TWI661935B - Laminated body temporarily, manufacturing method of laminated body temporarily, and laminated body with element wafer - Google Patents

Abstract

Provided are a temporarily bonded laminated body, a method for manufacturing a temporarily bonded laminated body, and a laminated body with an element wafer, which can easily release the temporary bonding of the element wafer and the support. The temporary bonding laminate according to the present invention is a temporary bonding laminate which is used to temporarily and releasably bond the element surface of a component wafer and a support, and includes a thermoplastic resin film and a layer containing a mold release agent. The agent is selected from a compound having a siloxane bond and a compound having a silicon atom and a fluorine atom; and the surface of the thermoplastic resin film on the element side and the region corresponding to the element surface includes at least a layer containing a release agent. After the element wafer and the support are temporarily adhered, when the support is peeled from the element surface of the element wafer, a laminate including at least the support and the thermoplastic resin film is peeled from the element.

Description

Laminated body temporarily, manufacturing method of laminated body temporarily, and laminated body with element wafer

The present invention relates to a method for manufacturing a temporary laminated body, a method for manufacturing a temporarily laminated body, and a laminated body with an element wafer. More specifically, the present invention relates to a temporary bonding laminate, a method for manufacturing a temporary bonding laminate, and a multilayer wafer with an element wafer, which can be preferably used in the manufacture of semiconductor devices and the like.

In the manufacturing process of a semiconductor device such as an image sensor, an integrated circuit (IC), and a large-scale integration (LSI), a plurality of ICs are formed on an element wafer. The wafer is diced to be diced.

With the further miniaturization, thin film, high performance, and low power consumption of electronic equipment, the IC chip mounted on the electronic equipment is also required to be further miniaturized and highly integrated. The direction of the integration of the integrated circuit is close to the limit.

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 the IC chip. However, in order to reduce the size of the IC chip, in-devices have been known in recent years. A through hole is provided on the wafer, and a metal plug as an external terminal is integrated with the integrated body so as to penetrate the through hole. Method of circuit connection (so-called method of forming a through silicon electrode (TSV)). However, simply by forming the through-silicon electrodes, it is not possible to sufficiently respond to the recent demand for further accumulation of IC chips.

In view of the foregoing, there is known a technique for increasing the integration degree per unit area of an element wafer by multilayering an integrated circuit in an IC wafer. However, the multi-layer circuit of the integrated circuit increases the thickness of the IC wafer, and therefore, the thickness of the components constituting the IC wafer needs to be reduced. The reduction in thickness of such components, such as the reduction in thickness of element wafers, is not only related to the miniaturization of IC wafers, but also saves labor in the process of manufacturing through-holes of element wafers in the manufacture of through-silicon electrodes. have a future. Furthermore, in semiconductor devices such as power devices and image sensors, from the viewpoint of increasing the integration degree or increasing the degree of freedom of the device structure, attempts have been made to reduce the thickness.

Element wafers are widely known that have a thickness of 700 μm to 900 μm. In recent years, attempts have been made to reduce the thickness of element wafers to 200 μm or less for the purpose of miniaturization of IC wafers and the like.

However, element wafers with a thickness of 200 μm or less are very thin, and components for manufacturing semiconductor elements based on the substrate are also very thin. Therefore, when further processing is performed on such a component, or only such a component is moved, It is difficult to stabilize and support the member without causing damage.

In order to solve the above-mentioned problems, a technique is known in which a silicon wafer is used to temporarily attach a component wafer before the thinning of the component on the surface and a support substrate for processing, and then grind the back surface of the component wafer to After the thickness is reduced, the silicon wafer is perforated with element through-holes, and then the supporting substrate for processing is removed from the element wafer. Away (see Patent Document 1). This technology can simultaneously achieve resistance to grinding resistance during backside grinding of element wafers, heat resistance during anisotropic dry etching steps, etc., chemical resistance during plating or etching, and the final support substrate for processing Smooth peeling, low adherend contamination.

In addition, as a method for supporting a wafer, a technique is also known in which a wafer is supported by a support layer system, and a plasma polymerization obtained by a plasma deposition method is installed between the wafer and the support layer system. The physical layer is used as a separation layer, so that the bonding between the support layer system and the separation layer becomes larger than that between the wafer and the separation layer. When the wafer is detached from the support layer system, the wafer can be separated from the separation layer. It is structured so as to be easily separated (see Patent Document 2).

Further, a technique is known in which temporary bonding is performed using a polyether fluorene and a tackifier, and the temporary bonding is released by heating (see Patent Document 3).

Further, a technique is also known in which temporary bonding is performed by including a mixture of carboxylic acids and amines, and temporary bonding is released by heating (see Patent Document 4).

In addition, a technique is known in which the element wafer and the support substrate are pressure-bonded in a state in which a bonding layer containing cellulose polymers and the like is heated, and subsequently, the component wafer and the support substrate are heated to the horizontal direction. By sliding in the direction, the element wafer is detached from the support substrate (see Patent Document 5).

Furthermore, an adhesive film is known which contains syndiotactic 1,2-polybutadiene and a photopolymerization initiator, and changes the adhesion by irradiating radiation (see Patent Document 6).

In addition, a technique is known in which a support substrate and an element wafer are temporarily adhered with a polycarbonate-based adhesive, the element wafer is processed, and then irradiated. The irradiation line is then heated to detach the processed element wafer from the support substrate (see Patent Document 7).

In addition, a technique is known in which a support substrate and an element wafer are temporarily adhered in two layers with different softening points, and after the element wafer is processed, the substrate is heated and slid in the lateral direction, thereby causing the support substrate and the element to slide. Technology for wafer detachment (see Patent Document 8).

Further, Patent Document 9 discloses a method of temporarily fixing a support and a substrate via a temporary fixing material including a cycloolefin polymer, a silicone structure, a fluorinated alkyl structure, and fluorination. A compound having at least one structure of an alkenyl structure and an alkyl structure having 8 or more carbon atoms, and at least one structure of a polyalkylene oxide structure, a structure having a phosphate group, and a structure having a sulfo group.

Further, Patent Document 10 discloses a method of bonding an element wafer to a support using an adhesive composition containing an elastomer and wax including a styrene unit as a constituent unit of a main chain.

In addition, Patent Document 11 discloses a method for manufacturing a semiconductor device, which includes temporarily fixing a film made of a specific polyimide resin containing a polyimide resin between a support member and an element wafer, and temporarily supporting the support member and the element wafer. The step of fixing the element wafer; the step of applying a predetermined process to the element wafer temporarily fixed on the supporting member; the organic solvent is brought into contact with the temporarily fixing film to dissolve a part or all of the temporarily fixing film, and the processing is separated from the supporting member and processed Of the component wafer; the step of singulating the processed component wafer.

Furthermore, Patent Document 12 discloses that the element surface of an element wafer is coated with The cloth forms an adhesive layer, and a release layer containing a fluorinated silane compound is coated on the surface of the support to form an adhesive layer on the element wafer and a release layer on the support. method.

Further, Patent Document 13 discloses a method for freely holding electronic parts and a substrate using a fluorine-based elastomer containing a hardened product containing a compound having at least two molecules in a molecule: Perfluorinated compounds with an alkenyl group and a divalent perfluoroalkylene or divalent perfluoropolyether structure in the main chain, (B) having at least two hydrosilyl groups in the molecule, and can be carried out with alkenyl groups Addition reaction compound, (C) addition reaction catalyst, (D) addition reaction control agent.

[Prior Art Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2011-119427

[Patent Document 2] Japanese Patent Publication No. 2009-528688

[Patent Document 3] Japanese Patent Laid-Open No. 2011-225814

[Patent Document 4] Japanese Patent Laid-Open No. 2011-052142

[Patent Document 5] Japanese Patent Publication No. 2010-506406

[Patent Document 6] Japanese Patent Laid-Open No. 2007-045939

[Patent Document 7] US Patent Publication No. 2011/0318938

[Patent Document 8] US Patent Publication No. 2012/0034437

[Patent Document 9] Japanese Patent Laid-Open No. 2013-241568

[Patent Document 10] Japanese Patent Laid-Open No. 2014-34632

[Patent Document 11] Japanese Patent Laid-Open No. 2014-29999

[Patent Document 12] International Publication WO2013 / 119976

[Patent Document 13] Japanese Patent Laid-Open No. 2005-236041

However, the surface of the element wafer on which the element is provided (that is, the element surface of the element wafer) and the support substrate (carrier substrate) are temporarily bonded to each other via the adhesive-containing layer known in Patent Document 1 and the like. In this case, in order to stably support the element wafer, a bonding force of a certain strength is required for the bonding layer.

Therefore, when the entire surface of the element surface of the element wafer and the support are temporarily bonded via the bonding layer, the temporary bonding of the element wafer and the support is too strong. Therefore, when the element wafer is detached from the support, , It is easy to cause the failure of the component or the component from the component wafer.

Furthermore, as shown in Patent Document 2, in order to suppress the excessive adhesion between the wafer and the support layer system, a method of forming a plasma polymer layer as a separation layer between the wafer and the support layer system by a plasma deposition method is used. There are the following problems: (1) under normal circumstances, the equipment cost for implementing the plasma deposition method is large; (2) the vacuum forming of the layer using the plasma deposition method or the accumulation of monomers takes time; (3) Even if a separation layer including a plasma polymer layer is provided, in the case where the wafer supplied to the process is supported, the bonding between the wafer and the separation layer is sufficient, but on the other hand, the support of the wafer is released In the case of this, it is not easy to control the bonding and the like where the wafer is easily detached from the separation layer.

Further, as described in Patent Document 3, Patent Document 4, and Patent Document 5 As described above, in the method of releasing the temporary connection by heating, when the element wafer is detached from the support, a failure of the element is likely to occur.

In addition, as in Patent Documents 6 and 7, in a method of irradiating an irradiation beam to release the temporary connection, it is necessary to use a support that transmits the irradiation beam.

Furthermore, as in the case of Patent Document 8, when the softening point of the bonding layer on the element wafer side is 20 ° C or more higher than that of the bonding layer on the substrate side, the bonding layer on the substrate side is transferred to the element crystal after peeling On the bonding layer on the round side, there is a problem that the cleanability of the element wafer is reduced.

In addition, when the adhesive of Patent Document 9 is used as a temporary fixing material, the peelability is insufficient, and therefore there is a problem that a defect such as breakage of a component easily occurs when the component wafer is peeled. In addition, the adhesion layer is likely to remain on the element wafer side.

Furthermore, in Patent Document 10, an adhesive composition is applied to an element wafer or the like to form an adhesive layer. Therefore, when the support is peeled from the element wafer, the adhesion layer is likely to remain on the element wafer side. In addition, in the method disclosed in Patent Document 10, the peelability of the support from the element wafer is insufficient.

Further, in Patent Document 11, an organic solvent is used to make a film for temporary fixation, and a film that is soluble in an organic solvent is used to bring the organic solvent into contact with the film for temporary fixation, thereby releasing the temporary support for the element wafer. Therefore, it takes time to release the temporary support. In addition, there is a phenomenon that a film for temporary fixation remains on the element wafer side, and the removal process of the remaining film requires an operation.

Furthermore, in Patent Document 12, the adhesive layer is formed by coating on the element surface of the element wafer. Therefore, when the support is peeled from the element wafer, the adhesion layer is likely to remain on the element wafer. Element wafer side.

Further, in Patent Document 13, the peelability is insufficient.

The present invention has been made in view of the background, and an object thereof is to provide a temporary bonding laminated body, a method for manufacturing a temporary bonded laminated body, and a device wafer with a component that can easily release the temporary bonding of the component wafer and the support. Laminated body.

The present inventors conducted intensive research in order to solve the above-mentioned problems, and as a result, they found that using the following temporary bonding laminate can temporarily bond the element wafer and the support with a high bonding force, and can easily release the wafer. The present invention completes the temporary bonding of the element wafer and the support, thereby completing the present invention by using a laminated body comprising a thermoplastic resin film and a layer containing a release agent selected from a compound having a siloxane bond and having a A compound of a silicon atom and a fluorine atom; and a region corresponding to the element surface on the element-side surface of the thermoplastic resin film and including at least a layer containing a release agent. The present invention provides the following.

<1> A laminated body for temporary bonding, which is used to temporarily and releasably peel off the element surface of a component wafer from a support, and then temporarily uses the laminated body to contain a layer of a thermoplastic resin film and a release agent, and the release The agent is selected from a compound having a siloxane bond and a compound having a silicon atom and a fluorine atom; the surface on the element side of the thermoplastic resin film, and the region corresponding to the element surface includes at least a layer containing a release agent; After temporarily bonding the element wafer and the support, the support includes at least the support and the thermoplastic resin film when the support is peeled from the element surface of the element wafer. The laminated body is peeled from the element.

<2> The laminated body for temporary bonding according to <1>, wherein the thermoplastic resin film contains a thermoplastic resin having a glass transition point of 50 ° C to 400 ° C.

<3> The laminated body for temporary bonding according to <1> or <2>, wherein the thermoplastic resin film contains a member selected from the group consisting of thermoplastic polyimide, polystyrene-based elastomer, polyester-based elastomer, and polyamide It is at least one thermoplastic resin of elastomer, polyether ether ketone, polyphenylene ether, modified polyphenylene ether, polyether fluorene, polyacetal resin, and cycloolefin polymer.

<4> The laminated body for temporary bonding according to any one of <1> to <3>, wherein the 1% weight reduction temperature of the thermoplastic resin film from 25 ° C to 20 ° C / min is 250 Above ℃.

<5> The laminated body for temporary bonding according to any one of <1> to <4>, wherein the thickness of the layer containing the release agent is 0.001 nm to 1000 nm.

<6> The laminated body for temporary bonding according to any one of <1> to <5>, wherein the layer containing the release agent is heated at 250 ° C for 2 hours and then measured under conditions of cooling to 25 ° C. The water contact angle is above 30 °.

<7> The laminated body for temporary bonding according to any one of <1> to <6>, wherein the release agent is a silane coupling agent having a silicon atom and a fluorine atom.

<8> The laminated body for temporary bonding according to any one of <1> to <7>, wherein the release agent is a compound having a silicon atom and a fluorine atom, and the content rate of the fluorine atom is 20% to 80 %.

<9> The laminated body for temporary adhesion according to any one of <1> to <6>, wherein the release agent is burned onto the thermoplastic resin by heating at 150 ° C or higher. Silicone resin on the film.

<10> A method for temporarily manufacturing a laminated body, comprising the step of forming a layer containing a release agent on the surface of a thermoplastic resin film, the release agent being selected from a compound having a siloxane bond and a silicon atom and Compounds of fluorine atom.

<11> A laminated body with an element wafer, comprising a temporarily bonded laminated body as described in any one of <1> to <9> between the element wafer and the support, and temporarily laminated laminated body The surface on the side of the release layer is in contact with the component surface of the component wafer, and the other surface is in contact with the surface of the support.

According to the present invention, it is possible to provide a temporary bonding laminate, a method for manufacturing a temporary bonding laminate, and a multilayer wafer with a component wafer, which can easily release the temporary bonding of the component wafer and the support.

11‧‧‧ Temporarily use the laminated body

11b‧‧‧ Adjacent layer

12‧‧‧ support

60‧‧‧component wafer

60a‧‧‧ thin component wafer

61‧‧‧ silicon substrate

61a, 61a1‧‧‧ component surface

61b, 61b1‧‧‧ back

62‧‧‧component chip

63‧‧‧ Structure

70‧‧‧Tape

100‧‧‧ Adhesive support

100a‧‧‧Adhesive support

110‧‧‧Release layer

111‧‧‧thermoplastic resin film

FIG. 1 is a schematic diagram showing an embodiment of a method for manufacturing a semiconductor device.

2 is a schematic cross-sectional view illustrating the release of a temporary bonding state between a conventional adhesive support and an element wafer.

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

In the description of the group (atomic group) in this specification, the descriptions of the substituted and unsubstituted expressions include a group (atomic group) having no substituent and a group (atomic group) having a substituent. For example, the term "alkyl" includes more than Substituted alkyl group), and also includes an alkyl group (substituted alkyl group) having a substituent.

The "actinic rays" or "radiation" in the present invention means, for example, that they include visible rays, ultraviolet rays, extreme ultraviolet rays, electron beams, X-rays, and the like.

In the present invention, "light" means actinic rays or radiation.

In this specification, the so-called "exposure" means not only exposure using mercury lamps, ultraviolet rays, far-ultraviolet rays, X-rays, and EUV light typified by excimer lasers, but also the use of electron beams and ions unless there is any particular limitation Beam and other particle beams.

In this specification, "(meth) acrylate" means acrylate and methacrylate, "(meth) acrylate" means acrylic and methacrylate, and "(meth) acryl" refers to propylene Fluorenyl and methacrylfluorenyl.

In the present specification, the weight average molecular weight and the number average molecular weight are defined as polystyrene conversion values measured by gel permeation chromatography (GPC). In this specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) can be, for example, HLC-8220 (manufactured by Tosoh Corporation), TSKgel Super AWM-H (manufactured by Tosoh Corporation), 6.0 mm ID × 15.0 cm was used as a column, and a 10 mmol / L lithium bromide N-Methyl Pyrrolidone (NMP) solution was used as the eluent.

In addition, in the embodiments described below, the same reference numerals are attached to the members and the like already described in the drawings referred to, and the description is simplified or omitted.

<Layer body is used for the time being>

The laminated body for temporary use in the present invention is used to connect the component surface and the support of the component wafer. The support is peelably and temporarily adhered with a laminated body, and the laminated body includes a thermoplastic resin film and a layer containing a release agent selected from a compound having a siloxane bond and a silicon atom and A compound of fluorine atom; the surface of the thermoplastic resin film on the element side and the region corresponding to the element surface contains at least a layer containing a release agent; and then a laminated body is used to temporarily bond the element wafer and the support, and then from the element When the support is peeled off from the element surface of the wafer, at least the laminate including the support and the thermoplastic resin film is peeled from the element. Hereinafter, a layer containing a release agent is referred to as a "release layer".

The laminated body for temporary bonding of the present invention is on the element-side surface of the thermoplastic resin film, and the region corresponding to the element surface includes the release layer. Therefore, the temporary bonding of the element wafer and the support can be easily released, and the peelability is excellent. . In addition, the mold release layer is formed on the surface of the thermoplastic resin film, and the surface of the thermoplastic resin film is excellent in flatness. Therefore, the mold release layer can be formed with a substantially uniform film thickness. That is, if a laminated body for temporary bonding is formed by spin coating, outgassing caused by the residual solvent, wrinkles caused by dry shrinkage, and thickening of the periphery due to edge bead Etc. However, the problem can be suppressed by using the film-shaped person as a laminated body for temporary adhesion. Therefore, when the element wafer and the support are temporarily adhered, it is difficult for the thermoplastic resin film to directly contact the element surface, and more excellent peelability can be achieved. Therefore, after the element wafer and the support are temporarily adhered, when the support is peeled from the element surface of the element wafer, the laminated body including at least the support and the thermoplastic resin film is peeled from the element, so it does not remain on the element wafer side. The thermoplastic resin film simplifies operations such as cleaning of the component wafer after releasing the temporary connection between the component wafer and the support.

In addition, since a thermoplastic resin film is used, the device wafer and the support Heating during crimping, the thermoplastic resin softens. As a result, the fine unevenness of the element wafer is also followed, and excellent adhesion can be achieved without generating voids.

In addition, in this specification, "the element surface of the element wafer and the support are peelably temporarily adhered" means a state in which the element wafer and the support are temporarily adhered and integrated (the buildup with the element wafer) Body), the temporary bonding state between the element wafer and the support is released, and the two are separated. The release of the temporary bonding state is preferably a release by mechanical peeling.

Furthermore, in this specification, "the surface on the element side of the thermoplastic resin film and a region corresponding to the element surface" means that when the element surface of the element wafer and the support are temporarily adhered, the element crystal of the laminated body is temporarily adhered. The area where the round side surface is in contact with the element surface of the element wafer.

In the laminated body for temporary bonding of the present invention, when the supporting body is peeled from the element surface of the element wafer after temporarily bonding the element wafer and the supporting body, at least the laminated body including the supporting body and the thermoplastic resin film is peeled from the element. The peeling of both may be the peeling of the interface between the element surface and the release layer, the peeling of the interface of the release layer and the thermoplastic resin film, or the peeling of the inside of the release layer.

That is, the peeling residue of a release layer may adhere to the element surface of the element wafer after peeling a support body from an element wafer. Further, it is preferable that the peeling residue of the thermoplastic resin film is not adhered in a range of 99% or more of the area of the element surface. Furthermore, the "laminate including at least a support and a thermoplastic resin film" is preferably a layer of the entire area of the thermoplastic resin film on the support, and a part of the thermoplastic resin film (preferably a thermoplastic resin film) may be peeled from the support. 10% or less, and more preferably 5% or less).

In addition, "the peeling residue of a mold release layer" means the mold release agent contained in a mold release layer. In addition, "the peeling residue of a thermoplastic resin film" means the thermoplastic resin contained in a thermoplastic resin film. The peeling residue of the release layer and the peeling residue of the thermoplastic resin film can be observed by visual inspection, an optical microscope, a scanning electron microscope, and the like. In the present invention, the peeling surface is measured by visual observation.

In addition, the "laminate including at least a support and a thermoplastic resin film" does not require the entire surface of the thermoplastic resin film to be bonded to the support, and a part of the thermoplastic resin film may not be bonded to the support.

Hereinafter, the laminated body of the present invention will be described in detail for the time being.

<< Thermoplastic resin film >>

In the laminated body for temporary bonding of the present invention, the thermoplastic resin film can be processed into a film shape by a method such as injection molding, extrusion molding, and coating. By using a thermoplastic resin film, the shape of the wafer and the like on the element wafer is deformed, so the adhesion between the element wafer and the support is good. In addition, the support body and the element wafer may be temporarily adhered without causing a gap.

The average thickness of the thermoplastic resin film is not particularly limited. For example, it is preferably 0.1 μm to 500 μm, more preferably 0.1 μm to 300 μm, and even more preferably 1 μm to 150 μm. As long as the average thickness of the thermoplastic resin film is within the above range, the flatness is good, and it can be uniformly bonded to the element surface of the element wafer. In addition, it is also difficult to generate an increase in outgassing at the time of subsequent processing or a shift at the time of bonding.

In addition, in the present invention, the average thickness of the thermoplastic resin film is defined as an average of the following values: In a cross section along one direction of the thermoplastic resin film, The end faces the other end face, and the value of the thickness at five positions is measured by a micrometer at equal intervals.

In the present invention, the “cross section along one direction of the thermoplastic resin film” is a cross section orthogonal to the longitudinal direction when the thermoplastic resin film is polygonal. When the thermoplastic resin film has a square shape, it is a cross section orthogonal to any one side. When the thermoplastic resin film is circular or oval, it is a cross section passing through the center of gravity.

The thermoplastic resin film preferably has a cross section along one direction of the thermoplastic resin film, and the difference between the maximum film thickness and the minimum film thickness is 10% or less of the average film thickness, and more preferably 5% or less.

The thermoplastic resin film is preferably 250 ° C or higher, more preferably 300 ° C or higher, and even more preferably 350 ° C or higher, for a 1% weight reduction temperature that is increased at a temperature of 20 ° C / min from 25 ° C. If the 1% weight reduction temperature of the thermoplastic resin film is 250 ° C or more, the mechanical resin or the chemical treatment of the element wafer can suppress the decomposition of the thermoplastic resin even when exposed to high temperatures, and can effectively suppress the generation of voids. The "weight reduction temperature" is a value measured by a thermogravimetric measurement device (TGA) under a nitrogen flow under the above-mentioned temperature increase conditions.

The solvent content of the thermoplastic resin film is preferably 5% by mass or less, more preferably 1% by mass or less, and particularly preferably not contained. With this aspect, outgassing can be suppressed, and voids can be prevented from being generated when heating is performed in a temporarily-adhered state. The solvent content of the thermoplastic resin film can be measured by gas chromatography (GC).

<<< thermoplastic resin >>>

In the laminated body for temporary bonding of the present invention, the thermoplastic resin film preferably contains a thermoplastic resin. The thermoplastic resin is preferably selected from thermoplastic polyimide, polystyrene-based elastomer, polyester-based elastomer, polyamido-based elastomer, polyetheretherketone, polyphenylene ether, and modified polyphenylene ether. At least one of polyether fluorene, polyacetal resin, and cycloolefin polymer. Further, from the viewpoint of heat resistance, it is more preferably selected from the group consisting of polystyrene-based elastomers, polyester-based elastomers, polyamide-based elastomers, polyetheretherketones, polyphenylene ethers, modified polyphenylene ethers, At least one of polyether fluorene, polyacetal resin, and cycloolefin polymer, and more preferably thermoplastic polyfluorene imine. The thermoplastic resin may be used singly or in combination of two or more kinds.

The thermoplastic resin film containing the above-mentioned thermoplastic resin also follows the fine unevenness of the element wafer, and can achieve excellent adhesion without generating voids. In addition, when the support is peeled from the element wafer, the support can be peeled (preferably mechanically peeled) from the element wafer without applying stress to the element wafer or the like, and breakage or peeling of the element or the like can be prevented.

In the present invention, the "thermoplastic resin" is a resin that softens at 150 ° C to 350 ° C. The storage elastic modulus at 25 ° C is preferably 10 ⁴ Pa to 10 ¹² Pa, and more preferably 10 ⁵ Pa ~ 10 ¹¹ Pa, most preferably 10 ⁶ Pa ~ 10 ¹⁰ Pa. The storage elastic modulus at 150 ° C to 300 ° C is preferably 10 ² Pa to 10 ⁷ Pa, more preferably 10 ¹ Pa to 10 ⁶ Pa, and most preferably 10 ⁰ Pa to 10 ⁵ Pa. The storage elastic modulus is a value measured by a dynamic viscoelasticity measuring device (DMA). The "softening" means a state in which the storage elastic modulus at 150 ° C to 300 ° C is 100 times or more the storage elastic modulus at 25 ° C.

The glass transition temperature (hereinafter also referred to as "Tg") of the thermoplastic resin is preferably 50 ° C to 400 ° C, more preferably 75 ° C to 400 ° C, and even more preferably 110 ° C to 350 ° C. When Tg is within the above range, the thermoplastic resin film is softened when the element wafer and the support are temporarily adhered, and the fine unevenness of the element wafer is also followed, and excellent adhesion can be achieved without generating voids. When the thermoplastic resin has two or more kinds of Tg, the Tg value indicates a low glass transition point.

The melting point of the thermoplastic resin is preferably 100 ° C to 450 ° C, and more preferably 120 ° C to 400 ° C. When the melting point is within the above range, the fine unevenness of the element wafer is also followed, and excellent adhesion can be achieved without generating voids. When the thermoplastic resin has two or more melting points, the value of the melting point indicates a low melting point.

The weight average molecular weight of the thermoplastic resin is preferably 2,000 to 200,000, more preferably 10,000 to 200,000, and most preferably 50,000 to 100,000. By being in this range, heat resistance can be made good.

<<<< Thermoplastic polyimide >>>>

The thermoplastic polyfluorene imine can be obtained by subjecting a tetracarboxylic dianhydride and a diamine to a condensation reaction by a known method.

Known methods include, for example, mixing tetracarboxylic dianhydride and diamine in an organic solvent in approximately equal amounts, reacting them at a reaction temperature of 80 ° C or lower, and subjecting the obtained polyamic acid to Closed loop dehydration methods. Here, the term "approximately equal molarity" means that the molar ratio of tetracarboxylic dianhydride to diamine is around 1: 1. In addition, if necessary, the composition ratio of the tetracarboxylic dianhydride and the diamine is set to be 1.0 mol relative to the total of the tetracarboxylic dianhydride, and the total of the diamine is 0.5 mol to 2.0 mol. Line adjustment. By adjusting the composition ratio of the tetracarboxylic dianhydride to the diamine within the above range, the weight average molecular weight of the polyfluoreneimide resin can be adjusted.

Examples of the thermoplastic polyfluorene imide resin include a thermoplastic polyfluorene imide resin having a repeating structural unit represented by the following general formula (1).

In the general formula (1), X is directly bonded, -SO _2- , -CO-, -C (CH ₃ ) _2- , -C (CF ₃ ) _2- , or -S-, R ¹ , R ² , R ³ and R ⁴ are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group, a halogenated alkyl group, a halogenated alkoxy group, or a halogen atom, and Y is selected from the group consisting of the following formula (2) The base of the group.

The thermoplastic polyfluorene imide resin having a repeating structural unit represented by the general formula (1) can use an ether diamine of the following general formula (3) and a tetracarboxylic dianhydride of the following general formula (4) as raw materials. They are reacted in the presence or absence of an organic solvent, and the obtained polyamide acid is chemically or thermally imidized to produce it.

In the general formula (3), R ¹ , R ² , R ^3, and R ⁴ each have the same meaning as the symbol in the formula (1).

In the general formula (4), Y represents the same meaning as the symbol in the general formula (1).

Specific examples of R ¹ , R ² , R ³ , and R ⁴ in the general formula (1) and the general formula (3) include a hydrogen atom, an alkyl group such as a methyl group and an ethyl group, and an alkyl group such as a methoxy group and an ethoxy group. Oxygen, halogenated alkyl such as fluoromethyl and trifluoromethyl, halogenated alkoxy such as fluoromethoxy, and halogen atoms such as chlorine and fluorine. A hydrogen atom is preferred. Moreover, X in the formula is a direct bond, -SO _2- , -CO-, -C (CH ₃ ) _2- , -C (CF ₃ ) ₂ -or -S-, preferably a direct bond, -SO _2- , -CO-, -C (CH ₃ ) _2- .

In the general formula (1) and the general formula (4), Y is represented by the formula (2), and a pyromellitic dianhydride is preferably used as the acid dianhydride.

The thermoplastic polyfluorene imide resin preferably has a repeating structural unit represented by the following formula (5).

As the thermoplastic polyfluorene imide resin, a thermoplastic polyfluorene imide resin having a repeating structural unit of the following formula (6) and formula (7) can also be cited as a preferable specific example.

In formulas (6) and (7), m and n represent the molar ratio of each structural unit (not necessarily a block polymer), and m / n is 4 to 9, more preferably 5 to 9, and even more preferably A number in the range of 6 to 9.

Thermoplastic polyfluorene having repeating structural units of formula (6) and formula (7) The amine resin can use the corresponding ether diamine and tetracarboxylic dianhydride as raw materials, and react them in the presence or absence of an organic solvent to chemically or thermally imidize the obtained polyamic acid. And manufacture. For these specific production methods, the conditions of a known method for producing polyimide can be used.

As the thermoplastic polyimide resin, a thermoplastic polyimide resin having a repeating structural unit represented by the following formula (8) can also be used.

The thermoplastic polyfluorene imide resin having a repeating structural unit of the formula (8) can use the corresponding ether diamine and tetracarboxylic dianhydride as raw materials, and react them in the presence or absence of an organic solvent. Polyamic acid is chemically or thermally fluorinated to produce it. For these specific production methods, the conditions of a known method for producing polyimide can be used.

The thermoplastic polyimide resin is excellent in heat resistance. The thermoplastic polyfluorene imide resin has a weight reduction temperature of 1% from 25 ° C at a temperature of 20 ° C / min. The temperature is preferably 250 ° C or higher, more preferably 300 ° C or higher, and still more preferably 350 ° C or higher.

The Tg of the thermoplastic polyfluorene imide resin is preferably 200 ° C to 400 ° C, more preferably It is 250 ° C to 375 ° C, and more preferably 300 ° C to 350 ° C. When Tg is within the above range, the fine unevenness of the element wafer is also followed, and excellent adhesion can be achieved without generating voids.

Commercial products of thermoplastic polyimide include, for example, "AURUM (registered trademark)" manufactured by Mitsui Chemicals Co., Ltd., and "Midfil (registered trademark)" manufactured by Kurabo Industries Co., Ltd. , "Vespel (registered trademark) TP" manufactured by DuPont, etc.

<<<< Polystyrene elastomer >>>>

The polystyrene-based elastomer is not particularly limited, and can be appropriately selected depending on the purpose. Examples include styrene-butadiene-styrene block copolymer (SBS), styrene-isoprene-styrene block copolymer (SIS), and styrene-ethylene-butene-styrene block Copolymer (SEBS), styrene-butadiene-butene-styrene copolymer (SBBS) and hydrides thereof, styrene-ethylene-butene-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 repeating unit derived from styrene in the polystyrene-based elastomer is preferably from 10% by mass to 90% by mass. From the viewpoint of easy peelability, the lower limit value is preferably 25% by mass or more, and more preferably 51% by mass or more.

The polystyrene elastomer is preferably a block copolymer of styrene and other resins, more preferably a block polymer having styrene at one end or both ends, and particularly preferably an insert having styrene at both ends. Paragraph polymer. When a polystyrene-based elastomer is made of a styrene block polymer (repeating units derived from styrene) at both ends, there is thermal stability. Qualitative tendency to improve further. The reason for this is that a repeating unit derived from styrene having high heat resistance exists at the terminal. In particular, it is preferable that the block portion of the repeating unit derived from styrene is a reactive polystyrene-based hard block, which tends to be more excellent in heat resistance and chemical resistance. In addition, when these are block copolymers, it is considered that phase separation of hard blocks and soft blocks is performed at 200 ° C or higher. This phase-separated shape is thought to contribute to suppressing the occurrence of unevenness on the substrate surface of the element wafer. In addition, 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 hydride, the stability to heat is improved, and deterioration such as decomposition or polymerization is unlikely to occur. It is also more preferable from the viewpoints of solubility in a solvent and resistance to a resist solvent.

In addition, the "repeated unit derived from styrene" in this specification is a structural unit derived from styrene contained in a polymer when styrene or a styrene derivative is polymerized, and may have a substituent. Examples of the styrene derivative include α-methylstyrene, 3-methylstyrene, 4-propylstyrene, and 4-cyclohexylstyrene. Examples of the substituent include an alkyl group having 1 to 5 carbons, an alkoxy group having 1 to 5 carbons, an alkoxyalkyl group having 1 to 5 carbons, ethoxyl, carboxyl, and the like.

Examples of commercially available polystyrene-based elastomers include "Septon" (Septon S2104, etc.) manufactured by Kuraray Co., Ltd., "HYBRAR", and Asahi Kasei "Tuftec" manufactured by Chemical Co., Ltd. and "Dynaron" manufactured by JSR Co., Ltd.

<<<< Polyester elastomer >>>>

The polyester-based elastomer is not particularly limited, and can be appropriately selected depending on the purpose. Examples thereof include those obtained by polycondensing a dicarboxylic acid or a derivative thereof with a diol compound or a derivative thereof.

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

Examples of the diol compound include fats such as ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,10-decanediol, and 1,4-cyclohexanediol. Group diols, alicyclic diols, dihydric phenols represented by the following structural formulas, and the like.

In the formula, Y ^DO represents any of an alkylene group having 1 to 10 carbon atoms, a cycloalkylene group having 4 to 8 carbon atoms, -O-, -S-, and -SO _2- , or The benzene rings are directly bonded to each other (single bond). 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-based elastomer include bisphenol A, bis- (4-hydroxyphenyl) methane, bis- (4-hydroxy-3-methylphenyl) propane, and resorcinol. These may be used alone or in combination of two or more.

Further, as the polyester-based elastomer, an aromatic polyester (such as polybutylene terephthalate) portion may be used as a hard segment component, and an aliphatic polyester (such as polybutylene glycol) portion may be used as a soft segment component. Multiblock copolymer of ingredients. As the multiblock copolymer, various grades of multiblock copolymers can be enumerated according to the types, ratios, and molecular weights of the hard segment and the soft segment. Specific examples include "Premalloy" manufactured by Mitsubishi Chemical Corporation, "PELPRENE" manufactured by Toyobo Corporation, and "Hytrel" manufactured by Toray DuPont Co., Ltd. )"Wait.

<<< Polyamine-based elastomer >>>>

The polyamide elastomer is not particularly limited, and can be appropriately selected depending on the purpose. For example, polyamines such as polyamine-6, polyamine-11, and polyamine-12 are used in the hard segment, and polyoxyethylene, polyoxypropylene, polybutylene glycol, etc. are used in the soft segment. Polyether and / or polyester elastomers. This elastomer can be roughly classified into two types, a polyether block fluorene type and a polyether ester fluorene type. Commercially available products include `` Daiamid '', `` Vestamid E '' manufactured by Daicel Evonik Co., Ltd., and `` TPAE '' manufactured by T & K TOKA Co., Ltd. "Wait.

<<<< Polyetheretherketone >>>>

The polyetheretherketone can be used without particular limitation, and examples thereof include "VICTREX" manufactured by Victrex Japan Co., Ltd. PEEK) "," EXPEEK "made by Kurabo Industries Co., Ltd.," VESTAKEEP "made by Daicel Evonik Co., Ltd., etc.

<<<< Polyphenylene ether, modified polyphenylene ether >>>>

The polyphenylene ether or modified polyphenylene ether can be used without particular limitation. For example, `` NORYL '' manufactured by Saudi Basic Industrial Innovation Plastic Japan Co., Ltd., `` Zylon '' manufactured by Asahi Kasei Chemical Co., Ltd., `` Iupiace '' manufactured by Mitsubishi Engineering Plastics Co., Ltd., "Lemalloy", "VESTORAN" manufactured by Daicel Evonik Co., Ltd., etc.

<<< Polyether 碸 >>>

Examples of polyether fluorene include Japanese Patent Laid-Open No. 2006-89595, Japanese Patent Laid-Open No. 2004-352920, Japanese Patent Laid-Open No. 2002-338688, Japanese Patent Laid-Open No. 07-97447, and Japanese Patent Laid-Open No. Hei. Polyether hydrazone described in 04-20530.

In polyether fluorene, by using polyether fluorene having an aromatic hydrocarbon structure in the polymer, the crystallinity of the film is increased, and it is easy to obtain that even in a high temperature environment above a certain temperature, the processing of the element wafer can be maintained. In terms of the added shearing force, the laminated body can be temporarily adhered while maintaining the shearing adhesive force of the element wafer. Examples of the polyether fluorene having an aromatic hydrocarbon structure include polyether fluorene having a structural unit represented by formula (IV).

[Chemical 8]

In formula (IV), R ¹ to R ³ are divalent organic groups having an aromatic hydrocarbon structure, in which the bonding bond in formula (IV) and the aromatic hydrocarbon structure in R ¹ to R ³ are directly bonded (that is, formula ( IV) -OR ¹ -O-, -OR ² -SO ₂ -and -SO ₂ -R ³ -O- -O- and -SO ₂ -are directly bonded to the aromatic structure in R ¹ ~ R ³ End). 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 naphthalene diyl group, an anthracene diyl group, and a perylene diyl group; and -C ₆ H ₄ -C ₆ H ₄ -and two arylene groups are directly bonded A group having a divalent hydrocarbon group between two arylene groups represented by the formulae (IV-1) to (IV-3), and the like.

In the formulae (IV-1) to (IV-3), * represents a bonding bond.

The weight average molecular weight (Mw) of the polyether fluorene is preferably 1,000 to 1,000,000, more preferably 5,000 ~ 500,000. When the number average molecular weight of the polyether fluorene is Mn, the molecular weight distribution expressed by Mw / Mn is preferably 1 to 5, and more preferably 1 to 3.5.

Polyether fluorene can also use a commercial item. Examples include the "Ultrason E Series" (Ultrason E6020P, etc.) manufactured by BASF, the "RADEL A Series" manufactured by Solvay Performance Polymers, and Sumitomo Chemical Co., Ltd. Co., Ltd.'s "SUMIKAEXCEL PES series", Japan's Solvay Special Polymer Co., Ltd.'s "VERADEL" and so on. The `` SUMIKAEXCEL series '' can be exemplified by SUMIKAEXCEL (registered trademark) PES3600P, SUMIKAEXCEL (registered trademark) PES4100P, SUMIKAEXCEL (registered trademark) PES4100MP, SUMIKAEXCEL (registered trademark) PES4800P, SUMIKAEXCEL (registered trademark) PES5003P, SUMIKAEXCEL (registered trademark) PES5200P, Sumitomo Excel (registered trademark) Trademark) PES5400P.

<<<< Polyacetal resin >>>>

The polyacetal resin can be used without particular limitation. Examples include "Delrin" manufactured by DuPont Co., Ltd., "DURACON" manufactured by Polyplastics Co., Ltd., "Tenac" manufactured by Asahi Kasei Chemical Co., Ltd., "Iupital" manufactured by Mitsubishi Engineering Plastics Co., Ltd.

<<<< cycloolefin polymer >>>>

The cycloolefin polymer can be used without particular limitation. For example, `` ZEONEX '', `` ZEONOR '', and `` TOPAS ADVANCED POLYMERS GmbH '' manufactured by Japan's Rion Co., Ltd. (TOPAS) "," APEL "manufactured by Mitsui Chemicals Co., Ltd.," ARTON "manufactured by JSR Co., Ltd., etc.

The thermoplastic resin film preferably contains the thermoplastic resin in an amount of 50% to 100% by mass relative to the total solid content of the thermoplastic resin film, more preferably 70% to 100% by mass, and particularly preferably 88%. Mass% ~ 100%. According to this aspect, it is easy to obtain a temporary bonding laminated body having excellent adhesiveness and peelability.

The thermoplastic resin may be only one kind, or two or more kinds. When there are two or more types of thermoplastic resins, it is preferable that the total thereof is within the above range.

<<< Antioxidant >>>

The thermoplastic resin film may contain an antioxidant from the viewpoint of preventing the lower molecular weight or gelation of the polymer component due to oxidation during heating. As the antioxidant, a phenol-based antioxidant, a sulfur-based antioxidant, a phosphorus-based antioxidant, a quinone-based antioxidant, an amine-based antioxidant, or the like can be used.

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

Examples of the sulfur-based antioxidant include 3,3'-distearylthiopropionate, "Sumilizer (registered trademark) TPM" manufactured by Sumitomo Chemical Co., Ltd., and "Sumilizer (registered trademark)" Sumilizer (registered trademark) TPS "," Sumilizer (registered trademark) TP-D ", etc.

Examples of the phosphorus-based antioxidant include tris (2,4-di-third-butylphenyl) phosphite, bis (2,4-di-third-butylphenyl) pentaerythritol diphosphite, and poly (di Propylene glycol) phenylphosphite, diphenylisodecylphosphite, 2-ethylhexyldiphenylphosphite, triphenylphosphite, `` Irgafos (Irgafos ( (Registered trademark) 168 "," Irgafos (registered trademark) 38 ", etc.

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

Examples of the amine-based antioxidant include dimethylaniline and phenothiazine.

Antioxidants are preferably Irganox (registered trademark) 1010, Irganox (registered trademark) 1330, 3,3'-distearylthiopropionate, sumelet Sumilizer (registered trademark) TP-D, more preferably, Irganox (registered trademark) 1010, Irganox (registered trademark) 1330, particularly preferred is Lunarus (Irganox) (registered trademark) 1010.

Among the antioxidants, it is preferred to use a phenol-based antioxidant with a sulfur-based antioxidant or a phosphorus-based antioxidant, and it is most preferable to use a phenol-based antioxidant and a sulfur-based antioxidant in combination. It is particularly preferable to use a phenol-based antioxidant and a sulfur-based antioxidant in combination. With such a combination, it is expected that the peroxygen generated during the thermal oxidation process can be supplemented. Multiplicative effect of converting radicals (ROOH) as decomposition products into stable ROH radicals from radicals. In the case of using a phenol-based antioxidant and a sulfur-based antioxidant together, the quality of the phenol-based antioxidant and the sulfur-based antioxidant is better: phenol-based antioxidant: sulfur-based antioxidant = 1: 10 ~ 10: 1, more preferably It is 1: 5 ~ 5: 1.

The combination of antioxidants is preferably Irganox (registered trademark) 1010 and Sumilizer (registered trademark) TP-D, Irganox (registered trademark) 1330 and Soviet Sumilizer (registered trademark) TP-D, and Sumilizer (registered trademark) GA-80 and Sumilizer (registered trademark) TP-D, more preferably Irganox (registered trademark) 1010 and Sumilizer (registered trademark) TP-D, Irganox (registered trademark) 1330 and Sumilizer (registered trademark) ) TP-D, particularly preferred are Irganox (registered trademark) 1010 and Sumilizer (registered trademark) TP-D.

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.

In the case where the thermoplastic resin film contains an antioxidant, the content of the antioxidant is preferably 0.001% to 20.0% by mass, and more preferably 0.005% to 10.0% by mass, relative to the total solid content of the thermoplastic resin film. .

The antioxidant may be only one kind, or two or more kinds. When there are two or more antioxidants, it is preferable that the total thereof is in the above range.

<<< Interactive Agent >>>

The thermoplastic resin film may contain a surfactant. Surfactants can use fluorine Surfactants, nonionic surfactants, cationic surfactants, anionic surfactants, silicone surfactants, and other surfactants are preferred, and fluorine surfactants are preferred. By including a surfactant, the liquid characteristics (especially fluidity) can be improved, and the uniformity of coating thickness or the liquid saving property can be further improved.

The fluorine-based surfactant preferably has a fluorine content of 3 to 40% by mass, more preferably 5 to 30% by mass, and even more preferably 7 to 25% by mass. A fluorine-based surfactant having a fluorine content ratio within this range is effective in terms of the uniformity of the thickness of the coating film or the liquid-saving property. In addition, the solubility is also good.

Examples of the fluorine-based surfactants include Megafac F-251, Megafac F-281, Megafac F-430, and Megafac manufactured by DIC Corporation. F-444, Megafac F-477, Megafac F-510, Megafac F-552, Megafac F-553, Megafac F-554, Mega (Megafac) F-555, Megafac (F-556), Megafac (F-557), Megafac (F-558), Megafac (F-559), Megafac (F) -560, Megafac F-561, Megafac F-562, Megafac F-563, Megafac F-565, Megafac F-567, Megafac (Megafac) F-568, Megafac F-569, Megafac F-570, Megafac F-571, Megafac R-40, Megafac R- 41.Megafac R-43, Megafac R-94, FC-4430, FC-4432 manufactured by Sumitomo 3M Co., Ltd., Surflon manufactured by AGC Tsingmei Chemical Co., Ltd. S-242, Surflon S-243, Surflon S-386, Surflon S-651, Surflon S-611, Surflon S-420, PF-636, PF-656, PF-6320, PF-6520, PF-7002, etc. manufactured by OMNOVA.

Non-ionic surfactants include glycerol, trimethylolpropane, trimethylolethane, and these ethoxylates and propoxylates (e.g. glycerol propoxylate, glycerol ethoxylate) Base compounds, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene ole alkenyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol Dilaurate, polyethylene glycol distearate, and the like.

Examples of the cationic surfactant include EFKA-745 manufactured by Morishita Industrial Co., Ltd., Polyflow No. 75, Polyflow No. 90, and Poli manufactured by Kyoeisha Chemical Co., Ltd. Flo (Polyflow) No. 95 and the like.

Examples of the silicone-based surfactants include TSF-4440, TSF-4300, TSF-4445, TSF-4460, and TSF-4452 manufactured by Momentive Advanced Materials Japan Contracts, and KP-341 and KF manufactured by Shin-Etsu Silicone Co., Ltd. -6001, KF-6002, BYK-307, BYK-323, BYK-330, etc. manufactured by BYK Chemical Co., Ltd.

When the thermoplastic resin film contains a surfactant, the content of the surfactant is preferably 0.001% by mass to 2.0% by mass, and more preferably 0.005% by mass to 1.0, with respect to all solid components of the thermoplastic resin film. quality%.

The surfactant may be only one kind, or two or more kinds. When there are two or more kinds of surfactants, it is preferable that the total thereof is within the above range.

<< Other additives >>

The thermoplastic resin film can be formulated with various additives such as plasticizers, phase solvents, fillers, adhesion promoters, ultraviolet absorbers, aggregation inhibitors, silane coupling agents, and the like, as long as the effects of the present invention are not impaired. When these additives are blended, the total blended amount is preferably 3% by mass or less of all solid contents of the thermoplastic resin film.

<< Release layer >>

In the present invention, the laminated body is temporarily used on the surface of the element side of the thermoplastic resin film, and the region corresponding to the element surface includes a layer containing a release agent (release layer) selected from the group having a siloxane bond. Compounds and compounds having a silicon atom and a fluorine atom. The mold release agent is preferably a compound having a silicon atom and a fluorine atom. In this state, better peelability can be achieved.

The thickness of the release layer is not particularly limited because the effect can be obtained even with a thin film. For example, it is preferably 0.001 nm to 1000 nm, more preferably 0.1 nm to 500 nm, and still more preferably 1 nm to 100 nm. If it is the said range, it can prevent direct contact of a thermoplastic resin film and an element wafer at the time of a temporary bonding of an element wafer and a support body, and can achieve more favorable peelability.

In the present invention, the average thickness of the release layer is defined as the average of the following values: In a section along one direction of the release layer, from one end to the other end, it is measured at equal intervals by the elliptical polarization method Value of thickness at 5 positions. "A cross section along one direction of the release layer" is synonymous with the "cross section along one direction of the thermoplastic resin film".

When the mold release layer contains a compound having a silicon atom and a fluorine atom, it is preferable that the mold release layer contains 5% to 100% by mass of a solid atom selected from fluorine atoms with respect to all solid components of the mold release layer. The compound containing at least one kind of silicon atom is more preferably 50% by mass to 100% by mass, and even more preferably 90% by mass to 100% by mass.

When the release layer contains a compound having a siloxane bond, it is preferable that the release layer contains 5% to 100% by mass of the siloxane bond with respect to all solid components of the release layer. The compound is more preferably 50% by mass to 100% by mass, and even more preferably 90% by mass to 100% by mass.

When the release layer contains a compound having a silicon atom and a fluorine atom and a compound having a siloxane bond, it is preferable that the release layer contains 30% to 95% by mass of all the solid components of the release layer. A compound having a silicon atom and a fluorine atom by mass, a compound having a siloxane bond in an amount of 5 to 70% by mass, a compound containing a silicon atom and a fluorine atom, more preferably 40 to 90% by mass, 10% to 60% by mass of a compound having a siloxane bond.

The release agent may be only one kind, or two or more kinds. When there are two or more mold release agents, it is preferable that the total thereof is within the above range.

The release layer is preferably heated at 250 ° C for 2 hours, and the water contact angle measured under the conditions of cooling to 25 ° C is 30 ° or more, more preferably 40 ° or more, and even more preferably 50 ° or more. . The upper limit is not particularly limited. For example, it is preferably 140 ° or less, more preferably 130 ° or less, and still more preferably 120 ° or less. When the water contact angle is 30 ° or more, excellent peelability is obtained.

In addition, in the present invention, the water contact angle is measured using a film having various release layers formed on a Si wafer having a thickness of 100 mm. As a measuring device for the contact angle, a contact angle meter (model: CA-D) manufactured by Kyowa Interface Science Co., Ltd. was used. At a room temperature of 25 ° C. and a humidity of 50%, 70 pL of water droplets were added dropwise to measure the contact angles at five locations. The contact angles at 5 points were averaged to be the contact angle of each sample.

<<< Compound with Siloxane Bond >>>

The compound having a siloxane bond is preferably a silicone resin.

As the silicone resin, any of a solvent-free type, an oil type, a solution type, an emulsion type, and a burn-in type silicone resin can be preferably used.

The silicone resin is preferably, for example, a silicone that can be burned on the surface of a thermoplastic resin film by heating at 150 ° C or higher (more preferably 200 ° C or higher, further more preferably 250 ° C or higher, and particularly preferably 300 ° C or higher). Resin. The upper limit is preferably 450 ° C or lower, more preferably 400 ° C or lower, and still more preferably 350 ° C or lower. If it is a silicone resin which can be burned at the said temperature, when a mechanical or chemical process at high temperature is performed, a mold release layer will hardly decompose, and it will be excellent in heat resistance. In addition, generation of voids can be effectively suppressed.

In addition, the "burnable on the surface of a thermoplastic resin film" refers to a state in which a silicone resin is heated and reacted after being formed into a film, and is strongly bonded to the thermoplastic resin without being easily peeled off.

The weight average molecular weight of the silicone resin is preferably 10,000 to 10,000,000, and more preferably 50,000 to 5,000,000.

The silicone resin is preferably a linear organic polysiloxane and / or an organic polysiloxane having a branched structure. The organopolysiloxane can use, for example, the following general formula (1) The indicated organopolysiloxane and the like.

[化 10] M ¹ _a T _b D _c M ² _d ………… (1)

In the formula (1), M ¹ is a structural unit represented by the general formula (2), T is a structural unit represented by the general formula (3), D is a structural unit represented by the general formula (4), and M ² is In the structural unit represented by the formula (5), an oxygen atom in the formula shares an adjacent structural unit to form a siloxane bond. R ¹ is alkenyl, R ² is a substituted or unsubstituted monovalent organic group, a is an integer of 2 or more, b is an integer of 5 to 100, c is an integer of 2,000 to 20,000, and d is 0 or a positive integer And is a number satisfying a + d = b + 2.

Examples of the alkenyl group represented by R ¹ include a vinyl group, an allyl group, and a propenyl group.

Examples of the monovalent organic group represented by R ² include alkyl groups such as methyl, ethyl, propyl, and butyl; cycloalkyl groups such as cyclohexyl; alkenyl groups such as vinyl, allyl, and propenyl; phenyl, Some or all of the hydrogen atoms bonded to the carbon atoms of aryl groups such as tolyl, or chloromethyl, trifluoropropyl, cyanoethyl, etc., which are substituted by halogen atoms, cyano, amino groups, etc. Examples of the substituted or unsubstituted monovalent hydrocarbon group include an alkoxy group such as a methoxy group, an ethoxy group, a propoxy group, and a methoxyethoxy group, a hydroxyl group, and an epoxy group.

It is industrially preferable that R ¹ is a vinyl group, and industrially and characteristically it is preferable that at least 80 mol% of R ² is a methyl group.

B in the formula (1) is a number that determines the branch structure of the branched organic polysiloxane, and is an integer of 5 to 100, preferably an integer of 6 to 80. c is an integer of 2,000 to 20,000, preferably an integer of 5,000 to 10,000.

a and d are the number of siloxane units at the molecular end of the organopolysiloxane, a is an integer of 2 or more, and d is 0 or a positive integer. Considering the relationship between the number of branches and the number of molecular ends, it is necessary to satisfy a + d = b + 2.

The structural unit that must have an alkenyl group is only M ¹ , a is 2 or more, which means that the number of alkenyl groups in one molecule is 2 or more, and the alkenyl group is preferably arranged at the end of the molecular chain. If d = 0 and a + d = b + 2 can be satisfied, good hardenability is achieved, so d = 0 is more preferable.

The total values of a, b, c, and d limit the range of the degree of polymerization of the organopolysiloxane, and can be used to display the viscosity in practical use. The viscosity of highly polymerized polymers is generally expressed as the limiting viscosity ηr. The limiting viscosity ηr of the organopolysiloxane is particularly preferably in the range of 1.0 to 3.0. Around.

The compound having a siloxane bond may also contain a fluorine group. As the fluorine group, a known fluorine group can be used, and examples thereof include a fluorinated alkyl group and a fluorinated alkylene group.

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

The carbon number of the fluorinated alkylene is preferably 2 to 30, more preferably 2 to 20, and still more preferably 2 to 15. The fluorinated alkylene may be any of linear, branched, and cyclic. Moreover, it may have an ether bond. Further, the fluorinated alkylene group may be a perfluoroalkylene group in which all the hydrogen atoms are replaced with fluorine atoms.

Commercially available compounds having a siloxane bond can be used as KM-9736A, KM-9737A, KM-9738A, KM-9739, KM-722T, KM-740T, KM-742T, KM manufactured by Shin-Etsu Chemical Industry Co., Ltd. -780, KM-782, KM-785, KM-797, KM-9705, KM-860A, KM-862T, Silcast U, KF-96, KF-965, KF-54, KF -410, KF-412, KF-4701, KM-244F, KS-61, KS-702, KS-725, KS-707, KS-700, KS-7201, KS-7200, SEPA-COAT, Toray Dow Corning SM 7036 EX, SM 7060 EX, IE-7045, IE-7046T, BY 22-736 EX, BY 22-749 SR, SM 7001EX, SM 7002EX, SM 490EX, BY 22-744EX, SM 8706EX, SH 7024, SH 200, SH 203, 230 FLUID, SF 8416, SH 550, PRX 308, SH 7020, SR 2472, manufactured by Momentive Advanced Materials Japan Contracts TSF451 series, TSF4600, TSF4420, TSM620, TSM621, YSR3022, TSM6281, YSR6209, YSR6209B, TSM630, TSM630NF, TSM631, TSM632, TSM637, YMR7212, TSM6341, TSM6343, TSM647, TSM6344, TSM6345, TSM6362, TSM6363, TSM650, YG6144 and so on.

<<< Compounds with silicon and fluorine atoms >>>

The compound having a silicon atom and a fluorine atom is preferably a silane coupling agent. In addition, the content of the fluorine atom in the compound having a silicon atom and a fluorine atom is preferably 20% to 80%, and more preferably 24% to 80%. Here, the content rate of the fluorine atom was measured for each compound using an ICP emission spectrometer (model: ICPS-8100) manufactured by Shimadzu Corporation.

Examples of the silane coupling agent include compounds containing a group having at least one fluorine atom and at least one silane group.

A compound having a group generally called a perfluoroalkyl group or a perfluoroether group containing two or more fluorine atoms in one molecule as a group having at least one fluorine atom is preferred. The group having a fluorine atom may have a substituent. The substituent may be arbitrarily selected from the viewpoint of reactivity or thermal stability, and examples thereof include halogen atoms such as a chlorine atom, a bromine atom, and an iodine atom; alkoxy groups such as a methoxy group, an ethoxy group, and a third butoxy group; Aryloxy groups such as phenoxy and p-tolyloxy; alkoxycarbonyl groups such as methoxycarbonyl, butoxycarbonyl, and phenoxycarbonyl; ethoxy, propyl, and benzyloxy; Oxygen; fluorenyl groups such as ethenyl, benzamidine, isobutyl fluorenyl, propylene fluorenyl, methacryl fluorenyl, and methoxysulfenyl; alkyls such as sulfanyl and tertiary butylthio Thiol; benzene Arylthio groups such as methylthio and p-tolylthio; alkyl groups such as methyl, ethyl, third butyl, and dodecyl; rings such as cyclopentyl, cyclohexyl, cycloheptyl, and adamantyl Alkyl groups; aryl groups such as phenyl, p-tolyl, xylyl, cumyl, naphthyl, anthracenyl, and phenanthryl; hydroxy; carboxyl; formamyl; sulfonyl; cyano; alkyl Arylaminocarbonyl; arylaminocarbonyl; sulfonamido; silyl; amine; monoalkylamino; dialkylamino; arylamino; and diarylaminothioketone; or The combination of these.

The silyl group is preferably a silanol group or a hydrolyzable silyl group. The "hydrolyzable silyl group" is a hydrolyzable silyl group, and examples of the hydrolyzable group include an alkoxy group, a mercapto group, a halogen atom, an amido group, an ethoxy group, an amine group, and an isopropenyl group. The silane group is hydrolyzed to become a silanol group, and the silanol group is dehydrated and condensed to form a siloxane bond. Such a hydrolyzable silane group or a silanol group is preferably represented by the following formula (B-1).

In the formula (B-1), at least one of R ^h1 to R ^h3 represents a group selected from the group consisting of an alkoxy group, a mercapto group, a halogen atom, a fluorenylamino group, an ethoxyl group, an amine group, and an isopropenyloxy group. A group of hydrolyzable groups, 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 (for example, an alkyl group, an aryl group, an alkenyl group, an alkynyl group, and an aralkyl group).

In formula (B-1), a hydrolyzable group bonded to a silicon atom is particularly preferably an alkoxy group or a halogen atom, and more preferably an alkoxy group.

From the standpoint of releasability, the alkoxy group is preferably an alkoxy group having 1 to 30 carbon atoms. More preferred is an alkoxy group having 1 to 15 carbon atoms, even more preferred is an alkoxy group having 1 to 5 carbon atoms, particularly preferred is an alkoxy group having 1 to 3 carbon atoms, and most preferred is a methoxy group. Or ethoxy.

Examples of the halogen atom include an F atom, a Cl atom, a Br atom, and an I atom. From the viewpoint of ease of synthesis and stability, a Cl atom and a Br atom are preferred, and a Cl atom is more preferred.

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

The hydrolyzable group may be bonded to one silicon atom in a range of one to four. The total number of hydrolyzable groups in formula (B-1) is preferably in a range of 2 or 3. Particularly preferred is that three hydrolyzable groups are bonded to the silicon atom. When two or more hydrolyzable groups are bonded to a silicon atom, these may be the same as or different from each other.

Specific examples of the preferable alkoxy group include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, a third butoxy group, a phenoxy group, and a benzyloxy group. Each 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 to which an alkoxy group is bonded include trialkoxysilyl groups such as trimethoxysilyl group, triethoxysilyl group, triisopropoxysilyl group, and triphenoxysilyl group; Dialkoxy monoalkylsilyl groups such as dimethoxymethylsilyl, diethoxymethylsilyl groups; methoxydimethylsilyl groups, ethoxydimethylsilyl groups, etc. Monoalkoxydialkylsilyl.

Examples of the compound having a silicon atom and a fluorine atom include KBM-7103 manufactured by Shin-Etsu Chemical Industry Co., Ltd., OPTOOL DSX manufactured by Daikin Industry Co., Ltd., and Aifu manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd. Eftop, perfluorodecyltrimethoxysilane, perfluorodecyltriethoxysilane, trifluoropropyltrimethoxysilane, trifluoropropyltriethoxysilane, perfluorooctyltrimethoxy Silane, perfluorooctyltriethoxysilane, perfluorododecyltrimethoxysilane, perfluorododecyltriethoxysilane, perfluoropentyltriethoxysilane, perfluoropentyltrimethyl These compounds can be preferably used as oxysilane.

<<< Other ingredients >>>

In addition to the release agent, the release layer may further contain various compounds as needed, as long as the effect of the present invention is not impaired. For example, a thermal polymerization initiator, a sensitizing dye, a chain transfer agent, and an antioxidant can be preferably used. These can be used as described in the thermoplastic resin film.

<Manufacturing method of laminated body for temporary bonding>

Next, the manufacturing method of the laminated body of this invention is demonstrated temporarily.

The manufacturing method of the laminated body for temporary bonding of this invention includes the process of forming the said mold release agent containing layer (release layer) on the surface of the said thermoplastic resin film.

<< Manufacturing method of thermoplastic resin film >>

The thermoplastic resin film can be produced by a conventionally known method. For example, it can be manufactured by a melt film forming method, a solution film forming method, or the like. The melt film forming method is preferred. If molten The melt film method can thicken the film while maintaining flatness. In addition, a polymer component or other additives that are difficult to dissolve in a solvent may be used, and the degree of freedom in material selection is high. In particular, a highly heat-resistant additive that tends to be difficult to dissolve in a solvent can be used, and a thermoplastic resin film excellent in heat resistance can be easily obtained.

The melt film forming method is to obtain the film (sheet) by heating the raw material composition to melt it to achieve fluidity, and using an extrusion molding device or an injection molding device to form the molten liquid into a sheet shape and cooling. method. A long film with good flatness can be obtained by an extrusion molding method. The length of the long film is not particularly limited, and the lower limit is, for example, preferably 1 m or more, and more preferably 2 m or more. Although it is difficult to obtain a long film by the injection molding method, high film thickness accuracy is obtained. Other additives can also be added by mixing and melting. The release film can also be laminated on one or both sides of the film to make a "thermoplastic resin film with a release film".

The solution film forming method is a method in which a solvent is used to dissolve a raw material composition to achieve fluidity, and the solution is applied to a support such as a film, a drum, or a tape to form a sheet, and dried to obtain a film (sheet). .

As the solvent, a known solvent can be used without limitation, and an organic solvent is preferred.

As the organic solvent, ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate Esters, butyl butyrate, methyl lactate, ethyl lactate, alkyl oxyacetate (e.g. methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate (e.g. methyl methoxyacetate, Ethyl methoxyacetate, butyl methoxyacetate, ethoxyethyl Methyl ester, ethyl ethoxyacetate, etc.)), alkyl 3-oxypropionate (e.g. methyl 3-oxypropionate, ethyl 3-oxypropionate, etc. (e.g. 3-methyl Methyloxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)), alkyl 2-oxypropionates (E.g. methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, etc. (e.g. methyl 2-methoxypropionate, ethyl 2-methoxypropionate Ester, 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), methyl 2-oxy-2-methylpropionate and 2- Ethyloxy-2-methylpropanoate (e.g. methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, Ethyl pyruvate, propyl pyruvate, methyl ethyl acetate, ethyl ethyl acetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, acetic acid-1-methoxy- Ester such as 2-propyl ester; Diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, two Ethylene glycol monomethyl ether, diethylene glycol monoethyl ether, two Ethers such as glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate; methyl ethyl ketone, cyclohexanone, 2-heptane Ketones such as ketones, 3-heptanone, N-methyl-2-pyrrolidone (NMP), N-ethyl-2-pyrrolidone (NEP), γ-butyrolactone; methylene chloride, chloroform, Halogens such as 1,2-dichloroethane, 1,2-dibromoethane, chlorobenzene; aromatic hydrocarbons such as toluene, xylene, anisole, mesitylene; hydrocarbons such as limonene, p-menthane Wait.

From the viewpoint of improving the coating surface shape, it is also preferable that these solvents are in a form of mixing two or more kinds. In this case, it is particularly preferable to include Menthane, γ-butyrolactone, anisole, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol Dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, ethylcarbitol acetate, butylcarbitol acetate, propylene glycol methyl ether, and A mixed solution of two or more kinds of propylene glycol methyl ether acetate.

Examples of the method for applying the solution include a method of applying a solution by extruding the solution from a slit-shaped opening under pressure, a method of applying a solution by transferring the solution through a gravure or anilox roll, and a self-spraying device or dispenser. A method of scanning coating while spraying the solution, a method of immersing the solution in a storage tank, and performing a dip coating by using a film or a drum or a belt, and applying the coating while drawing the solution with a wire bar Method, etc.

After the solution is applied to the support, it is dried to become a solidified sheet, and then the sheet is mechanically peeled from the support to obtain a single-piece film (sheet). As a treatment for giving the mold release property to the support in advance for easy peeling, coating of the release layer, dipping treatment, gas treatment, electromagnetic wave irradiation treatment, plasma irradiation treatment, and the like can be performed. Alternatively, the film may be left without being peeled from the support, and a "thermoplastic resin film with a release film" may be produced in a state where a sheet is adhered to the film support. By continuously performing these processes, a roll-shaped long film can be obtained. In addition, a release film can be laminated on both sides of the film to form a "thermoplastic resin film with a release film on both sides".

<< Formation method of release layer >>

Examples of a method for forming a release layer on the surface of a thermoplastic resin film include lamination. Method, coating method, co-extrusion method.

The lamination method is to apply a composition containing at least the mold release agent on a release film to form a film-like release layer (release layer film), and to release the surface of the thermoplastic resin film without the release film and the release film. A method of laminating a layer film without surface contact of the release film.

For the lamination, a known device such as roll lamination (which may be heated or pressurized) or vacuum lamination (which may also be heated) may be used. By laminating a release layer film on both sides of the thermoplastic resin film, a release layer can be provided on both sides of the thermoplastic resin film.

The coating method is a method in which a solution for forming a release layer is applied to the surface of a thermoplastic resin film without a release film, followed by drying and forming. The composition for forming a release layer is preferably a solution containing the release agent and a solvent. Any solvent can be preferably used as long as the solvent is a soluble mold release agent. When a mold release agent contains the compound which has a silicon atom and a fluorine atom, the solvent which has a fluorine atom has high solubility, and it is preferable. Examples include Fluorinert FC-40 (manufactured by Sumitomo 3M Co., Ltd.).

When a thermoplastic resin film is produced by the solution film-forming method, the solution for film formation may be applied in-line, and after drying, the solution for mold release layer formation may be applied without winding, Allow to dry. In addition, when the physical properties of the solution are designed without compatibility between the solution for forming a film and the solution for forming a release layer, they can be applied and dried simultaneously.

Further, after the solution for forming a film is applied, the solution for forming a release layer may be applied without drying, and both may be simultaneously dried.

Furthermore, the solution for film formation and the solution for mold release layer formation are temporarily phased It is soluble, but when the concentration is increased by drying, when the phase separation physical properties are generated, a mixed solution may be applied and separated into a thermoplastic resin film and a release layer during drying.

In addition, by applying a release layer forming solution on both sides of the thermoplastic resin film, a release layer can be provided on both sides of the thermoplastic resin film.

The co-extrusion method is a method in which a material for forming a film and a material for forming a release layer are thermally melted separately and integrated while extruding simultaneously, thereby obtaining a sheet in which a thermoplastic resin film and a release layer are integrated. By releasing the material for mold release layer formation on both sides of the film formation material, a mold release layer can be provided on both surfaces of the thermoplastic resin film.

The laminated body for temporary bonding of the present invention preferably has a solvent content of 1% by mass or less, more preferably 0.1% by mass or less, and particularly preferably does not contain it.

The laminated body of the temporary bonding layer of the present invention can also be laminated with a release film on one or both sides of the laminated body to make a "temporary bonding layer with a releasing film". When the long temporary laminated body is wound into a roll shape, the surface of the laminated body can be temporarily scratched, or the trouble of sticking during storage can be prevented.

The release film can be peeled off during use. For example, when the release film is bonded on both sides, peel off the release film on one side, laminate the adhesive surface on the element wafer or support, and then peel off the remaining release film. Keep the surface of the sheet as clean as possible.

<Adhesive support>

Next, the adhesive support using the laminated body for temporary bonding using the present invention Explain.

The adhesive support body includes the temporary bonding laminated body on the surface of the support body.

The temporary bonding layer can be formed by laminating the temporary bonding layer according to the present invention on a support. For example, the laminated body for temporary bonding is placed on a vacuum laminator, the laminated body for temporary bonding is located on a support by this device, the laminated body for temporary bonding is brought into contact with the support under vacuum, and the roller is used. A method of performing pressure bonding to temporarily fix (laminate) a support with a laminated body, and the like. The laminated body for temporary bonding fixed to the support can be cut into a desired shape such as a circular shape, for example.

In the adhesive support, the laminated body for temporary bonding may be formed by forming a release layer on only one side of a thermoplastic resin film, or may be formed by forming a release layer on both sides. It is preferable to form the release layer only on one side of the thermoplastic resin film. When the release layer is formed only on one side of the thermoplastic resin film, the release layer is formed on the surface opposite to the support. Furthermore, it is preferable that one surface of the thermoplastic resin film is in contact with the surface of the support.

In the adhesive support, the support (also referred to as a “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 preferred in terms of the difficulty in contaminating a silicon substrate typically used as a substrate of a semiconductor device, or an electrostatic chuck that is commonly used in the manufacturing process of a semiconductor device, and the like.

The thickness of the support is not particularly limited. For example, it is preferably 300 μm to 100 mm, and more preferably 350 μm to 10 mm.

A release layer may be provided on the surface of the support. That is, the support may be a support with a release layer.

The release layer is preferably a low surface energy layer containing fluorine atoms and / or silicon atoms, and more preferably a material containing fluorine atoms and / or silicon atoms. The fluorine content of the release layer is preferably 30% to 80% by mass, more preferably 40% to 76% by mass, and particularly preferably 60% to 75% by mass.

As the material of the release layer, the same materials as those described in the release layer of the laminated body for temporary use can be used.

<Laminated body with element wafer>

Next, the laminated body with an element wafer of this invention is demonstrated.

The laminated body with an element wafer according to the present invention includes the temporarily bonded laminate according to the present invention between the element wafer and the support, and temporarily with the release layer-side surface of the laminated body and the components of the element wafer. The surfaces are in contact, and the other surface is in contact with the surface of the support.

The element wafer can be used without limitation, and examples thereof include a silicon substrate and a compound semiconductor substrate. Specific examples of the compound semiconductor substrate include a SiC substrate, a SiGe substrate, a ZnS substrate, a ZnSe substrate, a GaAs substrate, an InP substrate, and a GaN substrate.

A mechanical structure or circuit may also be formed on the surface of the element wafer. Examples of the device wafer on which a mechanical structure or a circuit is formed include micro electro mechanical systems (MEMS), power devices, image sensors, miniature sensors, LEDs, optical devices, interposers, and embedded devices. , Micro-components, etc.

The element wafer preferably has a structure such as a metal bump, a pad, and a hole. Present invention The temporary adhesive film can stably temporarily adhere even to an element wafer having a structure on the surface, and can easily peel off the element wafer. The height of the structure is not particularly limited, and it is preferably 1 μm to 100 μm, for example. The structure can also be formed by being buried inside the element wafer.

The film thickness of the element wafer before the mechanical or chemical treatment is preferably 500 μm or more, more preferably 600 μm or more, and still more preferably 700 μm or more. The upper limit is, for example, preferably 1000 μm or less, and more preferably 900 μm or less.

The film thickness of the element wafer after being thinned by mechanical or chemical treatment is preferably less than 500 μm, more preferably 400 μm or less, and still more preferably 300 μm or less. The lower limit is, for example, preferably 5 μm or more, and more preferably 10 μm or more.

In the multilayer body with an element wafer of the present invention, the support (carrier support) is synonymous with the support described in the adhesive support, and the preferred range is also the same.

The laminated body with an element wafer according to the present invention can be produced by heating and pressure-bonding the surface of the adhesive support on which the side of the laminated body is temporarily adhered to the element wafer. The conditions for the thermal compression bonding are preferably, for example, a temperature of 100 ° C. to 400 ° C., a pressure of 0.01 MPa to 1 MPa, and a time of 1 minute to 15 minutes.

Furthermore, the temporary bonding layered body of the present invention may be disposed between a support and an element wafer, and may be manufactured by thermal compression bonding.

<Method for Manufacturing Semiconductor Device>

Hereinafter, a semiconductor having undergone a step of manufacturing a laminated body with an element wafer An embodiment of a manufacturing method of the device will be described with reference to FIG. 1. The present invention is not limited to the following embodiments.

FIGS. 1 (A) to 1 (F) are schematic cross-sectional views explaining the temporary connection of the support body and the element wafer, respectively ((A) to (D) of FIG. 1), and then to the support body. A schematic cross-sectional view of a state where the element wafer is thinned (FIG. 1 (E)) and a state where the support and the element wafer are separated (FIG. 1 (F)).

In this embodiment, as shown in FIGS. 1 (A) to 1 (B), a release layer 110 formed on the surface area layer of the thermoplastic resin film 111 is temporarily laminated with a laminate 11 on a support. On the surface of the body 12, an adhesive support 100 having a mold release layer 110 disposed on the outermost surface is prepared. The adhesive support 100 can be manufactured by the method.

The entire surface of one surface of the support body 12 of the adhesive support body 100 in this embodiment is temporarily covered with the laminated body 11. Such an adhesive support is effective when the total thickness variation (TTV) of a thin element wafer is to be further reduced (that is, when the flatness of the thin element wafer is to be further improved).

That is, in the case of thinning an element wafer temporarily adhered by using a laminated body temporarily, firstly, the structure on the surface of the element wafer is protected by a temporary adhesive film. The uneven shape of the structure basically disappeared. As a result, the TTV of the thin element wafer finally obtained can be further reduced.

As shown in FIG. 1 (C), the element wafer 60 is provided with a plurality of element wafers 62 on the surface (element surface) 61 a of the silicon substrate 61.

The thickness of the silicon substrate 61 is preferably 200 μm to 1200 μm, for example. The element wafer 62 is preferably a metal structure, for example, and its height is preferably 10 μm to 100 μm.

Next, as shown in FIG. 1 (C) to FIG. 1 (D), the adhesive support 100 is pressed against the element surface 61a of the element wafer 60, and the support 12 and the element wafer 60 are temporarily adhered.

Next, the back surface 61b of the silicon substrate 61 is subjected to mechanical or chemical treatment (it is not particularly limited, for example, thin film processing such as sliding or chemical mechanical polishing (CMP), chemical vapor deposition (CVD)) Or physical vapor deposition (Physical Vapor Deposition, PVD) and other treatments under high temperature and vacuum, treatment with chemicals such as organic solvents, acidic treatment solutions or alkaline treatment solutions, plating treatment, actinic radiation, heating, cooling Processing, etc.), as shown in (E) of FIG. 1, the thickness of the silicon substrate 61 is reduced (for example, the average thickness is preferably less than 500 μm, more preferably 1 μm to 200 μm, even more preferably 1 μm to 100 μm), and Thin element wafer 60a.

Furthermore, as a mechanical or chemical treatment, a treatment may be performed in which a through hole (not shown) penetrating the silicon substrate from the back surface 61b1 of the thin element wafer 60a is formed after the thin film processing, and silicon is formed in the through hole Processing of a through electrode (not shown). The highest attainable temperature in the heat treatment is, for example, preferably 130 ° C to 450 ° C, and more preferably 180 ° C to 400 ° C. The heat treatment is, for example, preferably performed at the highest temperature reached for 30 seconds to 5 hours, and more preferably, it is heated at the highest temperature reached for 1 minute to 3 hours.

Next, as shown in FIG. 1 (F), the support 12 is made from a thin member One wafer 60a is detached. The method of detachment is not particularly limited, and it is preferred that the thin element wafer 60 a be pulled away from the end portion of the thin element wafer 60 a in a direction perpendicular to the thin element wafer 60 a without any treatment and peeled. That is, mechanical peeling is preferred.

The peeling interface may be the interface between the element surface 61 a and the release layer 110, the interface between the release layer 110 and the thermoplastic resin film 111, or the inside of the release layer 110. That is, the peeling residue of the release layer 110 may also be adhered to the element surface 61a1. When the peel strength of the laminated body 11 and the thin element wafer for temporary bonding is set to A and the peel strength of the thermoplastic resin film 111 and the release layer 110 is set to B, the following formula is preferably satisfied.

A <B ‥ 式 (1)

In addition, the peeling strength is a value when the peeling strength was measured five times by pulling from the end of the thin element wafer 60a in a direction perpendicular to the element wafer using a digital dynamometer manufactured by IMADA Co., Ltd. , Use its average.

Furthermore, the laminated body 11 may be temporarily contacted with the peeling liquid, and the thin element wafer 60a may be slid relative to the support body 12 as needed, and then the end of the thin element wafer 60a may be opposed to the element wafer. The vertical direction lifts and peels. As the peeling liquid, for example, the peeling liquid described in paragraph number 0203 to paragraph number 0212 of Japanese Patent Laid-Open No. 2014-80570 can be used. In addition, the present invention does not necessarily require a treatment using a peeling liquid or the like. The support body 12 and the support body 12 can be removed from the element surface 61a of the thin element wafer 60a only by mechanical peeling without peeling residue or the like. The thermoplastic resin film 111 is simultaneously removed.

After peeling the support from the thin element wafer 60a, it may be brought into contact with a cleaning solution described later to clean the element surface 61a. Various known processes are performed on the thin element wafer 60a as necessary to manufacture a semiconductor device including the thin element wafer 60a.

<Cleaning solution>

Hereinafter, the cleaning liquid will be described in detail.

The cleaning liquid is preferably an organic solvent in which the thermoplastic resin and the release agent are dissolved. Examples of the organic solvent include aliphatic hydrocarbons (hexane, heptane, Isopar E manufactured by Esso Chemical Co., Ltd., Isopar H, Isopar G, etc.), Aromatic hydrocarbons (toluene, xylene, etc.), halogenated hydrocarbons (dichloromethane, 1,2-dichloroethane, trichloroethylene, monochlorobenzene, etc.), and polar solvents. Examples of polar solvents include alcohols (methanol, ethanol, propanol, isopropanol, 1-butanol, 1-pentanol, 1-hexanol, 1-heptanol, 1-octanol, 2-octanol, 2- Ethyl-1-hexanol, 1-nonanol, 1-decanol, benzyl alcohol, ethylene glycol monomethyl ether, 2-ethoxyethanol, 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 monobenzyl ether, ethylene glycol Monophenyl ether, propylene glycol monophenyl ether, methylphenyl methanol, n-pentanol, methylpentanol, etc.), ketones (acetone, methyl ethyl ketone, ethyl butyl ketone, methyl isobutyl ketone, Cyclohexanone, etc.), esters (ethyl acetate, propyl acetate, butyl acetate, pentyl acetate, benzyl acetate, methyl lactate, butyl lactate, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether Ether acetate, diethylene glycol acetate, diethyl phthalate, butylacetate, etc.), Others (triethyl phosphate, tricresyl phosphate, N-phenylethanolamine, N-phenyldiethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, 4- (2-hydroxyethyl) morpholine , N, N-dimethylacetamide, N-methylpyrrolidone, etc.).

Moreover, by removing the thermoplastic resin film 111 on the support body 12, the support body 12 can be regenerated. The method of removing the thermoplastic resin film 111 includes a method of physically removing the thermoplastic resin film 111 by a brush, ultrasonic waves, ice particles, and aerosol blowing in a film-like state, and dissolving it in an aqueous solution or an organic solvent to dissolve it. Removal methods; chemical removal methods such as a method of irradiating actinic rays, radiation, and heat to decompose and vaporize them can use conventionally known cleaning methods depending on the support.

For example, when a silicon substrate is used as a support, conventionally known methods for cleaning silicon wafers can be used. For example, the aqueous solution or organic solvent that can be used for chemical removal includes strong acids, strong bases, strong oxidants, Or specific mixtures thereof include acids such as sulfuric acid, hydrochloric acid, hydrofluoric acid, nitric acid, and organic acids; bases such as tetramethylammonium, ammonia, and organic bases; oxidants such as hydrogen peroxide; or ammonia and peroxide A mixture of hydrogen, a mixture of hydrochloric acid and hydrogen peroxide water, a mixture of sulfuric acid and hydrogen peroxide water, a mixture of hydrofluoric acid and hydrogen peroxide water, a mixture of hydrofluoric acid and ammonium fluoride, and the like.

From the standpoint of releasability when using a regenerated support, it is preferred to use a support cleaning solution.

The support cleaning solution preferably contains an acid having a pKa of less than 0 and hydrogen peroxide. The acid having a pKa of less than 0 is selected from inorganic acids such as hydrogen iodide, perchloric acid, hydrogen bromide, hydrogen chloride, nitric acid, and sulfuric acid, or organic acids such as alkylsulfonic acid and arylsulfonic acid. Self-supporting From the viewpoint of the cleanability of the agent layer, an inorganic acid is preferred, and sulfuric acid is most preferred.

For the hydrogen peroxide, 30w / v% hydrogen peroxide water can be preferably used. The mixture of the strong acid and 30w / v% hydrogen peroxide water is preferably 0.1: 1 to 100: 1, and more preferably 1: 1. ~ 10: 1, the best is 3: 1 ~ 5: 1.

<< Existing embodiment >>

Next, a conventional embodiment will be described.

FIG. 2 is a schematic cross-sectional view illustrating a temporary bonding state between a conventional release adhesive support and an element wafer.

In the conventional embodiment, as shown in FIG. 2, as the adhesive support, an adhesive support 100 a formed by providing an adhesive layer 11 b formed of a conventional temporary adhesive on the support 12 is used. In the procedure described with reference to FIG. 1, the adhesive support 100 a and the element wafer are temporarily temporarily adhered, and the silicon substrate in the element wafer is subjected to a thin film treatment. Next, the thin type is peeled off from the adhesive support 100 a in the same manner as the procedure. Element wafer 60a.

However, if the existing temporary adhesive is used, the element wafer is temporarily adhered by a high adhesive force, and it is difficult to easily release the temporary adhesion of the support body and the element wafer without damaging the processed element wafer. For example, if a temporary adhesive with high adhesiveness among the existing temporary adhesives is used to make the temporary bonding between the element wafer and the support sufficient, the temporary bonding of the element wafer and the support tends to be too strong. Therefore, in order to release the excessively strong temporary bonding, for example, as shown in FIG. 2, an adhesive tape (for example, a dicing tape) 70 is attached to the back surface of the thin element wafer 60 a, and the thin element wafer 60 a is peeled from the self-adhesive support 100 a. Case, own structure The component wafer 62 of the object 63 peels off the structure 63 and the like, and the defect of the element wafer 62 is likely to occur.

On the other hand, if a temporary adhesive with low adhesiveness among the existing temporary adhesives is used, the temporary bonding to the element wafer can be easily released, but the temporary bonding between the element wafer and the support is too weak and easy. There is a problem that the element wafer cannot be reliably supported by the support.

In contrast, the laminated body for temporary bonding of the present invention can exhibit sufficient adhesion, and the temporary bonding of the element wafer 60 and the support 12 can be easily released. That is, if the laminated body for temporary bonding of the present invention is used, the element wafer 60 can be temporarily bonded by a high bonding force, and the thin element wafer 60 can be easily released without causing damage to the thin element wafer 60a. 60a temporarily follows.

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

Further, in the above-mentioned embodiment, the silicon wafer is exemplified as the element wafer, but the invention is not limited to this. In the method for manufacturing a semiconductor device, any member to be processed that can be mechanically or chemically processed may be used. Examples include compound semiconductor substrates, and specific examples of the compound semiconductor substrate include a SiC substrate, a SiGe substrate, a ZnS substrate, a ZnSe substrate, a GaAs substrate, an InP substrate, and a GaN substrate.

Furthermore, in the embodiment described above, the mechanical or chemical treatment of the element wafer (silicon substrate) may include a thin film process of the element wafer and a process of forming a silicon through-electrode, but it is not limited to these, and may be List arbitrary processes required in the method of manufacturing a semiconductor device.

In addition, the shape, size, number, arrangement position, and the like of the element wafer among the element wafers exemplified in the embodiment are arbitrary and are not limited.

[Example]

Hereinafter, the present invention will be described more specifically with reference to the examples. However, the present invention is not limited to the following examples as long as it does not exceed the gist thereof. In addition, unless otherwise specified, "part" and "%" are quality standards.

<Method for temporarily forming a laminated body from a thermoplastic resin film> (Example 1, Example 3, Example 8 to Example 12, Comparative Example 1 to Comparative Example 4)

The following coating liquid for forming a release layer was bar-coated on the thermoplastic resin film described below, and oven-dried at 120 ° C. for 1 minute to prepare a laminated body for temporary adhesion including a release layer on one side of the thermoplastic resin film. .

[Coating liquid for mold release layer formation]

． Mold release agent described in Table 1: parts by mass described in Table 1

． Solvents listed in Table 1: parts by mass described in Table 1

<Method for temporarily forming a laminated body from a solution of a thermoplastic resin> (Example 2, Example 4 to Example 7)

The film-forming composition described below was applied to a polyethylene terephthalate film (release film) having a thickness of 75 μm through a wire rod at a speed of 1 m / min, and was performed at 140 ° C. for 10 minutes. Drying in minutes, thereby producing a thermoplastic resin film having a film thickness of 100 μm.

Next, the following coating solution for forming a release layer was bar-coated on the thermoplastic resin film, and then oven-dried at 120 ° C for 1 minute to prepare a single bread on the thermoplastic resin film. A laminated body was temporarily used for the release layer-containing layer.

[Composition for film production]

． Thermoplastic resins described in Table 1: parts by mass shown in Table 1

． Irganox (registered trademark) 1010 (manufactured by BASF): 1 part by mass

． Sumilizer (registered trademark) TP-D (manufactured by Sumitomo Chemical Co., Ltd.): 1 part by mass

． Solvents listed in Table 1: parts by mass described in Table 1

[Coating liquid for mold release layer formation]

． Mold release agent described in Table 1: parts by mass described in Table 1

． Solvents listed in Table 1: parts by mass described in Table 1

The compounds described in Table 1 are shown below.

<Thermoplastic resin>

(a-1) Midfil (thermoplastic polyimide resin, 1% weight reduction temperature = 520 ° C, melting point = 388 ° C, Tg = 320 ° C, manufactured by Kurabo Industries Co., Ltd.)

(a-2) Ultrason E6020P (polyether hydrazone, 1% weight reduction temperature = 510 ° C, melting point = 225 ° C, Tg = 225 ° C, manufactured by BASF)

(a-3) EXPEEK (Polyetheretherketone, 1% weight reduction temperature = 480 ° C, melting point = 343 ° C, Tg = 320 ° C, manufactured by Kurabo Industries Co., Ltd.)

(a-4) Septon S2104 (polystyrene elastomer, 1% weight reduction temperature = 370 ° C, melting point = 170 ° C, Tg = 120 ° C, manufactured by Kuraray Corporation)

(a-5) NORYL APS130 resin (modified polyphenylene ether, 1% weight reduction temperature = 360 ° C, melting point = 132 ° C, Tg = 120 ° C, manufactured by Saudi Basic Industrial Innovation Plastics Japan)

(a-6) Septon S2002 (polystyrene elastomer, 1% weight reduction temperature = 310 ℃, melting point = 150 ℃, Tg = 100 ℃, manufactured by Kuraray Co., Ltd.)

(a-7) Delrin 100P BK602 (polyacetal resin, 1% weight reduction temperature = 280 ° C, melting point = 178 ° C, Tg = -50 ° C, manufactured by DuPont)

<Release Agent>

(b-1) OPTOOL DSX (compound with silicon atom and fluorine atom (fluorine-based silane coupling agent), Daikin Industry Co., Ltd.)

(b-2) KS-700 (compound having a siloxane bond (silicone resin), burning temperature = 250 ° C, manufactured by Shin-Etsu Chemical Industry Co., Ltd.)

(b-3) Trifluoropropyltrimethoxysilane (compound having silicon atom and fluorine atom, fluorine content rate = 26%, manufactured by Tokyo Chemical Industry Co., Ltd.)

(b-4) KS-7201 (compound with a siloxane bond (silicone resin), burning temperature = 200 ° C, manufactured by Shin-Etsu Chemical Industry Co., Ltd.)

(b-5) KS-7200 (compound having a siloxane bond (silicone resin), burning temperature = 230 ° C, manufactured by Shin-Etsu Chemical Industry Co., Ltd.)

(b-6) OPTOOL HD-1100 (compound with fluorine atom and no silicon element, manufactured by Daikin Industry Co., Ltd.)

(b-7) Trimethoxy (3- (phenylamino) propyl) silane (a compound having a silicon atom and no fluorine element, manufactured by Tokyo Chemical Industry Co., Ltd.)

(b-8) SEPA-COAT (compounds having a siloxane bond (silicone resin), (Burning temperature = 150 ℃, manufactured by Shin-Etsu Chemical Industry Co., Ltd.)

(b-9) Trifluoropropyltriethoxysilane (compounds with silicon and fluorine atoms, fluorine content = 22%, Shanghai Fuluda Rubber & plastic Materials Technology Co., Ltd. ., Ltd.)

The 1% weight reduction temperature of the thermoplastic resin is a value measured by heating at 25 ° C at a temperature of 20 ° C / min under a nitrogen flow under a thermogravimetry device (TGA).

<Production of Adherent Support>

The temporarily bonded laminate produced by the above method was placed on a vacuum laminator. Next, by using this device, the temporary bonding laminate is positioned on a 100 mm Si wafer, and the Si wafer is brought into contact with the surface (the thermoplastic resin film side) on the opposite side of the release layer of the temporary bonding laminate under vacuum. The laminated body and the Si wafer were temporarily fixed by a roller to prepare an adhesive support.

<Production of test strip>

The surface of the side of the adhesive support on which the laminated body was temporarily adhered was pressed against the element surface of the element wafer under vacuum, Tg + 50 ° C, and a pressure of 0.11 MPa for 3 minutes to prepare a test piece. As the element wafer, an element wafer including copper bumps having a diameter of 80 μm and a height of 40 μm was formed on a 100-mm Si wafer at a pitch of 200 μm.

<Comparative example 3>

The element surface of the element wafer was coated with 0.5 parts by mass of OPTOOL DSX (manufactured by Daikin Industries, Ltd.) and 99.5 parts by mass of Flolinet (Fluorinert) FC-40 (manufactured by Sumitomo 3M Co., Ltd.) for a release layer forming composition was dried to form a 10 nm release layer.

Next, Midfil (made by Kurabo Industries Co., Ltd.) was used as the thermoplastic resin film, and the thermoplastic resin film and the element surface of the element wafer were pressed under a vacuum at 370 ° C and a pressure of 0.11 MPa for 3 minutes. Then, make a test piece.

<Comparative Example 4>

100 parts of Si wafer was coated with 0.5 parts by mass of OPTOOL DSX (manufactured by Daikin Industry Co., Ltd.) and 99.5 parts by mass of Fluorinert FC-40 (manufactured by Sumitomo 3M Co., Ltd.) The support layer was formed by drying the composition for forming a release layer) to form a 10 nm release layer.

Next, Midfil (made by Kurabo Industries Co., Ltd.) was used as the thermoplastic resin film, and the thermoplastic resin film and the side of the support on which the release layer was formed were vacuumed at 370 ° C and a pressure of 0.11 MPa. Next, pressure bonding was performed for 3 minutes to prepare an adhesive support.

Next, the adhesive support and the element surface of the element wafer were compression-bonded under vacuum at 370 ° C and a pressure of 0.11 MPa for 3 minutes to prepare a test piece.

<Water contact angle of the release layer>

The water contact angle of the release layer is a release layer on a Si wafer with a thickness of 100 mm, under the same conditions as the film formation conditions for forming the release layer of various test pieces. The composition for forming was formed into a film, and a release layer having the same film thickness as the release layer of various test pieces was formed to prepare a test piece.

Next, the test piece was heated at 250 ° C for 2 hours, and then cooled to 25 ° C. A water contact angle was measured using a contact angle meter (model: CA-D) manufactured by Kyowa Interface Science Co., Ltd. The measurement was carried out by dropping 70 pL of water droplets on the surface of the release layer of each test piece at room temperature 25 ° C. and humidity 50%, and measuring the contact angles at five locations, and using the average of the five points as the contact angle.

<Peelability>

<< Evaluation of Peel Strength >>

Place the test piece with the cutting frame in the center of the cutting tape installation machine, and place the cutting tape from above. The test piece and the cutting tape are fixed by a roller (and vacuum), the cutting tape is cut on a cutting frame, and the test piece is mounted on the cutting tape.

The test piece was stretched under the condition of 500 mm / min in the vertical direction temporarily followed by the laminate, and the peelability was confirmed. Then, the prepared test piece was heated at 250 ° C. for 30 minutes, and then similarly stretched under the condition of 250 mm / min in the vertical direction of the laminated body temporarily, and the peelability after the thermal process was confirmed. The following criteria were used: Evaluate. In addition, the presence or absence of damage to the Si wafer was visually confirmed.

A: The maximum peeling force is less than 6N to peel.

B: The maximum peeling force is 6N or more and less than 12N to peel.

C: The maximum peeling force is 12 N or more and less than 20 N to peel.

D: The maximum peeling force is 20N or more, or the Si wafer is broken and cannot be peeled.

<< Evaluation of element surface >>

The external appearance of the element surface of the element wafer after the Si wafer was peeled off was visually observed, and evaluated according to the following criteria.

A: No residual of the thermoplastic resin film was found

B: A little residue of the release layer was found

C: Residue of mold release layer and thermoplastic resin film was found

<Heat resistance>

The test piece was heated at 300 ° C or 400 ° C in a vacuum and observed using an ultrasonic microscope (Hitachi Power Solutions Co., Ltd., model: FineSAT). The evaluation was performed by the following criteria.

A: No void was found in the laminated body for the time being

B: A gap with a diameter of less than 3 mm was found at several locations where the laminated body was temporarily continued

C: A gap with a diameter of 3 mm or more was found with the laminated body for the time being, or a gap was found with the entire surface

From these results, the peelability of Examples 1 to 14 was good.

On the other hand, Comparative Examples 1 to 4 had peeling residues of the thermoplastic resin on the element surface, and the peelability was poor.

Claims (11)

A temporary bonding layer is used to temporarily bond the element surface of a component wafer and a support to be peeled off. The temporary bonding layer includes a thermoplastic resin film and a layer containing a release agent, and the release agent. It is selected from the group consisting of a silicone resin and a silane coupling agent having a silicon atom and a fluorine atom which can be burned onto the thermoplastic resin film by heating at 150 ° C or higher; The region corresponding to the element surface includes at least the layer containing the release agent; the temporary bonding layer is used to temporarily bond the element wafer and the support, and then peel the support from the element surface of the element wafer. In the case of lamination, a laminated body including at least the support and the thermoplastic resin film is peeled from the element. The laminated body for temporary bonding according to item 1 of the scope of the patent application, wherein the thermoplastic resin film contains a thermoplastic resin having a glass transition point of 50 ° C to 400 ° C. The laminated body for temporary bonding according to item 1 or 2 of the scope of patent application, wherein the thermoplastic resin film contains a member selected from the group consisting of thermoplastic polyimide, polystyrene-based elastomer, polyester-based elastomer, and polymer. At least one thermoplastic resin of fluorene-based elastomer, polyether ether ketone, polyphenylene ether, modified polyphenylene ether, polyether fluorene, polyacetal resin, and cycloolefin polymer. The laminated body for temporary bonding according to item 1 or item 2 of the scope of patent application, wherein the 1% weight reduction temperature of the thermoplastic resin film which is increased from 25 ° C at 20 ° C / min is 250 ° C or more . The laminated body for temporary bonding according to item 1 or item 2 of the scope of patent application, wherein the thickness of the layer containing the release agent is 0.001 nm to 1000 nm. The laminated body for temporary bonding according to item 1 or item 2 of the scope of patent application, wherein the layer containing the release agent is heated at 250 ° C for 2 hours and then cooled to 25 ° C as measured by water. The contact angle is 30 ° or more. The laminated body for temporary bonding according to item 1 or 2 of the scope of application for a patent, wherein, in the case where the release agent-containing layer includes the silicone resin, the release agent-containing layer is larger than the release agent-containing layer. For all the solid content of the layer, the silicone resin is in an amount of 50% to 100% by mass. The laminated body for temporary bonding according to item 1 or item 2 of the scope of patent application, wherein the release agent is a silane coupling agent having a silicon atom and a fluorine atom, and the fluorine atom content rate is 20% to 80 %. A method for temporarily manufacturing a laminated body, comprising the step of forming a layer containing a mold release agent on a surface of a thermoplastic resin film, the mold release agent being selected from the group consisting of being burnt onto the thermoplastic by heating at 150 ° C or higher. A silicone resin on a resin film and a silane coupling agent having a silicon atom and a fluorine atom. The method for producing a laminated body for temporary bonding according to item 9 of the scope of application for a patent, wherein, in the case where the release agent-containing layer includes the silicone resin, the release agent-containing layer is larger than the release agent-containing layer. In terms of all solid contents, the silicone resin is in an amount of 50% to 100% by mass. A laminated body with an element wafer, comprising a temporarily bonded laminated body as described in any one of the items 1 to 8 of the scope of patent application between the element wafer and the support, said temporarily subsequently used The surface of the release layer side of the multilayer body is in contact with the element surface of the element wafer, and the other surface is in contact with the surface of the support body.