KR20160149245A - Temporary adhesion laminate, temporary adhesion laminate manufacturing method, and laminate equipped with device wafer - Google Patents

Abstract

It is possible to stably adhere the device wafer and the support to each other with good flatness on the adhesion surface with the device wafer or the support and to easily release adhesion between the device wafer and the support, A method of manufacturing a laminate for adhesion, and a laminate having a device wafer.
The adhesive laminate may be a laminate of a polystyrene type elastomer, a polyester type elastomer, a polyolefin type elastomer, a polyurethane type elastomer, a polyamide type elastomer, a polyacrylic type elastomer, a silicone type elastomer, a polyimide type elastomer, , Polyphenylene sulfide, polyphenylene ether, and polyethersulfone, and a film comprising at least one surface of a film of a release agent containing at least one selected from a fluorine atom and a silicon atom And a release layer.

Description

TECHNICAL FIELD [0001] The present invention relates to a laminate for adhesion, a method for manufacturing a laminate for adhesion, and a laminate for device wafer lamination,

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a laminate for adhesion, a method for manufacturing a laminate for adhesion, and a laminate with a device wafer. More particularly, the present invention relates to a laminate for adhesion, a method for manufacturing a laminate for adhesion, and a laminate having a device wafer, 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. For example, thinning of the device wafer has been studied, leading to miniaturization of the IC chip, and also making the manufacturing process of the through-hole of the device wafer in the production of the silicon through- It is promising in that it can be done. 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 μm or less is extremely thin, and a semiconductor device manufacturing member made of a base material is very thin. Therefore, such a member is subjected to additional processing or simply moved It is difficult to support the member stably and without damaging it.

In order to solve the problems described above, a device wafer before a thinning process, in which a device is provided on a surface thereof, and a working support substrate are adhered to each other by means of a silicon pressure sensitive adhesive and the back surface of the device wafer is ground to thin, And thereafter, the supporting substrate for processing is removed from the device wafer (refer to Patent Document 1). According to this technology, it is possible to simultaneously achieve the internal grinding resistance at the time of back grinding of the device wafer, the heat resistance in the anisotropic dry etching process, the chemical resistance at the time of plating and etching, the smooth peeling with the final supporting substrate for processing, It is said that it is possible to do.

As a method for supporting the wafer, there is a method of supporting the wafer by the support layer system, in which a plasma polymer layer obtained by the plasma deposition method is interposed between the wafer and the support layer system as a separation layer, A technique is known in which the adhesive bond between the separation layers is made larger than the bonding bond between the wafer and the separation layer so that the wafer is easily separated from the separation layer when the wafer is detached from the support layer system Reference).

Further, there is known a technique in which polyether sulfone and a viscosity-imparting agent are used to perform adhesion and releasing adhesion by heating (see Patent Document 3).

Further, there is also known a technique in which adhesion is performed by a mixture of carboxylic acids and amines and release of adhesion by heating (see Patent Document 4).

Further, there is known a technique in which a device wafer and a supporting substrate are adhered to each other by pressing and bonding in a state in which a bonding layer made of cellulose polymers or the like is heated, and the device wafer is removed from the supporting substrate by heating and sliding in the lateral direction Reference).

Further, an adhesive film made of syndiotactic 1,2-polybutadiene and a photopolymerization initiator and having an adhesive force changed by irradiation of radiation is known (refer to Patent Document 6).

Further, by the adhesive made of a polycarbonate, the support substrate and the device wafer are adhered to each other, the device wafer is treated, the irradiation line is irradiated, and then the wafer is heated, thereby removing the processed device wafer from the support substrate (See Patent Document 7).

Further, there is known a technique in which a support substrate and a device wafer are adhered to each other with two layers having different softening points, a device wafer is processed, and then heated and slid in the lateral direction to thereby separate the support substrate and the device wafer 8).

Patent Document 9 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 temporarily fixed by means of a temporary fixing material containing a compound having at least one kind of structure.

Patent Document 10 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 11 discloses a method for manufacturing a semiconductor device in which an adhesive layer is applied and formed on the device surface of a device wafer, a release layer containing a fluorinated silane compound is applied and formed on the surface of the support, an adhesive layer on the device wafer and a release layer on the support are bonded, Thereby bonding the device wafer and the support.

Patent Document 12 discloses that a device wafer and a support are adhered to each other by using a temporary film sheet having a low adhesion layer on both sides or one side of a temporary fixing film comprising a specific polyimide resin.

Patent Document 1: JP-A-2011-119427 Patent Document 2: Japanese Published Patent Application No. 2009-528688 Patent Document 3: JP-A-2011-225814 Patent Document 4: JP-A-2011-052142 Patent Document 5: Japanese Published Patent Application No. 2010-506406 Patent Document 6: JP-A-2007-045939 Patent Document 7: U.S. Patent Application Publication No. 2011/0318938 Patent Document 8: U.S. Patent Publication No. 2012/0034437 Patent Document 9: JP-A-2013-241568 Patent Document 10: JP-A-2014-34632 Patent Document 11: International Publication No. WO2013 / 119976 Patent Document 12: JP-A-2014-29999

In the case where the surface of the device wafer on which the device is provided (that is, the device surface of the device wafer) and the supporting substrate (carrier substrate) are adhered to each other via a layer made of a pressure sensitive adhesive known in Patent Document 1 or the like, In order to stably support the adhesive layer, a certain degree of tackiness is required for the adhesive layer.

Therefore, when the entire surface of the device surface of the device wafer and the support are adhered to each other with the adhesive layer interposed therebetween, sufficient adhesion between the device wafer and the support can be ensured and the device wafer can be supported stably On the other hand, a too strong adhesion between the device wafer and the support tends to cause defects such as breakage of the device or removal of the device from the device wafer when removing the device wafer from the support.

A method of forming a plasma polymer layer as a separation layer by a plasma deposition method between a wafer and a support layer system in order to suppress adhesion between the wafer and the support layer system from being too strong is as follows: 1) In general, the facility cost for carrying out the plasma deposition method is large; (2) Formation of a layer by the plasma deposition method requires time for vacuuming in the plasma apparatus or deposition of the monomers; And (3) even when a separation layer made of a plasma polymer layer is provided, in the case of supporting a wafer provided for processing, in the case of releasing the support of the wafer while making sufficient adhesion bonding between the wafer and the separation layer, It is not easy to control the wafer with an adhesive bond that is easily separated from the separation layer; And the like.

Also, in the method of releasing the adhesion by heating, as described in Patent Documents 3, 4 and 5, a defect that the device is damaged when the device wafer is detached from the support tends to occur.

In addition, as in Patent Documents 6 and 7, in the method of releasing adhesion by irradiating a radiation, it is necessary to use a support that transmits radiation.

When the softening point of the bonding layer on the device wafer side is 20 ° C or more higher than the softening point of the bonding layer on the substrate side as in Patent Document 8, the bonding layer on the substrate side is transferred to the bonding layer on the device wafer side after peeling, The cleaning property of the device wafer is deteriorated.

In addition, when the adhesive of Patent Document 9 is used as a temporary fixture, the peelability is insufficient, and there is a problem that a defect that the device is damaged when the device wafer is peeled easily occurs.

In Patent Document 10, the adhesive composition is applied to a device wafer or a support to form an adhesive layer. When the adhesive layer was applied and formed, the thickness deviation easily occurred. If a thickness variation occurs in the adhesive layer, the adhesion to the device wafer or the support tends to be poor. In addition, in the method disclosed in Patent Document 10, the peelability of the support from the device wafer was insufficient.

In Patent Document 11, since the adhesive layer and the release layer are applied to the device wafer or the support respectively, the adhesive layer and the release layer tend to be easily varied in thickness, and the adhesion tends to be poor. However, Resulting in a problem that the back surface of the device wafer can not be treated uniformly.

In the method disclosed in Patent Document 12, the followability to the shape of the surface of the device is insufficient, the adhesiveness is not sufficient, and vacancies are generated. If the back surface of the device is ground to be thinned, there is a problem that it can not be thinned to a uniform thickness.

SUMMARY OF THE INVENTION The present invention has been made in view of the above background, and an object of the present invention is to provide a device wafer and a method of manufacturing a device wafer, A method for manufacturing a laminate for adhesion, and a laminate having a device wafer, which can easily release adhesion of a support.

Means for Solving the Problems As a result of intensive investigations in order to solve the above problems, the present inventors have found that when an adhesive film having a release layer containing a releasing agent containing at least one selected from a fluorine atom and a silicon atom is formed on one side or both sides of a specific film It has been found that the device wafer and the support can be adhered to each other by a high adhesive force and the adhesion between the device wafer and the support can be easily released, I have come to completion. The present invention provides the following.

≪ 1 > A laminate for adhesion, which is used for releasably adhering a device surface of a device wafer and a support in a peelable manner, comprising a polystyrene elastomer, a polyester elastomer, a polyolefin elastomer, a polyurethane elastomer, , A film comprising at least one selected from the group consisting of a polyacrylic elastomer, a silicone-based elastomer, a polyimide elastomer, a polyetheretherketone, polyphenylene sulfide, polyphenylene ether and polyether sulfone, And a releasing layer comprising a releasing agent containing at least one selected from a fluorine atom and a silicon atom on one surface thereof.

≪ 2 > The adhesive laminate according to < 1 >, wherein the film comprises at least one selected from the group consisting of polystyrene elastomer and polyethersulfone.

≪ 3 > The adhesive laminate according to < 1 >, wherein the film comprises a polystyrene-based elastomer.

≪ 4 > The adhesive layered laminate according to any one of < 1 > to < 3 >, wherein the polystyrene-based elastomer is a hydrogenated product.

<5> The laminate for adhesion according to any one of <1> to <4>, wherein the 5% thermal mass reduction temperature of the polystyrene-based elastomer heated from 25 ° C. to 20 ° C./min is 250 ° C. or higher.

<6> The adhesive layered laminate according to any one of <1> to <5>, wherein the releasing agent is a silane coupling agent.

<7> The laminate for adhesion according to any one of <1> to <6>, wherein the release layer is provided on both surfaces of the film.

<8> The laminate for adhesion according to any one of <1> to <6>, wherein the release layer is provided on only one surface of the film.

<9> The resin composition according to any one of <1> to <9>, wherein the polyolefin elastomer is at least one selected from the group consisting of polystyrene elastomer, polyester elastomer, polyolefin elastomer, polyurethane elastomer, polyamide elastomer, polyacrylic elastomer, silicone elastomer, polyimide elastomer, Comprising a step of forming a release layer comprising a release agent containing at least one selected from a fluorine atom and a silicon atom on a surface of a film comprising at least one member selected from the group consisting of a fluorine atom and a polyethersulfone, Wherein the method comprises the steps of:

<10> A laminate for adhering according to any one of <1> to <8>, which is provided between a device wafer and a support, wherein one surface of the adherent laminate is in contact with a device surface of the device wafer, Wherein the surface is in contact with the surface of the support.

<11> The device wafer laminate according to <10>, wherein the adhesive laminate has a release layer on both surfaces of the film.

<12> The laminate for adhering a device wafer according to <10>, wherein the adhesive laminate has a release layer on only one surface of the film, and the release layer is in contact with the surface of the device wafer.

<13> The device wafer laminate according to <10>, wherein the adhesive layer laminate has a release layer on only one surface of the film, and the release layer is in contact with the support.

According to the present invention, it is possible to stably adhere the device wafer and the support to each other with good flatness on the adhesion surface with the device wafer or the support, and to easily release adhesion between the device wafer and the support It is possible to provide a laminate for adhesion, a method for manufacturing a laminate for adhesion, and a laminate with a device wafer.

1 is a schematic view of an embodiment showing a method of manufacturing a semiconductor device.
Fig. 2 is a schematic cross-sectional view illustrating release of the adhesion state between a conventional adhesive support and a device wafer. Fig.

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 "actinic ray" or "radiation" 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 "light" means an actinic ray or radiation.

As used herein, the term "exposure" 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.

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

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 this 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), TSKgel Super AWM- 6.0 mm ID x 15.0 cm) of 10 mmol / L lithium bromide NMP (N-methylpyrrolidinone) solution as an eluent.

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.

&Lt; Adhesive laminate &

The adhesive laminate according to the present invention is a laminate for adhesive lamination which is used for releasably adhering a device surface of a device wafer and a support in a peelable manner. The laminate is a polystyrene elastomer, a polyester elastomer, a polyolefin elastomer, At least one selected from the group consisting of phosphorus-based elastomer, polyamide-based elastomer, polyacrylic elastomer, silicone-based elastomer, polyimide elastomer, polyetheretherketone, polyphenylene sulfide, polyphenylene ether and polyether sulfone (Hereinafter also referred to as an adhesive film), and a release layer comprising a release agent containing at least one selected from a fluorine atom and a silicon atom on at least one surface of the film.

Since the adhesive laminate of the present invention uses a film, flatness on the adhesion surface with the device wafer or the support is good. That is, when a coating film or the like formed by coating is used as the adhesive layer, since the solvent is contained in the adhesive layer, the film thickness is unlikely to be uniform due to drying shrinkage or the like and the adhesiveness is lowered. However, The content of the solvent in the adhesive layer can be reduced and the nonuniformity of the thickness of the adhesive layer can be suppressed and consequently the adhesiveness can be improved. Further, since the adhesive film includes the above-described material, it is possible to achieve more excellent adhesiveness by following the fine irregularities of the device wafer and the support by appropriate anchor effect. Since the surface layer of the adhesive film has a release layer containing a release agent containing at least one selected from a fluorine atom and a silicon atom, excellent peelability can be achieved. As a result, the self-adhesive laminate of the present invention is excellent in flatness, adhesiveness, and peelability.

In this specification, "a device wafer and a supporting member are peelably adhered" in this specification means that a device wafer and a supporting member are adhered to each other, The bonding state is released to separate the two. It is preferable that release by the mechanical peeling is released.

In the present specification, the term "film" means flat film or plate. Means that the difference between the maximum film thickness and the minimum film thickness is preferably 20% or less, more preferably 5% or less, of the average film thickness of the film in a cross section along one direction of the film . Alternatively, the coating film tends to cause a thickness variation, and further, since the coating film contains a solvent, it is difficult for the film thickness to become uniform due to drying shrinkage or the like.

The solvent content of the film is, for example, preferably 20 mass% or less, more preferably 5 mass% or less, and particularly preferably not contained. The solvent content of the film can be measured by gas chromatography.

The film can be produced by, for example, a melt film-forming method, a solution film-forming method, or the like which will be described later.

Hereinafter, the adhesive layer laminate of the present invention will be described in detail.

<< Adhesive film >>

In the adhesive laminate of the present invention, the average thickness of the adhesive film is not particularly limited, but is preferably 0.1 to 500 m, more preferably 0.1 to 200 m, further preferably 10 to 200 m , And particularly preferably from 50 to 200 mu m. When the average thickness of the adhesive film is within the above range, flatness is good. Further, in the case of the coated film, the flatness tends to decrease as the thickness increases (for example, 10 탆 or more), but the flatness is excellent even if the thickness is large.

In the present invention, the average thickness of the adhesive film is set such that the thickness of the adhesive film in a section along one direction from the one end face to the other end face and at five places at equal intervals, It is defined as the average of the values measured by the tree.

In the present invention, "a cross section along one direction of the adhesive film" is a cross section perpendicular to the long side direction when the adhesive film is rectangular. When the adhesive film is in the form of a square, the cross section is orthogonal to either one of the sides. When the adhesive film is circular or elliptical, it is a cross section passing through the center of gravity.

In the adhesive film of the present invention, the difference between the maximum film thickness and the minimum film thickness in a cross section along one direction of the adhesive film is preferably 20% or less of the average film thickness, and more preferably 5% or less.

In the adhesive laminate of the present invention, the adhesive film may be a thermoplastic film or a thermosetting film. Preferably, it is a thermoplastic film. By being a thermoplastic film, excellent adhesiveness can be obtained. In addition, even if the surface of the device wafer has irregularities, the conformability to the irregularities is good.

In the present invention, the thermoplastic film of, for example, a glass transition temperature of -50 ~ 300 ℃, the storage elastic modulus at 150 ~ 300 ℃, preferably from 10 ¹ ~ 10 ⁹ Pa preferably, 10 ² to 10 and more preferably of ⁸ Pa it is, 10 ³ to 10 ⁷ Pa, it is the most preferred. The storage elastic modulus is a value measured using a viscoelasticity measuring device under a constant temperature elevation condition. As the dynamic viscoelastic device, for example, Rheogel-E4000 (manufactured by UBM) can be used.

<<< Polymer Component >>>

In the adhesive laminate of the present invention, the adhesive film may be formed of a material selected from the group consisting of a polystyrene elastomer, a polyester elastomer, a polyolefin elastomer, a polyurethane elastomer, a polyamide elastomer, a polyacrylic elastomer, a silicone elastomer, a polyimide elastomer , Polyether ketone, polyphenylene sulfide, polyphenylene ether, and polyether sulfone. The polymer component is preferably at least one elastomer selected from a polystyrene elastomer, a polyester elastomer, a polyolefin elastomer, a polyurethane elastomer, a polyamide elastomer, a polyacrylic elastomer, a silicone elastomer and a polyimide elastomer, A polystyrenic elastomer is particularly preferred. The elastomer is preferably a hydrogenated product. Particularly, a hydrogenated product of a polystyrene type elastomer is preferable.

The adhesive film containing the polymer component can follow the fine irregularities of the support and the device wafer, and can form an adhesive layer having excellent adhesiveness by an appropriate anchor effect. Further, when the support is peeled from the device wafer, the support can be peeled from the device wafer without applying stress to the device wafer or the like, so that breakage or peeling of the device or the like can be prevented. Particularly, when the elastomer and further the polystyrene-based elastomer are used, the above effect is remarkable.

When the elastomer is a hydrogenated product, the thermal stability and the storage stability are improved. Further, the peelability and the cleaning removability of the laminate for adhesion after peeling are improved. When the hydrogenated product of the polystyrenic elastomer is used, the above effect is remarkable.

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 is instantaneously deformed according to its external force and has a property of recovering its original shape in a short time when an external force is removed.

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 assumed to be 100%, and the property of returning to 130% or less in a short time when the external force is removed .

The glass transition temperature of the polymer component (hereinafter also referred to as Tg) is preferably -50 to 300 ° C, more preferably 0 to 200 ° C. When the Tg is within the above range, it is possible to produce a laminate for adhesion having good adhesion with respect to the surface of the device wafer at the time of bonding and without voids. When the polymer component has two or more kinds of Tg, the value of Tg means a lower glass transition temperature.

The melting point of the polymer component is preferably -50 to 300 占 폚, more preferably 0 to 200 占 폚. When the melting point is within the above range, it is possible to produce a laminate for adhesion which has good followability to the surface of the device wafer at the time of bonding and has good adhesion without voids. When the polymer component has two or more kinds of melting points, the melting point means a lower melting point.

The weight average molecular weight of the polymer component is preferably 2,000 to 200,000, more preferably 10,000 to 200,000, and most preferably 50,000 to 100,000. In this range, even when the support is peeled from the device wafer and the adhesive layer laminate remaining on the device wafer and / or the support is removed, the solubility in the solvent is excellent, so that the residue remains on the device wafer or the support There is an advantage such as not.

The polymer component preferably has a 5% thermal mass reduction temperature from 25 캜 to 20 캜 / min of 250 캜 or higher, more preferably 300 캜 or higher, still more preferably 350 캜 or higher, Is most preferable. 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 a laminate for adhesion with excellent heat resistance. Particularly, it is easy to form a laminate for adhesion which can be used in an environment of 250 DEG C or more. The mass reduction temperature is a value measured under the temperature elevation condition under a nitrogen stream by a thermogravimetric analyzer (TGA).

<<<< 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 easy releasability, the lower limit value is preferably 25 mass% or more, more preferably 51 mass% or more.

The polystyrene-based elastomer is preferably a block copolymer of styrene and another resin. More preferably, the polystyrene-based elastomer is a block polymer of styrene at one terminal or both terminals, and particularly preferably a block polymer of styrene at both terminals. When the both ends of the polystyrene-based elastomer are styrene block polymers (repeating units derived from styrene), the thermal stability 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 believed that the shape of the phase separation contributes to suppressing the generation of irregularities on the substrate surface of the device wafer. Such a resin is more preferable from the viewpoint 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. In view of solubility in a solvent and resistance to a resist solvent, it is more preferable.

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.

The elastomer preferably has a 5% thermal mass reduction temperature from 25 占 폚 to 20 占 폚 / min of 250 占 폚 or higher, more preferably 300 占 폚 or higher, still more preferably 350 占 폚 or higher, desirable. 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 a laminate for adhesion with excellent heat resistance.

Examples of commercially available polystyrene elastomers include toughprene A, toughprene 125, toughprene 126S, solfrene T, asaprene T-411, asaprene T-432, asaprene T-437, , Asafrene T-439, Tuftec H1272, Tuftec P1500, Tuftec H1052, Tuftec H1062, Tuftec M1943, Tuftec M1911, Tuftec H1041, Tuftec MP10, Tuftec M1913, Tuftec H1051, Tuftec H1053 (Manufactured by Asahi Kasei Corporation), Elastomer AR-850C, Elastomer AR-815C, Elastomer AR-840C, Elastomer AR-830C, Elastomer AR-860C, Elastomer AR-875C, Elastomer Elastomer AR-SC-0, elastomer AR-SC-5, elastomer AR-710, elastomer AR-SC-65, elastomer AR-SC-30, elastomer AR- , Elastomer AR-SC-45, elastomer AR-720, elastomer AR-741, elastomer AR-731, elastomer AR- FL-85N, elastomer AR-FL-60N, elastomer AR-1050, elastomer AR-1060, elastomer AR-1040, elastomer AR-760, elastomer AR- (Aaron Gassée now), Kraton D1111, Kraton D1113, Kraton D1114, Kraton D1117, Kraton D1119, Kraton D1124, Kraton D1126, Kraton D1161, Kraton D1162, Kraton D1163, Kraton 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, Kraton Kleiton D1171, Kraton D1173, Kraton D1133, Kraton D1152, Kraton D1153, Kraton D1124, Kraton D1173, Creighton D1155 , Kraton D1184, Kraton D1186, Kraton D1189, Kraton D1191, Kraton D1192, Kraton DX405, Kraton DX408, Kraton DX410, Kraton DX414, Kraton DX415, Kraton A1535, Kraton A1536, Kr Leyton 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 , Kraton G1660, Kraton G1726, Kraton G1701, Kraton G1702, Kraton G1730, Kraton G1750, Kraton G1765, Kraton G4609, Kraton G4610 (manufactured by Kraton), TR2000, TR2001, TR2003, TR2250, TR2500 , TR2601, TR2630, TR2787, TR2827, TR1086, TR1600, SIS5002, SIS5200, SIS5250, SIS5405, SIS5505, DYNARON 6100P, DYNARON 4600P, DYNARON 6200P, DYNARON 4630P, DYNARON 8601P, DYNARON 8630P, DYNARON 8600P , Dynalon 8903P, Dynalon (DENARON 1321P, DYNARON 1320P, DYNARON 2324P, DYNARON 9901P (manufactured by JSR Corporation), Denka STR series (Manufactured by Sumitomo Chemical Co., Ltd.), Quartz 3450, Quintax 3460 (manufactured by Nippon Zeon), TPE-SB series (manufactured by Sumitomo Chemical Co., Ltd.), Lavalon series (manufactured by Mitsubishi Kagaku KK), Septon 1001, Septon, 8004, The following examples are provided to illustrate the invention and are not to be construed as limiting the scope of the present invention as defined by the appended claims. The invention is not limited to the following examples, but are not to be construed as limiting the scope of the present invention, as defined in the claims: 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 (available from Riken Vinyl High Strength Co., Ltd.), stearic acid (manufactured by Sumitomo Bakelite Co., Ltd.) 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 naphthalene dicarboxylic acid and aromatic dicarboxylic acids in which the hydrogen atoms of the aromatic nuclei are substituted with methyl, ethyl, phenyl and the like, adipic acid, Alicyclic dicarboxylic acids having 2 to 20 carbon atoms such as dicarboxylic acid, and cycloaliphatic 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, Aliphatic diols such as 1,4-cyclohexanediol, alicyclic diols, and divalent phenols represented by the following structural formulas.

[Chemical Formula 1]

^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 Toray DuPont), Pelprene (manufactured by Toyobo Co., Ltd.), Primaloy (manufactured by Mitsubishi Kagaku), Nuberan (manufactured by Deijin Gosei), Espel 1612 and 1620 Kasei Kogyo Co., Ltd.), and Primaloy CP300 (manufactured by Mitsubishi Kagaku 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 Co., Ltd.), Thermolun (Mitsubishi Kagaku Co., Ltd.), EXACT (Exxogaku Co., Ltd.), ENGAGE (manufactured by DOW CHEMICAL Co., Ltd.), S-pollex (Sumitomo Chemical Co., (New Jersey), 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 polymer (long chain) diol and diisocyanate, and a hard segment composed of low molecular weight glycol and diisocyanate 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), miractran (manufactured by Nippon Miraclast), ELASTOLAN (manufactured by BASF) , Pelletan (manufactured by Dow Chemical), Iron Rubber (manufactured by NOK), Mobil Ron (manufactured by Nisshinbo Chemical), and the like.

<<<< 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 Hulls), PEBAX (manufactured by Toray Industries, Inc.), Grilon ELY PAA-200, PA-201, TPAE-12, TPAE-32, polyester amide TPAE-32, 617, and TPAE-617C (manufactured by T & K TOKA Co., Ltd.).

<<<< Polyimide elastomer >>>>

The polyimide-based elastomer is not particularly limited and may be appropriately selected depending on the purpose. For example, an engineering plastic such as an aromatic polyimide and a block polymer composed of a rubber segment such as polyether, polyester or polyolefin having a soft segment of several hundreds to several hundreds of molecular weight, and alternately hard segments and soft segments are polycondensed Can be preferably used. Specific examples of commercially available products include, for example, UBESTA XPA9040F1 (manufactured by Ube Kosan Co., Ltd.) and the like.

<<<< Polyacrylic elastomer >>>>

The polyacrylic elastomer is not particularly limited and may be appropriately selected depending on the purpose. For example, there may be mentioned acrylic acid esters such as ethyl acrylate, butyl acrylate, methoxyethyl acrylate, ethoxyethyl acrylate and the like as the main components, acrylic esters and glycidyl methacrylate, allyl glycidyl ether And the like. And those obtained by copolymerizing acrylonitrile and crosslinking point monomers such as ethylene and the like. 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. The epoxy-based elastomer can be obtained by copolymerizing a part or all of the epoxy groups of a bisphenol F type epoxy resin, a bisphenol A type epoxy resin, a salicylaldehyde type epoxy resin, a phenol novolak type epoxy resin or a cresol novolak type epoxy resin, Terminal carboxylic acid-modified butadiene-acrylonitrile rubber, and terminal amino-modified silicone rubber.

<<<< Polyetherketone >>>>

Examples of the polyetherketone include ketone 1000 PEEK series, ketron HPV PEEK series, ketron GF30 PEEK series, ketron GA30 PEEK series (manufactured by Quadrant Polyphenko Japan Co., Ltd.) ).

<<<< Polyphenylene sulfide >>>>

Polyphenylene sulfide can be used without particular limitation, and examples thereof include Techtron 1000 PPS and Techtron HPVPPS (manufactured by Quadrant Polyphenko Japan).

<<<< Polyphenylene ether >>>>

As the polyphenylene ether, there can be used without particular limitation, and examples of the polyphenylene ether include Nippi Ace series, Remalo series (manufactured by Mitsubishi Engineering Plastic Co.), XYRON series (XYRON S201A etc.) (manufactured by Asahi Kasei Chemicals Co., Manufactured by SABIC Innovative Plastics Japan).

<<< Polyether sulfone >>>

As the polyethersulfone, there can be mentioned, for example, JP-A No. 2006-89595, JP-A No. 2004-352920, JP-A No. 2002-338688, JP-A No. 07-97447, And polyethersulfone disclosed in Japanese Patent Publication No. 04-20530.

By using polyethersulfone having an areene structure in the polymer among the polyethersulfone, the crystallinity of the film is increased, and the device wafer can be maintained with respect to the shearing force added during processing of the device wafer even under a high- It is easy to obtain a laminate for adhesion which is capable of maintaining a shear adhesive force which can be obtained. The polyethersulfone having an arene structure includes, for example, polyethersulfone having a constituent unit represented by the formula (IV).

(2)

In the formula (IV), R ¹ to R ³ are divalent organic groups having an arene structure, and the bond in formula (IV) is directly connected to the areene structure in R ¹ to R ³ (that is, is directly connected to, R ¹ ~ R ³ arene structure of -) of _{^{-OR 1 -O-, -OR 2 -SO 2}} - and -SO ₂ -R ³ -O- -O- and -SO ₂ in the have). R ¹ to R ³ may be the same or different.

Examples of the divalent organic group include an arylene group such as a phenylene group, a naphthalenediyl group, an anthracenediyl group and a pyrandiyl group; A group in which two arylene groups such as -C ₆ H ₄ -C ₆ H ₄ - are directly bonded; And groups having a bivalent hydrocarbon group between two arylene groups represented by the formulas (IV-1) to (IV-3).

(3)

In the formulas (IV-1) to (IV-3), * represents bonded hands.

The weight average molecular weight (Mw) of the polyethersulfone is preferably 1,000 to 1,000,000, more preferably 5,000 to 500,000. When the number average molecular weight of the polyethersulfone is Mn, the molecular weight distribution represented by Mw / Mn is preferably 1 to 5, more preferably 1 to 3.5.

As the polyethersulfone, a commercially available product may be used. Examples of commercially available products of polyether sulfone include "Ultrason E series" (Ultrason E 6020, etc.) manufactured by BASF, "Radial A series" manufactured by Solvay Advanced Polymer, and "Sumika Excel series" have. Examples of the "Sumika Excel series" include Sumika Excel (registered trademark) PES 3600P, Sumika Excel (registered trademark) PES4100P, Sumika Excel (registered trademark) PES4100MP, Sumika Excel (registered trademark) PES4800P, , Sumika Excel (registered trademark) PES5200P, and Sumika Excel (registered trademark) PES5400P.

The adhesive film preferably contains the polymer component in an amount of 50 to 100 mass%, more preferably 70 to 100 mass%, and particularly preferably 88 to 100 mass%, based on the entire solid content of the film. According to this embodiment, it is easy to obtain a laminate for adhesion with excellent adhesion and peelability. The polymer component may contain plural kinds of the above-mentioned kinds.

The polymer component preferably contains a styrene-based elastomer in an amount of 50 to 100 mass%, more preferably 80 to 100 mass%, further preferably 90 to 100 mass%, more preferably a styrene- Is particularly preferable. According to this embodiment, it is easy to obtain a laminate for adhesion with excellent adhesion and peelability.

<<< Antioxidants >>>

The adhesive film may contain an antioxidant from the viewpoint of preventing low molecular weight or gelation of the polymer component due to oxidation at the time of heating. 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 (registered trademark) 1010, Irganox (registered trademark) 1350 ", "Irganox (registered trademark) 3114 "," Irganox (registered trademark) 1035 ", Sumilizer (registered trademark) MDP-S made by Sumitomo Chemical Co., .

Examples of the sulfur-based antioxidant include 3,3'-thiodipropionate distearyl, Sumilizer (registered trademark) TPM, Sumilizer (registered trademark) TPS, Sumilizer (registered trademark) Registered trademark) TP-D ".

Examples of the phosphorus antioxidant include tris (2,4-di-tert-butylphenyl) phosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, poly Irgafos (registered trademark) 168, Irgafos (registered trademark) 38, etc., manufactured by BASF Co., Ltd., and the like can be used. .

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 (registered trademark) 1010, Irganox (registered trademark) 1330, 3,3'-thiodipropionate distearyl, Sumilizer (registered trademark) TP- , Irganox (registered trademark) 1330 is more preferable, and Irganox (registered trademark) 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, it is expected that the deterioration of the elastomer by the oxidation reaction can be effectively suppressed. 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.

Examples of combinations of antioxidants include Irganox TM 1010, Sumilizer TM TP-D, Irganox TM 1330 and Sumilizer TM TP-D, and Sumilizer TM GA-80 and Sumilizer TM (registered trademark) Irganox TM 1010 and Sumilizer TM TP-D, Irganox TM 1330 and Sumilizer TM TP-D are more preferred, and Irganox TM (registered trademark) ) 1010 and Sumilizer (registered trademark) TP-D are particularly preferred.

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 film 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 film.

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.

<<< Polymer compound >>>

The adhesive film may have a polymer compound other than the above-mentioned polymer component, if necessary.

In the present invention, any of the polymer compounds may be used. The polymer compound is a compound having a weight average molecular weight of 2000 or more, and is usually a compound that does not contain a polymerizable group. The weight average molecular weight of the polymer compound is preferably 10,000 to 1,000,000, more preferably 50,000 to 500,000, and further preferably 100,000 to 300,000.

Specific examples of the polymer compound include a hydrocarbon resin, a novolak resin, a phenol resin, an epoxy resin, a melamine resin, a urea resin, an unsaturated polyester resin, an alkyd resin, a polyvinyl chloride resin, a polyvinyl acetate resin, Synthetic resin such as polyamide resin, polyacetal resin, polycarbonate resin, polystyrene terephthalate resin, polyethylene terephthalate resin, polysulfone resin, polyethersulfone resin and polyarylate resin, and natural rubber And the like. Among them, a hydrocarbon resin and a novolac resin are preferable, and a hydrocarbon resin is more preferable. The polymer compound may be used in combination of two or more as necessary.

As the hydrocarbon resin, any one can 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 Polyolefin copolymers, 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).

[Chemical Formula 4]

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) W represents SiR ¹⁸ _p D _{3 -p} (R ¹⁸ represents a hydrocarbon group having 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 APEL and has a glass transition temperature (Tg) of, for example, APL8008T (Tg 70 DEG C), APL6013T (Tg 125 DEG C) or APL6015T 145 占 폚) and the like. Pellets such as TOPAS8007, 5013, 6013 and 6015 are commercially available from Polyplastics Co., Ltd. Appear3000 is also 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 from JSR Corporation under the trade name of Arton G or Aton F. Zeonor ZF14, ZF16, Zeonex 250, 280, and 480R, and these can be used.

When the adhesive film has a polymer compound, the content of the polymer compound is preferably 5% by mass or more, more preferably 10% by mass or more, further preferably 20% by mass or more based on the total solid content of the adhesive film. The upper limit of the content of the polymer compound is preferably 70% by mass or less, more preferably 60% by mass or less, more preferably 50% by mass or less, and even more preferably 40% by mass or less based on the total solid content of the temporary fixing adhesive Particularly preferred.

The adhesive film may be configured so as not to substantially contain a polymer compound other than the polymer component. Means that the content of the polymer compound is preferably 1% by mass or less, more preferably 0.1% by mass or less, relative to the total solid portion of the adhesive film, and more preferably, Is more preferable.

<<< Surfactant >>>

The adhesive film may contain a surfactant. As the surfactant, various surfactants such as a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicone-based surfactant can be used, and a fluorine-based surfactant is preferable. By containing the surfactant, the liquid property (particularly, the fluidity) is improved, and uniformity of the coating thickness and liquid-repellency can be further improved when the adhesive film is applied and formed.

The fluorine-containing surfactant preferably has a fluorine content of 3 to 40% by mass, more preferably 5 to 30% by mass, and further preferably 7 to 25% by mass. The fluorine-based surfactant having a fluorine content within this range is effective in terms of uniformity of the thickness of the coating film and liquidity. Further, the solubility is also good.

Examples of the fluorochemical surfactant include Megapak F171, F172, F173, F176, F177, F141, F142, F143, F144, R30, F437, F475, F479, (Manufactured by Sumitomo 3M Co., Ltd.), Surflon S-382, SC-101 (manufactured by Sumitomo 3M Co., Ltd.), F- (Manufactured by Asahi Glass Co., Ltd.), PF636, PF656 (manufactured by Asahi Kasei Corporation), SC-103, SC-104, SC-105, SC1068, SC- , PF6320, PF6520, PF7002 (manufactured by OMNOVA), and the like.

Examples of the nonionic surfactant include glycerol, trimethylol propane, trimethylol ethane, and their ethoxylates and propoxylates (for example, glycerol propoxylate, glycerin ethoxylate and the like), polyoxyethylene Polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol di-laurate, polyethylene glycol di Stearate and consumptive fatty acid ester (Pluronic L10, L31, L61, L62, 10R5, 17R2, 25R2, Tetronic 304, 701, 704, 901, 904, 150R1, Ltd.) and the like.

Examples of the cationic surfactant include phthalocyanine derivatives (trade name: EFKA-745, manufactured by Morishita Sangyo Co., Ltd.), organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.) Lt; / RTI &gt; 75, No. 90, No. 95 (manufactured by Kyoeisha Chemical Co., Ltd.) and W001 (manufactured by Yusoh Co., Ltd.).

Examples of the anionic surfactant include W004, W005 and W017 (manufactured by Yusoh Co., Ltd.).

Examples of silicone based surfactants include fluorine-based surfactants such as TORAY Silicon DC3PA, TORAY Silicone SH7PA, TORAY Silicon DC11PA, TORAY Silicone SH21PA, TORAY Silicone SH28PA, TSF-4440 "," TSF-4445 "," TSF-4460 "," TSF-4440 "," TSF- KP341 ", " KF6001 ", "KF6002 ", manufactured by Shin-Etsu Silicone Co., Ltd., BYK307, BYK323 and BYK330 manufactured by Big Chemie.

When the adhesive film has a surfactant, the content of the surfactant is preferably 0.001 to 2.0% by mass, more preferably 0.005 to 1.0% by mass, based on the total solid content of the adhesive film.

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 film may contain various additives, for example, a curing agent, a curing catalyst, a filler, an adhesion promoter, an ultraviolet absorber, an anti-aggregation agent, and the like within a range that does not impair the effects of the present invention. When these additives are compounded, the total amount is preferably 3% by mass or less of the total solid content of the adhesive film.

<< Disclaimer >>

The adhesive laminate of the present invention has a release layer comprising a release agent containing at least one selected from a fluorine atom and a silicon atom on one surface (one surface) or both surfaces (both surfaces) of the adhesive film.

The film thickness of the release layer is not particularly limited as it is effective even if it is a thin film. For example, it is preferably 0.001 to 1 μm, more preferably 0.01 to 0.5 μm. Within the above-mentioned range, the adhesive layer laminate has an appropriate adhesive force, so that the adhesiveness to the device wafer or the support is good, and the adhesive layer laminate can be easily peeled off from the substrate or the support.

In the present invention, the average thickness of the release layer is set such that the thickness of the release layer in a section along one direction from one end face to the other end face and at five locations at equal intervals, It is defined as the average of the values measured by the tree. The "cross-section along one direction of the release layer" is synonymous with the above-mentioned "cross-section along one direction of the adhesive film ".

The fluorine content of the release layer is preferably 5 to 90% by mass, more preferably 20 to 80% by mass, and particularly preferably 50 to 75% by mass. The fluorine content 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".

The releasing layer preferably contains 5 to 100 mass%, more preferably 50 to 100 mass%, of the releasing agent containing at least one kind selected from a fluorine atom and a silicon atom based on the total solid content of the releasing layer, And more preferably 90 to 100 mass%. The releasing layer may have a plurality of kinds of releasing agents.

<<< Release Agent >>>

The releasing agent is preferably a compound containing at least a fluorine atom, more preferably a compound containing a fluorine atom and a silicon atom.

The releasing agent is preferably a silane coupling agent, more preferably a silane coupling agent containing at least a fluorine atom.

The releasing agent containing at least one kind selected from a fluorine atom and a silicon atom may be a thermosetting compound or a non-thermosetting compound. As the thermosetting compound, for example, a silane coupling agent can be given. Such a compound is preferably a compound containing two or more fluorine atoms in one molecule and generally having a group called perfluoro group. When the releasing agent contains a monomer component, at least a part of the monomer component is polymerized to exist as a polymer.

<<<< Thermosetting compounds >>>>

As the thermosetting compound, a compound having a fluorine atom and a crosslinkable group can be preferably used. Examples of the crosslinkable group include a silyl group having a hydroxyl group or a hydrolyzable group (e.g., an alkoxysilyl group, an acyloxysilyl group, etc.), a group having a reactive unsaturated double bond (a (meth) acryloyl group, A hydroxyl group, a carboxyl group, an amino group, a carbamoyl group, a mercapto group, a β-ketoester group (eg, Group, hydrosilyl group, silanol group, etc.), acid anhydride, group which may be substituted by nucleophilic agent (active oxygen atom, sulfonic acid ester etc.).

Among them, a silyl group having a hydroxyl group or a hydrolyzable group (e.g., an alkoxysilyl group or an acyloxysilyl group) or a group having a reactive unsaturated double bond (such as a (meth) acryloyl group, an allyl group, A vinyloxy group, etc.) is preferable.

Specific examples of the compound having a silyl group having a hydroxyl group or a hydrolyzable group include a group having at least one fluorine atom and a compound having at least one silyl group. The group having at least one fluorine atom is preferably a compound having two or more fluorine atoms in one molecule and generally having a group called a perfluoroalkyl group or a perfluoroether group. The group having a fluorine atom may have a substituent. The substituent may be arbitrarily selected from the viewpoints of reactivity and thermal stability, and includes, for example, a halogen atom such as a chlorine atom, a bromine atom and an iodine atom; An alkoxy group such as methoxy group, ethoxy group and tert-butoxy group; An aryloxy group such as a phenoxy group and a p-tolyloxy group; Alkoxycarbonyl groups such as a methoxycarbonyl group, a butoxycarbonyl group and a phenoxycarbonyl group; An acyloxy group such as acetoxy group, propionyloxy group and benzoyloxy group; An acyl group such as acetyl group, benzoyl group, isobutyryl group, acryloyl group, methacryloyl group and methoxyl group; Alkylsulfanyl groups such as methylsulfanyl group and tert-butylsulfanyl group; Arylsulfanyl groups such as phenylsulfanyl group and p-tolylsulfanyl group; Alkyl groups such as methyl group, ethyl group, tert-butyl group and dodecyl group; A cycloalkyl group such as a cyclopentyl group, a cyclohexyl group, a cycloheptyl group and an adamantyl group; An aryl group such as a phenyl group, a p-tolyl group, a xylyl group, a cumene group, a naphthyl group, an anthryl group and a phenanthryl group; A hydroxyl group; Carboxy group; Form Diary; Sulfone diazonium; Cyano; An alkylaminocarbonyl group; An arylaminocarbonyl group; Sulfonamido groups; Silyl group; An amino group; Monoalkylamino groups; A dialkylamino group; An arylamino group; And diarylamino group thio groups; Or a combination thereof.

The silyl group is preferably a silyl group or a hydrolyzable silyl group. The hydrolyzable silyl group is a hydrolyzable silyl group. Examples of the hydrolyzable group include an alkoxy group, a mercapto group, a halogen atom, an amido group, an acetoxy group, an amino group, and an isopropenoxy group. The silyl group is hydrolyzed to a silanol group, and the silanol group is dehydrated and condensed to form a siloxane bond. Such a hydrolyzable silyl group or silanol group is preferably represented by the following formula (B-1).

[Chemical Formula 5]

In formula (B-1), at least one of R ^h1 to R ^h3 is a substituent selected from the group consisting of an alkoxy group, a mercapto group, a halogen atom, an amido group, an acetoxy group, an amino group, and an isopropenoxy group A hydrolyzable group, or a hydroxyl group. The remaining R ^h1 to R ^h3 each independently represent a hydrogen atom, a halogen atom, or a monovalent organic substituent group (for example, an alkyl group, an aryl group, an alkenyl group, an alkynyl group or an aralkyl group).

In the formula (B-1), as the hydrolyzable group bonded to the silicon atom, an alkoxy group and a halogen atom are particularly preferable, and an alkoxy group is more preferable.

The alkoxy group is preferably an alkoxy group having 1 to 30 carbon atoms from the viewpoint of releasability. More preferably an alkoxy group having 1 to 15 carbon atoms, more preferably an alkoxy group having 1 to 5 carbon atoms, particularly preferably an alkoxy group having 1 to 3 carbon atoms, and most preferably a methoxy group or an ethoxy group.

Examples of the halogen atom include an F atom, a Cl atom, a Br atom and an I atom. In view of ease of synthesis and stability, the halogen atom is preferably a Cl atom and a Br atom, and more preferably a Cl atom.

The compound having at least one of the hydrolyzable silyl group and silanol group is preferably a compound having at least one group represented by the above formula (B-1), and a compound having at least two groups may be used.

The hydrolyzable group may be bonded to one silicon atom in a range of 1 to 4, and the total number of hydrolysable groups in the formula (B-1) is preferably in the range of 2 or 3. Particularly, it is preferable that three hydrolyzable groups are bonded to a silicon atom. When two or more hydrolyzable groups are bonded to a silicon atom, they may be the same or different.

Specific examples of the preferable alkoxy group include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, a tert-butoxy group, a phenoxy group and a benzyloxy group. A plurality of these alkoxy groups may be used in combination, or a plurality of different alkoxy groups may be used in combination.

Examples of the alkoxysilyl group bonded with an alkoxy group include a trialkoxysilyl group such as a trimethoxysilyl group, a triethoxysilyl group, a triisopropoxysilyl group, and a triphenoxysilyl group; Dialkoxymonoalkylsilyl groups such as a dimethoxymethylsilyl group and a diethoxymethylsilyl group; A monoalkoxydialkylsilyl group such as a methoxydimethylsilyl group, an ethoxydimethylsilyl group and the like.

Specific examples of the compound having a fluorine atom and a silyl group include trichloro (1H, 1H, 2H, 2H-heptadecafluorodecyl) silane, trimethoxy (1H, 1H, 2H, 2H-heptadecafluorodecyl (1H, 1H, 2H, 2H), in the same manner as in Example 1, except that the starting materials were used in the same manner as in Example 1, 1H, 2H, 2H-tridecafluoro-n-octyl) silane, triethoxy (1H, (1H, 1H, 2H, 2H-tridecafluoro-n-octyl) silane, dimethylchloro Fluoro-n-octyl) silane, Optol DSX (manufactured by Daikin) and F-TOP DB2-EOS (manufactured by Mitsubishi Materials Denshi Kasei Co., Ltd.).

Examples of the compound having a fluorine atom and a reactive unsaturated double bond include a radically polymerizable monomer having a fluorine atom, and a compound represented by the following general formula (1) is preferable.

General formula (I): Rf {-L-Y} n

(Wherein Rf represents a straight or cyclic n-valent group containing at least a carbon atom and a fluorine atom, which may contain either an oxygen atom or a hydrogen atom, and n represents an integer of 2 or more.) L represents a single bond Or a divalent linking group, and Y represents a polymerizable group.

In the general formula (I), Y is a polymerizable group, and examples thereof include a silyl group having a hydroxyl group or a hydrolyzable group (e.g., an alkoxysilyl group, an acyloxysilyl group, etc.), a group having a reactive unsaturated double bond (Such as a (meth) acryloyl group, an allyl group, a vinyloxy group, etc.), ring-opening polymerization reactive groups (epoxy group, oxetanyl group, oxazolyl group, etc.), groups having active hydrogen atoms (e.g., An amino group, a carbamoyl group, a mercapto group, a? -Ketoester group, a hydrosilyl group, a silanol group, etc.), an acid anhydride, a group which may be substituted by a nucleophilic agent (an active hydrogen atom or a sulfonic acid ester) Do.

More preferably, Y represents a radical polymerizable group, and a group having a reactive unsaturated double bond is more preferable. Specifically, it is preferable that T represents a radical polymerizable functional group represented by the following general formula (9).

[Chemical Formula 6]

(In the general formula (9), R ⁹⁰¹ to R ⁹⁰³ each independently represent a hydrogen atom, an alkyl group or an aryl group, and the dotted line represents a bond to a group connected to L.)

Examples of the alkyl group are preferably an alkyl group having 1 to 8 carbon atoms, and examples thereof include a methyl group, ethyl group, propyl group, octyl group, isopropyl group, tert-butyl group, isopentyl group, -Methylhexyl group, and cyclopentyl group. The aryl group is preferably an aryl group having 6 to 12 carbon atoms, and examples thereof include a phenyl group, a 1-naphthyl group and a 2-naphthyl group. As R ⁹⁰¹ to R ⁹⁰³ , a hydrogen atom or a methyl group is particularly preferable.

L represents a single bond or a divalent linking group. Examples of the divalent linking group include a divalent linking group obtained by combining two or more kinds of a divalent aliphatic group, a divalent aromatic group, -O-, -S-, -CO-, -N (R) -, Provided that R represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.

When L has an alkylene group or an arylene group, the alkylene group and the arylene group are preferably substituted with a halogen atom, and more preferably substituted with a fluorine atom.

Rf represents a straight or cyclic n-valent group which contains at least a carbon atom and a fluorine atom and may contain either an oxygen atom or a hydrogen atom. Rf may be a linear or branched polymer structure having a repeating unit having a fluorine atom.

As such a monomer having a fluorine atom, compounds described in paragraphs 0019 to 0033 of JP-A No. 2011-48358 can also be preferably used, and these contents are incorporated herein by reference.

The radically polymerizable monomer having a fluorine atom is also preferably at least one selected from the compounds represented by the following structural formulas (1), (2), (3), (4) and (5)

CH ₂ = CR ¹ COOR ² R ^f ????? (1)

(Formula (1) of, R ¹ represents a hydrogen atom, or a methyl group R ² _{is, -C p H 2p -.,} -C (C p H 2p + 1) H-, -CH 2 C (C p . H _{2p + 1)} H-, or -CH ₂ CH ₂ O- represents a R ^f _{is, -C n F 2n +1, -} (CF 2) n H, -C n F 2n + 1 -CF 3, _{- (CF 2) p OC n} H 2n C i F 2i +1, - (CF 2) p OC m H 2m C i F 2i H, -N (C p H 2p + 1) COC n F 2n +1, or represents a _{-N (C p H 2p + 1} ) SO 2 C n F 2n + 1. However, p is an integer of 1 ~ 10, n is an integer of 1 ~ 16, m is an integer of 0 ~ 10, i is Represents an integer from 0 to 16, respectively.)

CF ₂ = CFOR ^g ????? (2)

(In the structural formula (2), R ^g represents a fluoroalkyl group having 1 to 20 carbon atoms.)

CH ₂ = CHR ^g ????? (3)

(In the structural formula (3), R ^g represents a fluoroalkyl group having 1 to 20 carbon atoms.)

CH ₂ = CR ³ COOR ⁵ R ^j R ⁶ OCOCR ⁴ = CH ₂ ????? (4)

(Structure 4 of, R ³ and R ⁴ represent a hydrogen atom, a methyl group or R ⁵ and R ⁶ _{is, -C q H 2q -.,} -C (C q H 2q + 1) H-, - CH ₂ C (C _q H _{2q + 1} ) H- or -CH ₂ CH ₂ O-, R ^j represents -C _t F _2t , q is an integer of 1 to 10, and t is an integer of 1 to 16 .)

CH ₂ = CHR ⁷ COOCH ₂ (CH ₂ R ^k ) CHOCOCR ⁸ = CH ₂ ????? (5)

(In the structural formula (5), R ⁷ and R ⁸ represent a hydrogen atom or a methyl group, R ^k is -CyF _{2y +1, and} y is an integer of 1 to 16.)

Examples of the monomer represented by the structural formula (1) include CF ₃ (CF ₂ ) ₅ CH ₂ CH ₂ OCOCH═CH ₂ , CF ₃ CH ₂ OCOCH═CH ₂ , CF ₃ (CF ₂ ) ₄ CH ₂ CH ₂ OCOC (CH ₃ ) ═CH ₂ , C ₇ F ₁₅ CON (C ₂ H ₅ ) CH ₂ OCOC (CH ₃ ) ═CH ₂ , CF ₃ (CF ₂ ) ₇ SO ₂ N (CH ₂ ) CH ₂ CH ₂ OCOCH = _{CH 2, CF 2 (CF 2} ) 7 SO 2 N (C 3 H 7) CH 2 CH 2 OCOCH = CH 2, C 2 F 5 SO 2 N (C 3 H 7) CH 2 CH 2 OCOC (CH 3) _{= CH 2, (CF 3)} 2 CF (CF 2) 6 (CH 2) 3 OCOCH = CH 2, (CF 3) 2 CF (CF 2) 10 (CH 2) 3 OCOC (CH 3) = CH 2, _{CF 3 (CF 2) 4 CH} (CH 3) OCOC (CH 3) = CH 2, CF 3 CH 2 OCH 2 CH 2 OCOCH = CH 2, C 2 F 5 (CH 2 CH 2 O) 2 CH 2 OCOCH = _{CH 2, (CF 3) 2} CFO (CH 2) 5 OCOCH = CH 2, CF 3 (CF 2) 4 OCH 2 CH 2 OCOC (CH 3) = CH 2, C 2 F 5 CON (C 2 H 5) _{CH 2 OCOCH = CH 2, CF} 3 (CF 2) 2 CON (CH 3) CH (CH 3) CH 2 OCOCH = CH 2, H (CF 2) 6 C (C 2 H 5) OCOC (CH 3) = _{CH 2, H (CF 2)} 8 CH 2 OCOCH = CH 2, H (CF 2) 4 CH 2 OCOCH = CH 2, H (CF 2) CH 2 OCOC (CH 3) = CH 2, CF 3 (CF 2 _{) 7 SO 2 N (CH 3} ) CH 2 CH 2 OCOC (CH 3) = CH 2, CF 3 (CF 2) 7 SO 2 N (CH 3) (CH 2) 10 OCOCH = CH 2 _{, C 2 F 5 SO 2 N} (C 2 H 5) CH 2 CH 2 OCOC (CH 3) = CH 2, CF 3 (CF 2) 7 SO 2 N (CH 3) (CH 2) 4 OCOCH = CH 2 , C ₂ F ₅ SO ₂ N (C ₂ H ₅ ) C (C ₂ H ₅ ) HCH ₂ OCOCH = CH ₂ , and the like. These may be used alone, or two or more kinds may be used in combination.

As the fluoroalkyl represented by the structural formula (2) or (3) alkylating olefins, _{e.g., C 3 F 7 CH = CH} 2, C 4 F 9 CH = CH 2, C 10 F 21 CH = CH 2, C 3 F ₇ OCF = CF ₂ , C ₇ F ₁₅ OCF = CF ₂ , C ₈ F ₁₇ OCF = CF ₂ , and the like.

As the monomer represented by the structural formula (4) or (5), for _{instance, CH 2 = CHCOOCH 2 (CF} 2) 3 CH 2 OCOCH = CH 2, CH 2 = CHCOOCH 2 (CF 2) 6 CH 2 OCOCH = CH 2 , CH ₂ = CHCOOCH ₂ CH (CH ₂ C ₈ F ₁₇ ) OCOCH = CH ₂ , and the like.

As the radically polymerizable monomer or oligomer having a fluorine atom, an oligomer having a repeating unit having a fluorine atom and a repeating unit having a radically polymerizable functional group is also preferably used.

The repeating unit having a fluorine atom is preferably selected from at least one kind of repeating units represented by the following formulas (6), (7) and (10).

(7)

(6) of, R ^1, R ^2, R ^3, and R ⁴ are, each independently represents a hydrogen atom, a halogen atom, a hydroxyl group, or a monovalent organic group for, R ^1, R ^2, R ^3, and R at least one ⁴ is a monovalent organic group having a fluorine atom, or a fluorine atom.

In formula (7), R ⁵ , R ⁶ and R ⁷ each independently represent a hydrogen atom, a halogen atom, a hydroxyl group or a monovalent organic group, Y ¹ represents a single bond or a group represented by -CO-, , -NH-, a divalent aliphatic group, a divalent aromatic group, and a combination thereof. Rf represents a fluorine atom or a monovalent organic group having a fluorine atom.

Equation (10), R ^8, R ^9, R ^10, R ^11, R ^12, R ¹³ are, each independently represents a hydrogen atom, a halogen atom, a hydroxyl group, or one group monovalent organic to, Y ² and Y ³ are , A single bond or a divalent linking group selected from the group consisting of -CO-, -O-, -NH-, a bivalent aliphatic group, a bivalent aromatic group, and combinations thereof. Rf represents a divalent organic group having a fluorine atom.

The monovalent organic group having a fluorine atom in the formulas (6) and (7) is not particularly limited, but is preferably a fluorinated alkyl group having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, Of fluorinated alkyl groups are particularly preferred. The fluorinated alkyl group is a straight-chain (for example, _{-CF 2 CF 3, -CH 2 (} CF 2) 4 H, -CH 2 (CF 2) 8 CF 3, -CH 2 CH 2 (CF 2) 4 H , etc. ) being even, the branch structure (e.g. _{-CH (CF 3) 2, -CH} 2 CF (CF 3) 2, -CH (CH 3) CF 2 CF 3, -CH (CH 3) (CF 2) 5 CF ₂ H and the like), and may have an alicyclic structure (preferably a 5-membered ring or a 6-membered ring such as a perfluorocyclohexyl group, a perfluorocyclopentyl group or an alkyl group substituted with these) (E.g., -CH ₂ OCH ₂ CF ₂ CF ₃ , -CH ₂ CH ₂ OCH ₂ C ₄ F ₈ H, -CH ₂ CH ₂ OCH ₂ CH ₂ C ₈ F ₁₇ , -CH ₂ CF ₂ OCF ₂ CF ₂ OCF ₂ CF ₂ H, etc.). It may also be a perfluoroalkyl group.

The divalent organic group having a fluorine atom in formula (10) is not particularly limited, but is preferably a fluorinated alkylene group having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, a fluorinated alkyl group having 1 to 15 carbon atoms Rhenylene is particularly preferred. A fluorinated alkylene group, a straight-chain (for example, _{-CF 2 CF 2 -, -CH 2} (CF 2) 4 -, -CH 2 (CF 2) 8 CF 2 -, -CH 2 CH 2 (CF 2) ₄ -, etc.), branched structures (for example, -CH (CF ₃ ) CF ₂ -, -CH ₂ CF (CF ₃ ) CF ₂ -, -CH (CH ₃ ) CF ₂ CF ₂ -, -CH _{CH 3) (CF 2) 5} CF 2 - which may have, etc.), and, again alicyclic structure (preferably, for a five-membered ring or 6-membered ring, such as perfluoro cyclohexyl group, perfluoro cyclo pentyl or their (E.g., -CH ₂ OCH ₂ CF ₂ CF ₂ -, -CH ₂ CH ₂ OCH ₂ C ₄ F ₈ -, -CH ₂ CH ₂ OCH ₂ CH ₂ C ₈ F ₁₆ -, -CH ₂ CF ₂ OCF ₂ CF ₂ OCF ₂ CF ₂ -, -CH ₂ CF ₂ OCF ₂ CF ₂ OCF ₂ CF ₂ -, polyperfluoroalkylene ether chain, etc.) do. The perfluoroalkylene group may also be a perfluoroalkylene group.

The monovalent organic group in the formulas (6), (7) and (10) is preferably an organic group composed of 3 to 10 valent nonmetallic atoms and includes, for example, 1 to 60 carbon atoms, 0 to 10 An organic group composed of at least one element selected from the group consisting of nitrogen atoms from 0 to 50, oxygen atoms from 1 to 100, hydrogen atoms from 0 to 20, and sulfur atoms have.

More specific examples include organic groups having the following structures singly or in combination.

The monovalent organic group may further have a substituent and examples of the substituent which can be introduced include a halogen atom, a hydroxyl group, a carboxy group, a sulfo group, a nitro group, a cyano group, an amido group, An alkenyl group, an alkynyl group, an aryl group, a substituted oxy group, a substituted sulfonyl group, a substituted carbonyl group, a substituted sulfonyl group, a sulfo group, a phosphono group, a phosphonato group, a silyl group and a heterocyclic group. The organic group may also include an ether bond, an ester bond, and a ureido bond.

The monovalent organic group is preferably an alkyl group, an alkenyl group, an alkynyl group or an aryl group. The alkyl group is preferably an alkyl group having 1 to 8 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, an octyl group, an isopropyl group, a t-butyl group, an isopentyl group, Hexyl group, and cyclopentyl group. An alkenyl group and an alkenyl group having 2 to 20 carbon atoms, and examples thereof include a vinyl group, an allyl group, a furyl group, a geranyl group and an oleyl group. The alkanyl group is preferably an alkanyl group having 3 to 10 carbon atoms, and examples thereof include an ethynyl group, a propargyl group, and a trimethylsilylethynyl group. The aryl group is preferably an aryl group having 6 to 12 carbon atoms, and examples thereof include a phenyl group, a 1-naphthyl group and a 2-naphthyl group. The heterocyclic group is preferably a heterocyclic group having 2 to 10 carbon atoms, and examples thereof include a furanyl group, a thiophenyl group, and a pyridinyl group.

In the formula (6) in the ^{R 1, R 2, R 3} , and R ^4, Equation ^{(7), R 5, R 6, R} 7, equation ^{(10), R 8, R} 9, R 10, R 11 , R ¹² and R ¹³ is preferably an alkyl group or an aryl group.

Examples of the alkyl group are preferably an alkyl group having 1 to 8 carbon atoms, and examples thereof include a methyl group, ethyl group, propyl group, octyl group, isopropyl group, tert-butyl group, isopentyl group, -Methylhexyl group, and cyclopentyl group. The aryl group is preferably an aryl group having 6 to 12 carbon atoms, and examples thereof include a phenyl group, a 1-naphthyl group and a 2-naphthyl group. As R ⁹⁰¹ to R ⁹⁰³ , a hydrogen atom or a methyl group is particularly preferable.

From the group consisting of -CO-, -O-, -NH-, bivalent aliphatic groups, bivalent aromatic groups and combinations thereof represented by Y ¹ in the formula (7) and Y ² and Y ³ in the formula (10) Specific examples of the divalent linking groups to be selected are described below. In the following example, the left side is bonded to the main chain and the right side is bonded to Rf.

L1 is an aliphatic group of the -CO-NH-2 -O-CO-NH-2 aliphatic group -O-CO-

L2: -CO-NH-2 aliphatic group -O-CO-

L3: -CO-2 aliphatic group -O-CO-

L4: -CO-O-2 aliphatic group -O-CO-

L5: -valent aliphatic group -O-CO-

L6: -CO-NH-2 aromatic group -O-CO-

L7: -CO-2 aromatic group -O-CO-

L8: -valent aromatic group -O-CO-

L9: an aliphatic group of -CO-O-2, an aliphatic group of -CO-O-2,

L10: an aliphatic group of -CO-O-2, an aliphatic group of -O-CO-2, an -O-

L11 represents an aromatic group of -CO-O-2, -CO-O-2 represents an aliphatic group -O-CO-

L12 represents an aromatic group of -CO-O-2, -O-CO-2 represents an aliphatic group -O-CO-

L13: an aliphatic group of -CO-O-2, an aromatic group of -CO-O-2, -O-CO-

L14: an aliphatic group of -CO-O-2, an aromatic group of -O-CO-2, -O-CO-

L15 is an aromatic group of -CO-O-2, -CO-O-2 is an aromatic group of -O-CO-

L16 represents an aromatic group of -CO-O-2, -O-CO-2 represents an aromatic group, -O-CO-

L17 represents an aromatic group of -CO-O-2, -O-CO-NH-2 represents an aliphatic group -O-CO-

L18 represents an aliphatic group of -CO-O-2, an aliphatic group of -O-CO-NH-2,

L19: An aromatic group-bivalent aliphatic group

L20: an aromatic group-having 2-valent aliphatic group -O-2 valent aliphatic group-

L21: an aromatic group-having 2-valent aliphatic group -O-2 valent aliphatic group -O-

L22: -CO-O-2 Aliphatic group -

L23: -CO-O-2 Aliphatic group -O-

Herein, the divalent aliphatic group means an alkylene group, a substituted alkylene group, an alkenylene group, a substituted alkenylene group, an alkenylene group, a substituted alkenylene group or a polyalkyleneoxy group. Among them, an alkylene group, a substituted alkylene group, an alkenylene group, and a substituted alkenylene group are preferable, and an alkylene group and a substituted alkylene group are more preferable.

The divalent aliphatic group is preferably a chain structure rather than a cyclic structure and more preferably a straight chain structure rather than a branched chain structure. The number of carbon atoms of the divalent aliphatic group is preferably from 1 to 20, more preferably from 1 to 15, still more preferably from 1 to 12, still more preferably from 1 to 10, even more preferably from 1 to 8 Still more preferably 1 to 4 carbon atoms.

Examples of the substituent of the divalent aliphatic group include a halogen atom (F, Cl, Br, I), a hydroxyl group, a carboxy group, an amino group, a cyano group, an aryl group, an alkoxy group, an aryloxy group, An aryloxycarbonyl group, an acyloxy group, a monoalkylamino group, a dialkylamino group, an arylamino group, and a diarylamino group.

Examples of the divalent aromatic group include a phenylene group, a substituted phenylene group, a naphthalene group and a substituted naphthalene group, and a phenylene group is preferable. Examples of the substituent of the divalent aromatic group include an alkyl group in addition to the examples of the substituent of the divalent aliphatic group.

The content of the repeating unit having a fluorine atom is preferably from 2 mol% to 98 mol%, more preferably from 10 mol% to 90 mol%, based on the total repeating units of the fluorine atom-containing radically polymerizable oligomer.

The repeating unit having a radical polymerizable functional group is preferably a repeating unit represented by the following formula (8).

[Chemical Formula 8]

(In the general formula (8), R ⁸⁰¹ to R ⁸⁰³ each independently represent a hydrogen atom, an alkyl group, or a halogen atom, and Y ⁸ represents a single bond or a group represented by -CO-, -O-, -NH -, a divalent aliphatic group, a divalent aromatic group, and a combination thereof, and T represents a structure having a radically polymerizable functional group.

The alkyl group as R ⁸⁰¹ to R ⁸⁰³ is preferably an alkyl group having 1 to 6 carbon atoms.

T is preferably a radical polymerizable functional group represented by the general formula (9).

[Chemical Formula 9]

(In the general formula (9), R ⁹⁰¹ to R ⁹⁰³ each independently represent a hydrogen atom, an alkyl group or an aryl group, and the dotted line represents a bond to a group connected to Y ⁸ .

Examples of the alkyl group are preferably an alkyl group having 1 to 8 carbon atoms, and examples thereof include a methyl group, ethyl group, propyl group, octyl group, isopropyl group, tert-butyl group, isopentyl group, -Methylhexyl group, and cyclopentyl group. The aryl group is preferably an aryl group having 6 to 12 carbon atoms, and examples thereof include a phenyl group, a 1-naphthyl group and a 2-naphthyl group. As R ⁹⁰¹ to R ⁹⁰³ , a hydrogen atom or a methyl group is particularly preferable.

Y ⁸ represents a single bond or a divalent linking group selected from the group consisting of -CO-, -O-, -NH-, a bivalent aliphatic group, a bivalent aromatic group, and a combination thereof. A concrete example of Y ⁸ composed of a combination is shown below. In the following example, the left side is bonded to the main chain and the right side is bonded to the formula (9).

L1 is an aliphatic group of the -CO-NH-2 -O-CO-NH-2 aliphatic group -O-CO-

L2: -CO-NH-2 aliphatic group -O-CO-

L3: -CO-2 aliphatic group -O-CO-

L4: -CO-O-2 aliphatic group -O-CO-

L5: -valent aliphatic group -O-CO-

L6: -CO-NH-2 aromatic group -O-CO-

L7: -CO-2 aromatic group -O-CO-

L8: -valent aromatic group -O-CO-

L9: an aliphatic group of -CO-O-2, an aliphatic group of -CO-O-2,

L10: an aliphatic group of -CO-O-2, an aliphatic group of -O-CO-2, an -O-

L11 represents an aromatic group of -CO-O-2, -CO-O-2 represents an aliphatic group -O-CO-

L12 represents an aromatic group of -CO-O-2, -O-CO-2 represents an aliphatic group -O-CO-

L13: an aliphatic group of -CO-O-2, an aromatic group of -CO-O-2, -O-CO-

L14: an aliphatic group of -CO-O-2, an aromatic group of -O-CO-2, -O-CO-

L15 is an aromatic group of -CO-O-2, -CO-O-2 is an aromatic group of -O-CO-

L16 represents an aromatic group of -CO-O-2, -O-CO-2 represents an aromatic group, -O-CO-

L17 represents an aromatic group of -CO-O-2, -O-CO-NH-2 represents an aliphatic group -O-CO-

L18 represents an aliphatic group of -CO-O-2, an aliphatic group of -O-CO-NH-2,

Herein, the divalent aliphatic group means an alkylene group, a substituted alkylene group, an alkenylene group, a substituted alkenylene group, an alkenylene group, a substituted alkenylene group or a polyalkyleneoxy group. Among them, an alkylene group, a substituted alkylene group, an alkenylene group, and a substituted alkenylene group are preferable, and an alkylene group and a substituted alkylene group are more preferable.

The divalent aliphatic group is preferably a chain structure rather than a cyclic structure and more preferably a straight chain structure rather than a branched chain structure. The number of carbon atoms of the divalent aliphatic group is preferably from 1 to 20, more preferably from 1 to 15, still more preferably from 1 to 12, still more preferably from 1 to 10, even more preferably from 1 to 8 Still more preferably 1 to 4 carbon atoms.

Examples of the substituent of the divalent aliphatic group include a halogen atom (F, Cl, Br, I), a hydroxyl group, a carboxy group, an amino group, a cyano group, an aryl group, an alkoxy group, an aryloxy group, An aryloxycarbonyl group, an acyloxy group, a monoalkylamino group, a dialkylamino group, an arylamino group, and a diarylamino group.

Examples of the divalent aromatic group include a phenylene group, a substituted phenylene group, a naphthalene group and a substituted naphthalene group, and a phenylene group is preferable. Examples of the substituent of the divalent aromatic group include an alkyl group in addition to the examples of the substituent of the divalent aliphatic group.

The content of the repeating unit having a radically polymerizable functional group is preferably from 2 mol% to 98 mol%, more preferably from 10 mol% to 90 mol%, based on the total repeating units of the fluoropolymerizable radically polymerizable oligomer Do.

The weight average molecular weight of the radically polymerizable oligomer having a fluorine atom in terms of polystyrene as determined by gel permeation chromatography (GPC) is preferably 2,000 to 20,000, more preferably 2,000 to 15,000, and most preferably 2,000 to 10,000 desirable.

The radically polymerizable monomer or oligomer having a silicon atom is preferably a silicone monomer or a silicone oligomer. For example, at least one terminal of the polydimethylsiloxane bond may be an ethylene (meth) acryloyl group such as a Unsaturated group, and a compound having a (meth) acryloyl group is preferable.

The number average molecular weight of a radically polymerizable oligomer having a silicon atom in terms of polystyrene determined by gel permeation chromatography is preferably 1,000 to 10,000.

As the radically polymerizable monomer having a silicon atom, a compound represented by the general formula (11) or (12) is preferable.

[Chemical formula 10]

(Formula (11) and (12) of, R ¹¹ ~ R ¹⁹ are, each independently, represent a hydrogen atom, alkyl group, alkoxy group, alkoxycarbonyl group, or an aryl group. Z ^11, Z ^12, and Z ¹³ is L ¹¹ , L ¹² and L ¹³ each independently represent a single bond or a divalent linking group, and n and m each independently represent an integer of 0 or more.

In the general formulas (11) and (12), R ¹¹ to R ¹⁹ each independently represent a hydrogen atom, an alkyl group, an alkoxy group, an alkoxycarbonyl group or an aryl group.

The alkyl group may be linear, branched or an alkyl group having 1 to 5 carbon atoms, and specific examples thereof include a methyl group, ethyl group, n-propyl group and isopropyl group. The alkoxy group means -OR ²⁰ , and R ²⁰ represents an alkyl group (preferably an alkyl group having 1 to 5 carbon atoms), and specific examples thereof include a methoxy group, ethoxy group, propoxy group, isopropoxy group, And the like. The alkoxycarbonyl group means -C (= O) R ²¹ , and R ²¹ represents an alkoxy group (preferably an alkoxy group having 1 to 5 carbon atoms), specifically, methoxycarbonyl, ethoxycarbonyl Propylcarbonyl, and the like. Examples of the aryl group include a phenyl group, a tolyl group and a naphthyl group. These groups may have a substituent. Examples of the aryl group include a phenylmethyl (benzyl) group, a phenylethyl group, a phenylpropyl group, a phenylbutyl group and a naphthylmethyl group.

L ¹¹ , L ¹² , and L ¹³ each independently represent a single bond or a divalent linking group. The divalent linking group is a divalent linking group selected from the group consisting of -CO-, -O-, -NH-, a bivalent aliphatic group, a bivalent aromatic group, and a combination thereof.

n and m each independently represent an integer of 0 or more, preferably an integer of 0 to 100, more preferably an integer of 0 to 50.

Z ¹¹ , Z ¹² and Z ¹³ each independently represent a radical polymerizable group, and a functional group represented by any one of the following formulas (i) to (iii) is particularly preferable.

(11)

(Wherein R ¹⁰¹ to R ¹⁰³ each independently represents a hydrogen atom or a monovalent organic group, X ¹⁰¹ represents an oxygen atom, a sulfur atom, or -N (R ¹⁰⁴ ) -, and R ¹⁰⁴ Represents a hydrogen atom or a monovalent organic group.)

In the general formula (i), R ¹⁰¹ to R ¹⁰³ each independently represent a hydrogen atom or a monovalent organic group. R ¹⁰¹ is preferably a hydrogen atom or an alkyl group which may have a substituent, and among these, a hydrogen atom and a methyl group are preferable because of high radical reactivity. R ¹⁰² and R ¹⁰³ are each independently preferably a hydrogen atom, a halogen atom, an amino group, a carboxyl group, an alkoxycarbonyl group, a sulfo group, a nitro group, a cyano group, , An aryl group which may have a substituent, an alkoxy group which may have a substituent, an aryloxy group which may have a substituent, an alkylamino group which may have a substituent, an arylamino group which may have a substituent, , Or an arylsulfonyl group which may have a substituent, and among these, a hydrogen atom, a carboxyl group, an alkoxycarbonyl group, an alkyl group which may have a substituent, and an aryl group which may have a substituent are preferable because of high radical reactivity.

X ¹⁰¹ represents an oxygen atom, a sulfur atom, or -N (R ¹⁰⁴ ) -, and R ¹⁰⁴ represents a hydrogen atom or a monovalent organic group. As the monovalent organic group, an alkyl group which may have a substituent may, for example, be mentioned. It is preferable that R ¹⁰⁴ is a hydrogen atom, a methyl group, an ethyl group, or an isopropyl group because of high radical reactivity.

Examples of the substituent which can be introduced include an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an alkoxy group, an aryloxy, a halogen atom, an amino group, an alkylamino group, an arylamino group, a carboxyl group, an alkoxycarbonyl group, , A cyano group, an amido group, an alkylsulfonyl group, and an arylsulfonyl group.

[Chemical Formula 12]

(Wherein R ²⁰¹ to R ²⁰⁵ each independently represents a hydrogen atom or a monovalent organic group, Y ²⁰¹ represents an oxygen atom, a sulfur atom, or -N (R ²⁰⁶ ) - R ²⁰⁶ represents a hydrogen atom or a monovalent organic group.)

In formula (ii), ^R201 to ^R205 each independently represent a hydrogen atom or a monovalent organic group. R ²⁰¹ to R ²⁰⁵ each independently represent a hydrogen atom, a halogen atom, an amino group, a carboxyl group, an alkoxycarbonyl group, a sulfo group, a nitro group, a cyano group, an alkyl group which may have a substituent, An aryloxy group which may have a substituent, an aryloxy group which may have a substituent, an alkylamino group which may have a substituent, an arylamino group which may have a substituent, an alkylsulfonyl group which may have a substituent, , And more preferably an aryl group which may have a hydrogen atom, a carboxyl group, an alkoxycarbonyl group, an alkyl group which may have a substituent, or a substituent.

The substituent which can be introduced includes the same substituents as those described in the general formula (i).

Y ²⁰¹ represents an oxygen atom, a sulfur atom, or -N (R ²⁰⁶ ) -. R ²⁰⁶ is synonymous with R ^{104 in} formula (i), and preferred examples are also the same.

[Chemical Formula 13]

(In the general formula (iii), R ³⁰¹ to R ³⁰³ each independently represent a hydrogen atom or a monovalent organic group, and Z ³⁰¹ represents an oxygen atom, a sulfur atom, -N (R ³⁰⁴ ) R ³⁰⁴ is the same as R ^{104 in the} general formula (i).)

In formula (iii), R ³⁰¹ to R ³⁰³ each independently represent a hydrogen atom or a monovalent organic group. R ³⁰¹ is preferably a hydrogen atom or an alkyl group which may have a substituent, and among them, a hydrogen atom or a methyl group is more preferable because of high radical reactivity. R ³⁰² and R ³⁰³ each independently represent a hydrogen atom, a halogen atom, an amino group, a carboxyl group, an alkoxycarbonyl group, a sulfo group, a nitro group, a cyano group, an alkyl group which may have a substituent, An aryloxy group which may have a substituent, an aryloxy group which may have a substituent, an alkylamino group which may have a substituent, an arylamino group which may have a substituent, an alkylsulfonyl group which may have a substituent, And more preferably an aryl group which may have a hydrogen atom, a carboxyl group, an alkoxycarbonyl group, an alkyl group which may have a substituent, or an aryl group which may have a substituent, from the viewpoint of high radical reactivity.

The substituent which can be introduced includes the same substituents as those described in the general formula (i). Z ³⁰¹ represents an oxygen atom, a sulfur atom, -N (R ³⁰⁴ ) - or a phenylene group which may have a substituent. R ³⁰⁴ is the same as R ^{104 in the} general formula (i), and examples of the monovalent organic group include an alkyl group which may have a substituent. Among them, the methyl group, the ethyl group and the isopropyl group have a high radical reactivity .

When the releasing agent has a radically polymerizable monomer or oligomer having a silicon atom, the content of the radically polymerizable monomer or oligomer having a silicon atom is preferably 0.01 to 15% by mass relative to the total solid content of the releasing agent. If it is 0.01% by mass or more, sufficient peeling property can be obtained. If it is 15 mass% or less, sufficient adhesion can be obtained. The radically polymerizable monomer or oligomer having a silicon atom may be only one kind or two or more kinds. When two or more types of radically polymerizable monomers or oligomers having a silicon atom are contained, the total amount is preferably in the above range.

Examples of the radically polymerizable monomer having a fluorine atom or a silicon atom include RS-75, RS-72-K, RS-76-E, RS-72-K manufactured by DIC K.K. X-22-164AS, X-22-164A, X-22-164B, X-22-164B manufactured by Shin-Etsu Chemical Co., Ltd., fluorine-based silane coupling agents, -22-164C, X-22-164E, EBECRYL 350 and EBECRYL 1360 manufactured by Daicel-Cytech Corporation, TEGORAD 2700 and UV-3500B (manufactured by BYK) manufactured by Degussa.

As the material having a fluorine atom or a silicon atom, in addition to the above, heptadecafluoro-1,1,2-tetrahydradecyl) trichlorosilane, (fluoro) alkylphosphonate, parylene fluoride, silicon Acrylate copolymers, copolymers of tetrafluoroethylene and 2,2-bis-trifluoromethyl-4,5-difluoro-1,3-dioxole, polymers having pendant perfluoroalkoxy groups, Ethylene-propylene copolymers, and the like.

<<<< Non-thermosetting compounds >>>>

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.

As the (meth) acrylic acid ester containing a perfluoroalkyl group, specifically, it is preferably a compound represented by the following formula (101).

(101)

[Chemical Formula 14]

In the general formula (101), R ¹⁰¹ , R ¹⁰² and R ¹⁰³ each independently represent a hydrogen atom, an alkyl group, or a halogen atom. Y ¹⁰¹ represents a single bond or a divalent linking group selected from the group consisting of -CO-, -O-, -NH-, a bivalent aliphatic group, a bivalent aromatic group and a combination thereof. Rf is a monovalent organic group having at least one of a fluorine atom and a fluorine atom.

Examples of the alkyl group represented by R ¹⁰¹ , R ¹⁰² and R ¹⁰³ in the general formula (101) are preferably an alkyl group having 1 to 8 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, an octyl group, , a tert-butyl group, an isopentyl group, a 2-ethylhexyl group, a 2-methylhexyl group, and a cyclopentyl group. The aryl group is preferably an aryl group having 6 to 12 carbon atoms, and examples thereof include a phenyl group, a 1-naphthyl group and a 2-naphthyl group. As R ¹⁰¹ to R ¹⁰³ , a hydrogen atom or a methyl group is particularly preferable.

Y ¹⁰¹ represents a single bond or a divalent linking group selected from the group consisting of -CO-, -O-, -NH-, a bivalent aliphatic group, a bivalent aromatic group and a combination thereof, A chain structure is preferable to a cyclic structure, and a straight chain structure is preferable to a chain structure having a branch. The number of carbon atoms of the divalent aliphatic group is preferably from 1 to 20, more preferably from 1 to 15, still more preferably from 1 to 12, still more preferably from 1 to 10, even more preferably from 1 to 8 Still more preferably 1 to 4 carbon atoms.

Examples of the divalent aromatic group include a phenylene group, a substituted phenylene group, a naphthalene group and a substituted naphthalene group, and a phenylene group is preferable.

As Y ¹⁰¹ , it is preferable that the Y ¹⁰¹ is an aliphatic group having a bivalent straight-chain structure.

The monovalent organic group having a fluorine atom represented by Rf is not particularly limited, but is preferably a fluorinated alkyl group having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and particularly preferably a fluorinated alkyl group having 1 to 15 carbon atoms desirable. The fluorinated alkyl group is a straight chain {e.g. _{-CF 2 CF 3, -CH 2 (} CF 2) 4 H, -CH 2 (CF 2) 8 CF 3, -CH 2 CH 2 (CF 2) 4 H , etc. }, and even, for example, {branch structure _{-CH (CF 3) 2, -CH} 2 CF (CF 3) 2, -CH (CH 3) CF 2 CF 3, -CH (CH 3) (CF 2) 5 CF ₂ H, etc.), and may have an alicyclic structure (preferably, a 5-membered ring or a 6-membered ring such as a perfluorocyclohexyl group, a perfluorocyclopentyl group, (E.g., -CH ₂ OCH ₂ CF ₂ CF ₃ , -CH ₂ CH ₂ OCH ₂ C ₄ F ₈ H, -CH ₂ CH ₂ OCH ₂ CH ₂ C ₈ F ₁₇ , -CH ₂ CF ₂ OCF ₂ CF ₂ OCF ₂ CF ₂ H, etc.). It may also be a perfluoroalkyl group.

The (meth) acrylic resin having a perfluoroalkyl group preferably has a repeating unit represented by the following formula (102).

Equation (102)

[Chemical Formula 15]

In the general formula (102), R ¹⁰¹ , R ¹⁰² , R ¹⁰³ , Y ¹⁰¹ and Rf each are the same as in the general formula (101), and the preferred embodiments are also synonymous.

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, methacrylonitrile, and the like can be given.

More specifically, for example, acrylic acid esters such as alkyl acrylate (preferably the number of carbon atoms in the alkyl group is from 1 to 20), (e.g., methyl acrylate, ethyl acrylate, propyl acrylate, Amyl acrylate, ethylhexyl acrylate, octyl acrylate, t-octyl acrylate, chloroethyl acrylate, 2,2-dimethylhydroxypropyl acrylate, 5-hydroxypentyl acrylate, trimethylolpropane monoacrylate, (For example, phenylacrylate and the like), pentaerythritol monoacrylate, glycidyl acrylate, benzyl acrylate, methoxybenzyl acrylate, furfuryl acrylate, and tetrahydrofurfuryl acrylate) , And alkyl methacrylates (preferably, the alkyl group has 1 to 20 carbon atoms) (for example, methyl methacrylate Acrylate, isobutyl methacrylate, ethyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, amyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, chlorobenzyl 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, methacrylic acid, And the like), styrenes such as styrene and alkylstyrene (e.g., methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, Butylene styrene, isoprene styrene, isoprene, styrene, butylene, diene, styrene, isobutylene, styrene, , Acetoxymethylstyrene, etc.), alkoxystyrene (e.g., methoxystyrene, 4-methoxy-3-methylstyrene, dimethoxystyrene and the like), halogensilane (e.g., But are not limited to, chlorostyrene, chlorostyrene, dichlorostyrene, dichlorostyrene, trichlorostyrene, tetrachlorostyrene, pentachlorostyrene, bromostyrene, dibromostyrene, iodostyrene, fluorostyrene, 2-bromo-4-trifluoromethylstyrene, 4-fluoro-3-trifluoromethylstyrene, etc.), acrylonitrile, methacrylonitrile acrylic acid, and carboxylic acid There may be mentioned water (acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, p- carboxyl styrene, and the metal salt, ammonium salt compounds of these acid groups, etc.). (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.

As a polymer compound having a non-polymerizable fluorine atom, commercially available products include Teflon (registered trademark) (DuPont), Teflon (DuPont), Fluon (Asahi Glass Co.), Hyler (Solvay Solexis) (DuPont), fluoropolymers such as Lumipulon (Asahi Glass Co.), Arplight (Asahi Glass Co.), Sepharose Soft (Central Glass Co.) Perfluorooctanes such as fluororubber of trade names such as Calretz (Du Pont) and SIFEL (Shin-Etsuga Kagaku Kogyo), Krytox (DuPont), Pombulin (Daitoku Tech), and Dhamnum Fluorine oils including polyether oils, fluorine-containing mold release agents such as Daihof FB Series (Daikin Kogyu Co., Ltd.) and Megapak Series (DIC Co., Ltd.) such as DaiFree FB962, and the like. But are not limited to, polymer compounds having non-polymerizable fluorine atoms If any can also be suitably used would.

Particularly, F-251, F-281, F-477, F-553, F-554, F-555, F-556, F-557, F- F-565, F-567, F-568, F-571, R-40, R-41, R-43 and R-94 manufactured by Neos Co., , 710FM, 710FS, 730FL, and 730LM can be preferably used.

The weight average molecular weight of the polymer compound having a non-polymerizable fluorine atom is preferably from 2,000 to 100,000, more preferably from 2,000 to 50,000, and most preferably from 2,000 to 10,000.

<<< Other Ingredients >>>

In addition to the release agent, the releasing layer may further contain various compounds depending on the purpose insofar as the effect of the present invention is not impaired. For example, a thermal polymerization initiator, a sensitizing dye, a chain transfer agent, an antioxidant, and a surfactant can be preferably used. These may be those described in the above-mentioned adhesive films.

&Lt; Method for producing laminate for adhesion &gt;

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

The method for producing a laminate for adhesion of the present invention comprises a step of forming a release layer comprising a release agent containing at least one selected from a fluorine atom and a silicon atom on the surface of the above-mentioned adhesive film.

&Lt; Production method of adhesive film &gt;

The adhesive film can be produced by a conventionally known method. For example, it can be produced by a melt film formation method, a solution film formation method, or the like. Preferably, this is a melt film-forming method. In the case of the melt film-forming method, it is possible to form a film while maintaining flatness. Further, a polymer component which is difficult to dissolve in a solvent and other additives can be used, and the flexibility of material selection is high. Particularly, it is possible to use a high heat resistant additive which tends to be difficult to dissolve in a solvent, and an adhesive film excellent in heat resistance tends to be obtained.

The melt film-forming method is a method of obtaining a film (sheet) by realizing fluidity by overheating a raw material composition and melting it, and forming the melt into a sheet form by using an extrusion molding apparatus or an injection molding apparatus and cooling. With the extrusion molding method, a long flat film with good flatness 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 500000 mm or less, for example, and more preferably 200000 mm or less. With the injection molding method, it is difficult to obtain a long film, but a high film thickness accuracy can be obtained. Other additives may also be added by mixing and stirring. The release film may be applied to one side or both sides of the film to form a "release film-adhering film ".

The solution film-forming method is a method for obtaining a film (sheet) by realizing fluidity by dissolving a raw material composition in a solvent and coating the solution on a support such as a film, a drum or a band to form a sheet, and drying.

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-oxobutoate, ethyl 2-oxobutoate, 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;

Aromatic hydrocarbons such as toluene, xylene, anisole, and mesitylene;

And hydrocarbons such as limonene and p-menthane.

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, it is particularly preferable to use at least one selected from the group consisting of mesitylene, p-mentine, gamma butyrolactone, anisole, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethylcellosolve acetate, Cyclohexanone, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether, and propylene glycol methyl ether, and the like. Ether acetate, and mixtures thereof.

Examples of the coating method of the solution include a method of extruding the solution from the slit-shaped opening by pressure and coating it, a method of transferring the solution by gravure or Aronix roller to coat the solution, a method of applying the solution by spraying or spraying from a sprayer or a dispenser, A dip coating method in which a film, a drum or a band is passed in a tank, and a method in which a wire bar solution is applied by scraping while pushing the solution.

After the solution is coated on the support and dried to form a solidified sheet, a single sheet (sheet) can be obtained by mechanically peeling the sheet from the support. As the treatment for giving the releasability on the support in advance, the releasing layer may be applied, immersed, gas treated, electromagnetic wave irradiated, plasma irradiated or the like so as to facilitate peeling. Alternatively, the film may be left as it is without being peeled off from the support, and the adhesive film with the release film may be left while the sheet is adhered on the film support. By performing these treatments continuously, a roll-shaped long film can be obtained. Alternatively, a release film may be laminated on both sides of the adhesive film to form an "adhesive film with a double-side release film ".

&Lt; Method of forming a release layer &gt;

Examples of the method of forming the release layer on the surface of the adhesive film include a laminating method, a coating method and a co-extrusion method.

In the laminating method, a composition including at least the releasing agent is applied to a releasing film to form a releasing layer (releasing layer film) in the form of a film, and a releasing film of the releasing film And the laminating is carried out.

For the laminating, a known device such as roller laminating (heating, pressurization may be performed), vacuum laminating (may be heated), or the like may be used. By laminating the release layer film on both sides of the adhesive film, the release layer can be provided on both sides of the adhesive film.

The coating method is a method in which a solution for forming a release layer is coated on the surface of the adhesive film on which no release film is formed, followed by drying. As the composition for forming a release layer, it is preferable to use a solution containing the above-described release agent and a solvent. Any solvent can be preferably used as long as the solvent can dissolve the release agent. For example, Fluorinert FC40 (manufactured by 3M), and the like.

When the adhesive film is prepared by a solution casting method, the solution for forming a release layer may be applied and dried in in-line without applying a solution for forming an adhesive film, drying, and winding.

When the physical properties of the solution are designed so that the solution for forming an adhesive film and the solution for forming a release layer are not compatible with each other, they may be simultaneously applied and dried at the same time.

Alternatively, the solution for forming a release layer may be applied after the application of the solution for forming an adhesive film and without drying, and the both may be simultaneously dried.

When the solution for forming an adhesive film and the solution for forming a release layer are used at the same time, if the solution is designed to have a phase-separating property when it is dried and its concentration becomes high, a mixed solution is applied and separated into an adhesive film and a release layer You can.

Further, by applying a solution for forming a release layer on both surfaces of the adhesive film, a release layer can be provided on both surfaces of the adhesive film.

In the co-extrusion method, a material for forming an adhesive film and a material for forming a release layer are thermally melted and simultaneously integrated by extrusion molding, thereby obtaining a sheet in which the adhesive film and the release layer are integrated. The release layer can be provided on both sides of the adhesive film by extruding the material for forming the release layer on both sides of the material for forming the adhesive film.

In the adhesive laminate of the present invention, the content of the solvent is preferably 1% by mass or less, more preferably 0.1% by mass or less, and particularly preferably is not contained.

The adhesive laminate of the present invention may be a laminate for adhering a release film and adhering a release film to one side or both sides of the adhesive laminate. According to this aspect, it is possible to prevent troubles such as scratches on the surface of the adhesive laminate or sticking to the adhesive tape during storage when the elongated adhesive layer laminate is rolled up in roll form.

The release film can be peeled and removed in use. For example, in the case where a release film is adhered to both sides, the release film on one side is peeled off, the adhesive surface is laminated to a device wafer or a support, and the remaining release film is peeled off, As much as possible.

<Adhesive Support>

Next, an adhesive support using the adhesive laminate of the present invention will be described.

The adhesive support has the above-described adhesive layer laminate on the surface of the support.

The adhesive laminate can be formed by laminating the above-described adhesive layer laminate of the present invention on a support. For example, the laminating adhesive laminate is set in a vacuum laminator. In this apparatus, the laminating adhesive laminate is placed on a support. Under vacuum, the laminating adhesive laminate and the support are brought into contact with each other, And a method of fixing (laminating) the adhesive laminate to a support. The adhesive layer laminate fixed to the support may be cut into a desired shape such as a circular shape.

In the adhesive support, the adhesive layer laminate may be formed by forming a release layer only on one side of the adhesive film, or by forming a release layer on both sides of the adhesive film. In the case where a release layer is formed only on one surface, the release layer may be disposed on the support side, or the release layer may be disposed on the surface opposite to the support.

In the adhesive support, the support (also referred to as carrier support) 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 support is not particularly limited, but is preferably 300 탆 to 100 mm, more preferably 300 탆 to 10 mm, for example.

The release layer may be provided on the surface of the support. That is, the support may be a release layer-attached support.

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 material for the release layer, the same materials as those described for the release layer of the above-described pressure-sensitive adhesive laminate can be used.

&Lt; Device Wafer Laminate &gt;

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 laminate of the present invention between the device wafer and the support, and the adhesive laminate is in contact with the device wafer and the support. That is, one surface of the laminate for adhesion is in contact with the device surface of the device wafer, and the other surface is in contact with the surface of the support.

When the adhesive layer for laminating has a release layer on both sides of the adhesive film, the release layer on one side is in contact with the device wafer and the release layer on the other side is in contact with the support. When the adhesive layer for laminating has a release layer on only one side of the adhesive film, the release layer is in contact with only one of the device wafer or the support.

The device wafer can be any known one 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. Examples of the device wafer on which the mechanical structure and the circuit are formed include MEMS (Micro Electro Mechanical Systems), a power device, an image sensor, a microsensor, an LED, an optical device, an interposer, a buried device and a microdevice.

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 탆, more preferably 5 to 100 탆, for example.

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, not more than 2000 mu m, more preferably not more than 1500 mu m.

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, for example, preferably 1 m or more, more preferably 5 m or more.

In the device wafer stacking laminate of the present invention, the support (carrier support) is in agreement with the support described in the above-mentioned adhesive support, and the preferable range is also the same.

The device wafer laminate of the present invention can be produced by heat-pressing a surface of the above-described adhesive support on the side where the adhesive laminate is formed and a device wafer. 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 laminate according to the present invention between the support and the device wafer, followed by hot pressing.

<Method of Manufacturing Semiconductor Device>

Hereinafter, one embodiment of a method for manufacturing a semiconductor device through a process for manufacturing a device wafer laminated body will be described with reference to FIG. However, the present invention is not limited to the following embodiments.

1 (A) to 1 (E) are schematic cross-sectional views (Figs. 1A and 1B) for explaining adhesion between a support and a device wafer, a state in which a device wafer adhered to a support is thin 1 (C)), a state in which the support and the device wafer are separated (Fig. 1 (D)), and a state after the adhesive layer is removed from the device wafer (Fig. 1 (E)).

In this embodiment, as shown in Fig. 1 (A), first, an adhesive supporting body 100 comprising the supporting body 12 and the adhesive layer 11 is prepared. The adhesive support 100 can be manufactured by the above-described method. The adhesive support (100) is preferably an embodiment that does not substantially contain a solvent.

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.

Subsequently, as shown in Fig. 1 (B), the adhesive supporting body 100 and the device wafer 60 are pressed together to bond the supporting body 12 and the device wafer 60 together.

It is preferable that the adhesive laminate 11 completely covers the device chip 62. When the height of the device chip is X m and the thickness of the adhesive laminate is Y m, X "is satisfied.

The reason why the adhesive layer stack 11 completely covers the device chip 62 is that the TTV (Total Thickness Variation) of the thin device wafer is further lowered (i.e., the flatness of the thin device wafer is further improved If you want to do so).

That is, when the device wafer is thinned, it is possible to substantially eliminate the irregularities on the contact surface with the support member 12 by protecting the plurality of device chips 62 with the adhesive layer 11. 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. As a result, TTV can be lowered.

Subsequently, as shown in Fig. 1 (C), the back surface 61b of the silicon substrate 61 is subjected to a mechanical or chemical treatment (such as, but not limited to, gliding or chemical mechanical polishing Treatment with a chemical such as an organic solvent, an acidic treatment solution or a basic treatment solution, a plating treatment, an irradiation with an actinic ray, and heating (such as a chemical treatment) (For example, an average thickness of less than 500 占 퐉, and more preferably 1 to 200 占 퐉 is preferable) by thinning the silicon substrate 61 as shown in Fig. 1 (C) ) To obtain a thin device wafer 60a.

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. Concretely, the maximum attained temperature in the heat treatment is preferably 130 ° C to 400 ° C, more preferably 180 ° C to 350 ° C. The maximum attained temperature in the heat treatment is preferably lower than the softening point 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. 1 (D), the support 12 is removed from the thin device wafer 60a. The method of desorption is not particularly limited, but 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. At this time, it is preferable that the peeling interface be peeled from the interface between the support member 12 and the adhesive layer 11. In this case, assuming that A is the peel strength at the interface between the support 12 and the adhesive layer 11, and B is the peel strength between the device wafer surface 61a and the adhesive layer 11, Is satisfied.

A <B ... (1)

When the thin film device wafer 60a is brought into contact with the peeling solution 11 described below and then the thin device wafer 60a is slid with respect to the support member 12 as required, It may be pulled up in the vertical direction with respect to the device wafer from the end portion and peeled 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 peeling liquid, an organic solvent which dissolves the adhesive layer 11 is preferable. Examples of the organic solvent include aliphatic hydrocarbons (such as hexane, heptane, Isopar E, H, and G (manufactured by Esso Chemicals)), aromatic hydrocarbon (toluene, xylene, (Such as methylene dichloride, ethylene dichloride, tricylene, 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.).

Further, 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% by mass of the peeling liquid, respectively.

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.

Examples of the alkali include sodium tertiary phosphate, potassium tertiary phosphate, ammonium tertiary phosphate, sodium secondary phosphate, dibasic potassium phosphate, ammonium secondary phosphate, sodium carbonate, potassium carbonate, ammonium carbonate, sodium hydrogen carbonate, An inorganic alkali such as potassium hydrogen carbonate, ammonium hydrogen carbonate, sodium borate, potassium borate, ammonium borate, sodium hydroxide, ammonium hydroxide, potassium hydroxide and lithium hydroxide; Diethylamine, triethylamine, monoisopropylamine, diisopropylamine, triisopropylamine, n-butylamine, monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, ethylene Organic alkali agents such as imine, ethylenediamine, pyridine, and tetramethylammonium hydroxide 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, 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 range, the peeling property of the adhesive layer 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, sodium 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 esters, alkylsulfuric 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, Phosphoric acid ester salts, polyoxyethylene alkyl ether phosphate ester salts, polyoxyethylene alkylphenyl ether phosphate ester salts, partial saponification products of styrene-maleic anhydride copolymer, partial saponification products of olefin-maleic anhydride copolymer, naphthalene sulfone And acid phosphomoline condensation products. 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 ethylene oxide adducts, fatty acid ethylene oxide adducts, polyhydric alcohol fatty acid ester ethylene oxide adducts, higher alkylamine ethylene oxide adducts, fatty acid amide ethylene oxide adducts, ethylene oxide adducts of fats and oils, polypropylene glycol ethylene oxide adducts, Dimethylsiloxane- (propylene oxide-ethylene oxide) block copolymers, fatty acid esters of polyhydric alcohol type glycerol, fatty acid esters of pentaerythritol, fatty acids of sorbitol and sorbitol Ester, fatty acid of sucrose Esters, alkyl ethers of polyhydric alcohols, fatty acid amides of alkanolamines, and the like. 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 a defoaming agent and a water softening agent may also be contained.

1 (E), a thin device wafer can be obtained by removing the adhesive layer 11 from the thin device wafer 60a.

The method of removing the adhesive laminate 11 may be, for example, a method of peeling off (removing the machine) the adhesive laminate as a film, a method of swelling the adhesive laminate with the peeling liquid, A method of dissolving and removing a laminate for adhesion by dissolving a laminate for adhesion in a peeling liquid, a method of dissolving and removing the laminate for adhesion by irradiation of an actinic ray, radiation, or heat Followed by decomposition and vaporization. A method in which the adhesive laminate is peeled off and removed in the form of a film, and a method of dissolving and removing the adhesive laminate in an aqueous solution or an organic solvent can be preferably used. It is preferable to remove the film in the form of a film from the viewpoint of reducing the use amount of the solvent. In order to remove the film while keeping the film shape, the peeling strength B between the device wafer surface 61a and the adhesive layer 11 2).

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

In the present invention, when peeling the support member 12 from the thin device wafer 60a, it is preferable to pull up the end portion of the thin device wafer 60a in the vertical direction with respect to the device wafer, As a method of removing the adhesive layer 11 on the wafer surface 61a, it is preferable to remove the adhesive layer 11 in a film form.

When the peel strength of the interface between the support 12 and the adhesive layer 11 is denoted by A and the peel strength between the surface of the device wafer 61a and the adhesive layer 11 is denoted by B, The support member 12 and the adhesive layer 11 can be removed from the device wafer in the above-described manner.

In addition, when the support is peeled from the device wafer and peeled off at the interface between the device wafer and the adhesive laminate (that is, when the adhesive laminate does not remain on the device wafer side) May be omitted.

After removing the support member 12 from the thin device wafer 60a, various known processes are performed on the thin device wafer 60a, if necessary, to manufacture a semiconductor device having the thin device wafer 60a .

Further, in the case where the adhesive laminate is attached to the support, the support can be regenerated by removing the adhesive laminate. Examples of the method for removing the adhesive laminate include a method of physically removing the film by spraying brushes, ultrasonic waves, ice particles, and aerosols while remaining in a film form, a method of dissolving and removing the film by dissolving in an aqueous solution or an organic solvent, And a method of chemical decomposition by decomposition or vaporization by irradiation of heat. Depending on the support, conventionally known cleaning methods can be used.

For example, in the case of using a silicon substrate as a support, a conventionally known silicon wafer cleaning method can be used. For example, as an aqueous solution or an organic solvent that can be used for chemical removal, a strong acid, a strong base, 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, and a mixture of hydrofluoric acid and ammonium fluoride.

From the viewpoint of adhesiveness in the case of using a regenerated support, it is preferable to use a supporter cleaning liquid.

The support cleaning liquid preferably 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 cleaning property of the adhesive layer on the support, it is preferably an inorganic acid, and sulfuric acid is most preferable.

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

<< Conventional Embodiment >>

Next, a conventional embodiment will be described.

2 is a schematic cross-sectional view for explaining the release of the adhesion state between the conventional adhesive support and the device wafer.

In the conventional embodiment, as shown in Fig. 2, an adhesive supporting body 100a comprising an adhesive layer 11b formed by a conventional adhesive agent on a supporting body 12 is used as an adhesive supporting body, Otherwise, similar to the procedure described with reference to Fig. 1, the adhesive supporting body 100a and the device wafer are adhered to each other, the thinning treatment of the silicon substrate is performed on the device wafer. Subsequently, The thin device wafer 60a is peeled off from the thin device wafer 100a.

However, according to the conventional adhesive, it is difficult to easily dispose the treated member with the treated member without having damage to the processed member by having the treated member with high adhesive force. For example, if a high adhesion property is employed among conventional adhesive agents in order to sufficiently bond the device wafer and the support, adhesion between the device wafer and the support tends to be too strong. Therefore, as shown in Fig. 3, a tape (for example, a dicing tape) 70 is attached to the back surface of the thin device wafer 60a, The thin film device wafer 60a is peeled off from the supporting substrate 100a by breaking the device chip 62 such that the structure 63 is removed from the device chip 62 provided with the structure 63, Defects are likely to occur.

On the other hand, among conventional adhesive agents, if the adhesive agent having a low adhesiveness is used, the holding of the processed member can be easily released. However, since the adhesion between the device wafer and the carrier substrate is too weak, It is likely that defects can not be surely supported.

On the other hand, the adhesive laminate of the present invention exhibits sufficient adhesiveness and can easily release the adhesion between the device wafer 60 and the supporting member 11. That is, according to the adhesive laminate of the present invention, the device wafer 60 can be adhered to the thin device wafer 60a with high adhesive force, and the device wafer 60 can be adhered to the thin device wafer 60a without damaging the thin device wafer 60a The adhesive can be easily released.

The manufacturing method of the semiconductor device of the present invention is not limited to the above-described embodiment, but can be appropriately modified and improved.

In the above-described embodiment, a silicon wafer is used as the device wafer. However, the present invention is not limited to this, but may be any workpiece that can be provided for mechanical or chemical treatment in the semiconductor device manufacturing method. Examples of the compound semiconductor substrate include SiC substrate, SiGe substrate, ZnS substrate, ZnSe substrate, GaAs substrate, InP substrate, GaN substrate, and the like.

In the above-described embodiment, the thinning process of the device wafer and the process of forming the silicon through electrode are exemplified as the mechanical or chemical process for the device wafer (silicon substrate). However, the present invention is not limited to this, And the like.

In addition, the shape, size, number, location, etc. of the device chip in the device wafer exemplified in the above-described embodiments are arbitrary and not limited.

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 it is beyond the ordinary knowledge. Unless otherwise specified, "part" and "%" are based on mass.

&Lt; Method for producing laminate for adhesion &gt;

The composition for film production described below was coated on a polyethylene terephthalate film (release film) having a thickness of 75 占 퐉 at a speed of 1 m / min by a wire bar and dried at 140 占 폚 for 10 minutes to obtain a 100 占 퐉- .

The composition for film production in the laminate for attachment layers 1-4, 1-5, 1-15, 1-16, 1-17, and 1-18 described in Table 1 below was melted at 300 ° C for 5 minutes And extruded from a slit having a width of 100 mu m to produce an extrusion-molded sheet (adhesive film) having a film thickness of 100 mu m.

The commercially available polyimide film (Capton, Toray DuPont) was extruded from the composition for film production in the laminate for adhesive lamination 1-R2 shown in the following Table 1 to obtain an extrusion-molded sheet Film).

Subsequently, the following coating liquid for forming a release layer was coated on the adhesive film, and oven drying was performed at 120 DEG C for 1 minute to form an adhesive layer laminate having a release layer having a thickness of 60 nm .

[Composition for film production]

Polymers listed in Table 1: The mass parts shown in Table 1

Irganox (registered trademark) 1010 (manufactured by BASF Corporation): 0.9 parts by mass

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

Solvents listed in Table 1: The mass parts shown in Table 1

[Application liquid for forming release layer]

The release agent described in Table 1: The mass part

Solvents listed in Table 1: The mass parts shown in Table 1

[Table 1]

The compounds listed in Table 1 are as follows.

<Polymer>

(a-1) Septon 2104 (hydrogenated polystyrene elastomer, 5% thermal mass reduction temperature = 400 ° C or more and less than 450 ° C, Mw = 50,000 or more and 100,000 or less, manufactured by Kuraray Co.,

(a-2) Tuftec P2000 (partially selective hydrogenated polystyrene elastomer, 5% thermal mass reduction temperature = 400 占 폚 or more and less than 450 占 폚, Mw = 50,000 or more and less than 100,000, manufactured by Asahi Kasei Corporation)

(a-3) Ultrason E6020 (polyether sulfone, 5% thermal mass reduction temperature = 450 ° C or higher, manufactured by BASF)

(a-4) Hytrel 7247 (polyester elastomer, 5% thermal mass reduction temperature = 350 DEG C or more and less than 400 DEG C, manufactured by Toray DuPont)

(a-5) Primalloy CP300 (polyester elastomer, 5% thermal mass reduction temperature = 350 DEG C or more and less than 400 DEG C, manufactured by Mitsubishi Kagaku Co., Ltd.)

(a-6) SIS-5200P (non-hydrogenated polystyrene type elastomer, at least 250 DEG C and less than 350 DEG C, Mw = 100,000 or more and less than 200,000, manufactured by JSR Corporation)

(a-7) Thermorun Z102B (polyolefin elastomer, manufactured by Mitsubishi Kagaku K.K.)

(a-8) PANDEX T-2185 (polyurethane-based elastomer, manufactured by DIC Corporation)

(a-9) UBESTA XPA9040F1 (polyamide elastomer, 5% thermal mass reduction temperature = 350 DEG C or more and less than 400 DEG C, manufactured by Ube Gosan Co., Ltd.)

(a-10) XYRON S201A (polyphenylene ether, manufactured by Asahi Kasei Corporation)

(Ra-1) capton (polyimide, 5% thermal mass reduction temperature = 450 ° C or higher, manufactured by Du Pont DuPont)

<Release Agent>

(b-1) Megafac F-553 (oligomer having fluorine group, hydrophilic group and hydrophilic group, oil, Mw = 0.2 to less than 2.0 million, manufactured by DIC)

(b-2) Megapac F-557 (fluorine group, hydrophilic group, hydrophilic group-containing oligomer, oil, Mw = 0.2 to less than 2.0 million, manufactured by DIC)

(b-3) Dyepree FB962 (fluorine-based releasing agent, Mw = 0.2 to less than 2.0 million, manufactured by Daikin)

(b-4) Megaparc RS-72-K (30 mass% solution, reactive fluorine compound, Mw = 0.2 to less than 2.0 million, manufactured by DIC)

(b-5) Optol DSX (20 mass% solution, fluorine-based silane coupling agent, manufactured by Daikin)

(b-6) trichloro (1H, 1H, 2H, 2H-tridecafluoro-n-octyl) silane (fluorine-based silane coupling agent, manufactured by Tokyo Kasei Kogyo Co.,

(b-7) trimethoxy (1H, 1H, 2H, 2H-heptadecafluorodecyl) silane (fluorine-based silane coupling agent, manufactured by Tokyo Kasei Kogyo Co.)

(b-8) triethoxy (1H, 1H, 2H, 2H-tridecafluoro-n-octyl) silane (fluorine-based silane coupling agent, manufactured by Tokyo Kasei Kogyo Co.,

(b-9) X-22-164 (silicone-based bifunctional monomer manufactured by Shin-Etsu Chemical Co., Ltd.)

<Solvent>

Fluorine Solvent 1: Fluorinert FC40 (3M)

PGMEA: propylene glycol-1-methyl ether acetate

<Production of Adhesive Support 1>

The adhesive film produced by the above method was set on a vacuum laminator. Then, in this apparatus, the adhesive film was placed on a 100 mm Si wafer (support), the Si wafer was brought into contact with the opposite side of the release layer of the adhesive film under vacuum, the adhesive film and the Si wafer were fixed with a roller, An adhesive support 1 was produced.

&Lt; Preparation of test piece &

The surface of the adhesive support 1 on which the adhesive film was formed and the device surface of a 100 mm Si wafer (device wafer) were pressed under vacuum at 190 DEG C and 0.11 MPa for 3 minutes to prepare test pieces.

&Lt; Adhesive layered product (1-R3) and method for producing test piece &gt;

28.2 parts by mass of the above polymer (a-1), 0.9 parts by mass of Irganox (registered trademark) 1010 (manufactured by BASF), 10 parts by mass of Sumilizer (registered trademark) TP-D (manufactured by Sumitomo Chemical Co., , And 70 parts by mass of mesitylene was spin-coated on a 100 mm Si wafer, baked at 110 占 폚 for 1 minute, and further baked at 190 占 폚 for 4 minutes to form an adhesive layer having a thickness of 100 占 퐉.

Next, on the surface of the adhesive layer, a composition containing 0.5 parts by mass of the above releasing agent (b-5) and 99.5 parts by mass of the above fluorine solvent 1 was applied by spin coating and baked at 120 DEG C for 30 seconds, Followed by heating for 3 minutes to form a release layer having a thickness of 60 nm to prepare an adhesive support 1 having the adhesive layer.

Next, the side of the adhesive support 1 on which the adhesive laminate was formed and the device side of a 100 mm Si wafer (device wafer) were subjected to compression under vacuum at 190 DEG C and 0.11 MPa for 3 minutes, .

<Flatness>

The average thickness of the adhesive laminate was measured from one end face of the adhesive support to the other end face at five places at equal intervals and the average value of the values measured by ellipsometry (Average film thickness), and the difference between the maximum thickness and the minimum thickness was measured and evaluated according to the following criteria.

A: | Average film thickness - Maximum thickness or minimum thickness | is 0 μm or more and less than 5 μm

B: Average film thickness - Maximum thickness or minimum thickness | is not less than 5 占 퐉 and less than 20 占 퐉

C: Average film thickness - Maximum thickness or minimum thickness |

<Adhesiveness>

The shear adhesive strength of the test specimen was measured in a direction along the face of the adhesive layer at a rate of 250 mm / min using a tensile tester (digital force gauge manufactured by Imada Corporation, model: ZP-50N) did.

A: Adhesion of 50 N or more

B: Adhesion of 10N or more and less than 50N

C: Adhesion less than 10N

<Peelability>

The test piece was set together with the dicing frame in the center of the dicing tape mounter, and the dicing tape was placed from above. The test piece and the dicing tape were fixed with rollers (and vacuum), the dicing tape was cut on the dicing frame, and the test piece was mounted on the dicing tape.

The test piece was pulled in the vertical direction of the adhesive layer under the condition of 500 mm / min to confirm the peelability. The prepared test piece was heated at 250 占 폚 for 30 minutes and then stretched in the vertical direction of the adhesive layer under the condition of 250 mm / min in the same manner. The peelability after the heat treatment was confirmed and evaluated according to the following criteria. The presence or absence of breakage of the Si wafer was visually confirmed.

A: The maximum peeling force was less than 6N and peeling was possible.

B: The maximum peeling force was 6N or more and less than 12N, and peeling was possible.

C: The maximum peel force was 12N or more and less than 20N, and peeling was possible.

D: The peeling force at the maximum was 20 N or more and could be peeled off, but the Si wafer was damaged.

&Lt; Removability (dissolution removal) &gt;

After completion of the peelability test, the Si wafer with the adhesive film was set on a spin coater with the adhesive film facing up and sprayed for 5 minutes using the solvent shown in Table 2 as a cleaning solvent. Further, spin drying was performed. Thereafter, the appearance was observed to visually check the presence or absence of the adhesive film remaining on the Si wafer, and the evaluation was made according to the following criteria.

A: Remaining adhesive film is not confirmed

B: Remaining adhesive film was confirmed

<Removability (film removal)>

After the peelability test was completed, a peeling tape (manufactured by LINTEC CORPORATION) was affixed onto a Si wafer with an adhesive film attached to a part of the outer periphery of the Si wafer, the peeling tape was pulled in the vertical direction, Peeled. Thereafter, the appearance was observed, and the presence or absence of the peeling residue of the adhesive film remaining on the thin device wafer was visually checked and evaluated according to the following criteria.

A: The adhesive film can be removed without breaking, and the peeling residue of the adhesive film can not be confirmed.

B: I broke in the middle of peeling. Alternatively, the adhesive film could be removed, but the residue remained.

[Table 2]

From the above results, in Examples 1 to 18, flatness, adhesiveness and peelability were good. Further, the removability of the adhesive layer was satisfactory in both of dissolution removal and film removal.

On the other hand, Comparative Examples 1 to 3 were inferior in flatness, adhesive property, and peelability.

11, 11a:
12: Support
60: device wafer
60a: thin device wafer
61: silicon substrate
61a: Surface
61b, 61b1:
62: Device chip
63: structure
100: Adhesive support

Claims (13)

A laminate for adhesive bonding, which is used for releasably adhering a device surface of a device wafer and a support,
Based elastomer, a polyimide elastomer, a polyether elastomer, a polyether elastomer, a polyether elastomer, a polyether elastomer, a polyurethane elastomer, a polyurethane elastomer, a polyamide elastomer, a polyacrylic elastomer, A film comprising at least one member selected from the group consisting of styrene,
And a releasing layer comprising a releasing agent containing at least one selected from a fluorine atom and a silicon atom on at least one surface of the film. The method according to claim 1,
Wherein the film comprises at least one selected from a polystyrenic elastomer and a polyethersulfone. The method according to claim 1,
Wherein the film comprises a polystyrene type elastomer. The method according to any one of claims 1 to 3,
Wherein the polystyrene type elastomer is a hydrogenated product. The method according to any one of claims 1 to 4,
Wherein the 5% thermal mass reduction temperature of the polystyrene-based elastomer heated from 25 占 폚 to 20 占 폚 / min is 250 占 폚 or higher. The method according to any one of claims 1 to 5,
Wherein the releasing agent is a silane coupling agent. The method according to any one of claims 1 to 6,
And the release layer is provided on both surfaces of the film. The method according to any one of claims 1 to 6,
And the release layer is formed on only one surface of the film. Based elastomer, a polyimide-based elastomer, a polyetheretherketone, a polyphenylene ether, and a polyimide-based elastomer, which are selected from the group consisting of a polystyrene elastomer, a polystyrene elastomer, a polyester elastomer, a polyolefin elastomer, a polyurethane-based elastomer, A step of forming a release layer comprising a releasing agent containing at least one selected from a fluorine atom and a silicon atom on a surface of a film containing at least one kind selected from the group consisting of &Lt; / RTI &gt; The device according to any one of claims 1 to 8, characterized in that it has a laminate for adhesive bonding as set forth in any one of claims 1 to 8 between the device wafer and the support, wherein one surface of the laminate for adhesion is in contact with the device surface of the device wafer, Wherein the substrate is in contact with the surface of the support. The method of claim 10,
The adhesive layer laminate has a release layer on both surfaces of the film. The method of claim 10,
Wherein the adhesive layer laminate has a release layer on only one surface of the film and the release layer is in contact with the surface of the device wafer. The method of claim 10,
The adhesive layer laminate has a release layer on only one surface of the film, and the release layer is in contact with the support.

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