoms on the surface of the adhesive film opposite to the support,
B is the presence ratio B of fluorine atoms on the surface of the adhesive film on the support side. The method according to claim 1,
The adhesion film is such that the presence ratio A of the fluorine atom and the presence ratio B of the fluorine atom satisfy the relation of the following formula (2) and the presence ratio A of the fluorine atom is 10 to 30% A method of producing a membrane;
A / B? 1.5 (2)
A is the ratio A of the presence of fluorine atoms on the surface of the adhesive film opposite to the support,
B is the presence ratio B of fluorine atoms on the surface of the adhesive film on the support side. The method according to claim 1 or 2,
Wherein the fluorine atom-containing compound has a hydrophilic group. The method according to any one of claims 1 to 3,
Wherein the adhesive composition comprises at least one selected from a binder and a radical polymerizable compound. The method of claim 4,
Wherein the binder is a block copolymer. The method according to claim 4 or 5,
Wherein the binder is a styrene block copolymer having one end or both ends of the styrene block. The method according to any one of claims 4 to 6,
Wherein the binder is a hydrogenation product of a block copolymer. The method of claim 4,
Wherein the binder is an elastomer. The method of claim 8,
Wherein the elastomer comprises a repeating unit derived from styrene. The method according to claim 8 or 9,
Wherein the elastomer is a hydrogenated product. The method according to any one of claims 8 to 10,
Wherein the elastomer is a styrene block copolymer having one end or both ends of the styrene block. The method according to any one of claims 8 to 11,
The elastomer comprises an elastomer A containing repeating units derived from styrene in a proportion of 10% by mass or more and 50% by mass or less in the total repeating units and an elastomer A containing 50% by mass or more and 95% by mass % Or less of the total amount of the elastomer (B). The method of claim 12,
Wherein the mass ratio of the elastomer A and the elastomer B is 5: 95 to 95: 5. The method of claim 4,
Wherein the radical polymerizing compound is a compound having two or more radically polymerizable groups. The method according to claim 4 or 14,
Wherein the radical polymerizing compound has at least one of partial structures represented by the following (P-1) to (P-4); However, * in the equation is a connecting hand.
[Chemical Formula 1]

The method according to any one of claims 4, 14 and 15,
(Meth) acrylate, isocyanuric acid ethylene oxide modified di (meth) acrylate, isocyanuric acid ethylene oxide modified tri (meth) acrylate, iso (meth) acrylate, (Meth) acrylate, pentaerythritol tetra (meth) acrylate, dimethylol propane tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, (Meth) acrylate, dipentaerythritol hexa (meth) acrylate, and tetramethylolmethane tetra (meth) acrylate. The method according to any one of claims 1 to 16,
Wherein the adhesive composition comprises the fluorine atom-containing compound in a total solid content of the adhesive composition in an amount of 0.03 mass% or more and less than 0.5 mass%. The method according to any one of claims 1 to 17,
Wherein the average thickness of the adhesive film is from 0.1 to 500 mu m. An adhesion film comprising a compound having a fluorine atom,
The adhesion film is a single-layer film,
The surface of the adhesive film was examined by X-ray photoelectron spectroscopy of the surface of the adhesive film, which was measured by irradiating a monochromated AlK? Line at 25 W to an analysis area of 1400 占 퐉 占 700 占 퐉 at an extraction angle of 45 占The abundance ratio is such that the abundance ratio B1 of the fluorine atoms on the one surface a of the adhesive film and the presence ratio B1 of fluorine atoms on the surface b of the adhesion film on the opposite side to the surface a satisfy the following relationship: An adhesion film satisfying the relationship of the following formula (11) and having a fluorine atom abundance ratio A1 of 5 to 40%;
A1 / B1? 1.3 (11)
A1 is the ratio A1 of the presence of fluorine atoms on the surface a of the adhesive film,
B1 is the presence ratio B1 of fluorine atoms on the surface b of the adhesive film. The method of claim 19,
The adhesion film is such that the presence ratio A1 of the fluorine atom and the presence ratio B1 of the fluorine atom satisfy the relation of the following formula (12) and the presence ratio A1 of the fluorine atom is 10 to 30% membrane;
A1 / B1? 1.5 (12)
A1 is the ratio A1 of the presence of fluorine atoms on the surface a of the adhesive film,
B1 is the presence ratio B1 of fluorine atoms on the surface b of the adhesive film. The method according to claim 19 or 20,
Wherein the fluorine atom-containing compound has a hydrophilic group. The method according to any one of claims 19 to 21,
Wherein the adhesive film comprises at least one kind selected from a binder and a radical polymerizable compound. The method as claimed in any one of claims 19 to 22,
Wherein the adhesive film contains the fluorine atom-containing compound in an amount of 0.03 mass% or more and less than 0.5 mass% in the total solid content of the adhesive film. An adhesive film obtained by the manufacturing method according to any one of claims 1 to 18 or the adhesive film according to any one of claims 19 to 23,
Wherein the adhesive layer has a base material on one side or both sides of the adhesive film. An adherent film obtained by a manufacturing method according to any one of claims 1 to 18 or an adherent film according to any one of claims 19 to 23 between a carrier substrate and a device wafer, Wherein a surface of the carrier substrate is in contact with a device surface of the device wafer and the other surface is in contact with a surface of the carrier substrate. 26. The method of claim 25,
Wherein the area of the film surface of the adhesive film is smaller than the area of the substrate surface of the carrier substrate. 26. The method of claim 25,
(C-200)? T? D when the diameter of the substrate surface of the carrier substrate is C m, the diameter of the substrate surface of the device wafer is D m, and the diameter of the film surface of the adhesive film is T m. . 26. The method of claim 25,
The diameter of the substrate surface of the carrier substrate is _C mu m, the diameter of the substrate surface of the device wafer is _D mu m, the diameter of the film surface of the adhesive film on the side in contact with the carrier substrate is T _C mu m, (C-200)? T _C > T _D ? _D when the diameter is T _D占 퐉. A composition for adhesion comprising a compound having a fluorine atom,
Wherein the fluorine atom-containing compound is contained in an amount of 0.03 mass% or more and less than 0.5 mass% in the total solid content of the adhesive composition. 29. The method of claim 29,
Wherein the fluorine atom-containing compound has a hydrophilic group. 29. The method of claim 29 or 30,
A binder, and a radical polymerizable compound. 32. The method of claim 31,
Wherein the binder is an elastomer.

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