KR101884258B1 - Layered body for temporary bonding, method for manufacturing layered body for temporary bonding, and layered body provided with device wafer - Google Patents

Abstract

The present invention provides a laminate for adhesion which is capable of easily releasing adhesion between a device wafer and a support, a production method of the laminate for adhesion and a laminate with a device wafer.
The adhesive layer laminate according to the present invention is a laminate for adhesive lamination which is used for releasably adhering a device surface of a device wafer and a support in a peelable manner. The laminate is composed of a thermoplastic resin film, a compound having a siloxane bond, And a layer containing a releasing agent in a region corresponding to the device surface as a surface on the device side of the thermoplastic resin film. The laminate including at least the support and the thermoplastic resin film is peeled from the device when the support is peeled from the device surface of the device wafer after the device wafer and the support are bonded.

Description

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

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a laminate for adhesion, a method for manufacturing a laminate for adhesion, and a laminate with a device wafer. More particularly, the present invention relates to a laminate for adhesion, a method for manufacturing a laminate for adhesion, and a laminate having a device wafer, which can be preferably used for manufacturing semiconductor devices and the like.

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

Further miniaturization and high integration of IC chips mounted on electronic devices are demanded due to the demand for further miniaturization and thinning of electronic devices and high performance and low power consumption. However, there is a limit to the high integration of integrated circuits in the plane direction of device wafers It is getting closer.

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

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

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

However, a device wafer having a thickness of 200 μm or less is extremely thin, and a semiconductor device manufacturing member made of a base material is very thin. Therefore, such a member is subjected to additional processing or simply moved It is difficult to support the member stably and without damaging it.

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

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

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

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

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

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

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

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

Patent Document 9 discloses a resin composition comprising a cycloolefin polymer and a structure having at least one of a silicone structure, a fluorinated alkyl group structure, an alkenyl fluoride structure and an alkyl structure having at least 8 carbon atoms, a structure having a polyoxyalkylene structure, , The support and the substrate are temporarily fixed by means of a temporary fixing material containing a compound having at least one kind of structure.

Patent Document 10 discloses that a device wafer and a support are adhered to each other by using an adhesive composition comprising an elastomer containing a styrene unit as a constituent unit of a main chain and a wax.

Patent Document 11 discloses a method for manufacturing a semiconductor device, which comprises a step of temporarily fixing a device wafer to a supporting member with a temporary fixing film comprising a specific polyimide resin interposed between the supporting member and the device wafer, A method for manufacturing a semiconductor device, comprising the steps of: subjecting a wafer to a predetermined process; contacting an organic solvent with a temporary film to dissolve a part or all of the temporary film and separating the processed device wafer from the support member; A method of manufacturing a semiconductor device is disclosed.

In Patent Document 12, an adhesive layer is applied and formed on the device surface of a device wafer, a release layer containing a fluorinated silane compound is applied and formed on the surface of the support, an adhesive layer on the device wafer and a release layer on the support are bonded, Thereby bonding the device wafer and the support.

Patent Document 13 discloses that (A) a perfluoro compound having at least two alkenyl groups in the molecule and having a divalent perfluoroalkylene or divalent perfluoropolyether structure in the main chain, (B) A fluorine-based elastomer having at least two hydrosilyl groups in the molecule and capable of addition reaction with an alkenyl group, (C) an addition reaction catalyst, and (D) a curing agent containing an addition reaction control agent, In a detachable manner.

Patent Document 1: JP-A-2011-119427 Patent Document 2: Japanese Published Patent Application No. 2009-528688 Patent Document 3: JP-A-2011-225814 Patent Document 4: JP-A-2011-052142 Patent Document 5: Japanese Published Patent Application No. 2010-506406 Patent Document 6: JP-A-2007-045939 Patent Document 7: U.S. Patent Application Publication No. 2011/0318938 Patent Document 8: U.S. Patent Publication No. 2012/0034437 Patent Document 9: JP-A-2013-241568 Patent Document 10: JP-A-2014-34632 Patent Document 11: JP-A-2014-29999 Patent Document 12: International Publication No. WO2013 / 119976 Patent Document 13: JP-A-2005-236041

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

As a result, in the case where the entire surface of the device wafer of the device wafer and the support are adhered to each other via the adhesive layer, adhesion between the device wafer and the support is so strong that when the device wafer is removed from the support, However, a defect that the device is detached from the device wafer tends to occur.

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

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

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

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

In addition, when the adhesive of Patent Document 9 is used as a temporary fixture, the peelability is insufficient, and there is a problem that a defect that the device is damaged when the device wafer is peeled easily occurs. Furthermore, the adhesive layer was liable to remain on the device wafer side.

In Patent Document 10, the adhesive composition is applied to a device wafer or the like to form an adhesive layer. As a result, when the support was peeled from the device wafer, the adhesive layer was likely to remain on the device wafer side. In addition, in the method disclosed in Patent Document 10, the peelability of the support from the device wafer was insufficient.

Further, in Patent Document 11, an organic solvent is used as a temporary fixing film and the organic solvent is used, and the organic solvent is brought into contact with the temporary fixing film to release the device wafer. As a result, there is a tendency that time is required to release the holding paper. Further, the temporary film may remain on the side of the device wafer, and the removal process of the remaining film may be troublesome.

Further, in Patent Document 12, since the adhesive layer is formed on the device surface of the device wafer, when the support is peeled from the device wafer, the adhesive layer is likely to remain on the device wafer side.

In Patent Document 13, the peelability was not sufficient.

SUMMARY OF THE INVENTION The present invention has been made in view of the background described above, and an object thereof is to provide an adhesive laminate capable of easily releasing adhesion between a device wafer and a support, a method of manufacturing a laminate for adhesion, And the like.

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have found that a thermoplastic resin film having a layer containing a siloxane bond-containing compound and a releasing agent selected from a compound containing a silicon atom and a fluorine atom, It is possible to adhere the device wafer and the support to each other by a high adhesive force using the adhesive laminate having at least the layer containing the release agent in the area corresponding to the device surface as the surface of the device side, It is possible to easily release adhesion of the support, and thus the present invention has been accomplished. The present invention provides the following.

≪ 1 > A laminate for adhesive bonding used for releasably adhering a device surface of a device wafer and a support,

Wherein the adhesive laminate has a layer comprising a thermoplastic resin film, a compound having a siloxane bond, and a releasing agent selected from a compound having a silicon atom and a fluorine atom, wherein the surface of the device side of the thermoplastic resin film, And at least a layer containing a releasing agent in a region corresponding to the layer,

Wherein the adhesive layer laminate is a laminated body including at least a support and a thermoplastic resin film peeled from the device when the support is peeled from the device surface of the device wafer after the device wafer and the support are bonded, sieve.

<2> The adhesive layer laminate according to <1>, wherein the thermoplastic resin film comprises a thermoplastic resin having a glass transition point of 50 to 400 ° C.

&Lt; 3 &gt; The thermoplastic resin film according to &lt; 3 &gt;, wherein the thermoplastic resin film is at least one selected from the group consisting of thermoplastic polyimide, polystyrene elastomer, polyester elastomer, polyamide elastomer, polyetheretherketone, polyphenylene ether, modified polyphenylene ether, , A polyacetal resin, and a cycloolefin polymer. The laminate according to &lt; 1 &gt; or &lt; 2 &gt;

<4> The laminate for adhesion according to any one of <1> to <3>, wherein the thermoplastic resin film has a 1% weight loss temperature of 250 ° C. or higher from 25 ° C. to 20 ° C./min.

&Lt; 5 &gt; The adhesive layered laminate according to any one of &lt; 1 &gt; to &lt; 4 &gt;, wherein the layer containing the release agent has a thickness of 0.001 to 1000 nm.

&Lt; 6 &gt; The layer containing a releasing agent described in any one of &lt; 1 &gt; to &lt; 5 &gt;, wherein the layer having a water contact angle of 30 DEG or more measured at a temperature of 250 DEG C for 2 hours and then cooled to 25 DEG C Layer laminate.

<7> The adhesive laminate according to any one of <1> to <6>, wherein the releasing agent is a silane coupling agent having a silicon atom and a fluorine atom.

<8> The adhesive layered laminate according to any one of <1> to <7>, wherein the releasing agent is a compound having a silicon atom and a fluorine atom, and the content of fluorine atoms is 20 to 80%.

<9> The laminate for adhesion according to any one of <1> to <6>, wherein the mold release agent is a silicone resin capable of being baked in a thermoplastic resin film by heating at 150 ° C. or higher.

&Lt; 10 &gt; A method for producing a laminate for adhesion, comprising a step of forming on a surface of a thermoplastic resin film a layer comprising a compound having a siloxane bond and a releasing agent selected from a compound having a silicon atom and a fluorine atom.

<11> A laminate for adhering according to any one of <1> to <9>, which is disposed between a device wafer and a support, wherein a surface of the release layer side of the adherent laminate is in contact with a device surface of a device wafer, And the other surface is in contact with the surface of the support.

According to the present invention, it becomes possible to provide a laminate for adhesion, a method for manufacturing a laminate for adhesion, and a laminate with a device wafer, which can easily release adhesion between a device wafer and a support.

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

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

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

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

In the present specification, the term "light" means an actinic ray or radiation.

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

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

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

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

&Lt; Adhesive laminate &

The adherence laminate of the present invention is a adherence laminate which is used for adhering a device surface of a device wafer and a support in a peelable manner. The adherence layer laminate includes a thermoplastic resin film and a siloxane bond And a releasing agent selected from a compound having a silicon atom and a fluorine atom and having at least a layer containing a releasing agent in a region corresponding to the device surface as a device side surface of the thermoplastic resin film, Layer laminate is such that a laminate including at least a support and a thermoplastic resin film is peeled from the device when the support is peeled from the device surface of the device wafer after the device wafer and the support are bonded. Hereinafter, the layer containing the releasing agent is also referred to as a releasing layer.

Since the adhesive laminate of the present invention has the release layer in the area corresponding to the device surface as the device-side surface of the thermoplastic resin film, adhesion between the device wafer and the support can be easily released, It is excellent. Further, the release layer is formed on the surface of the thermoplastic resin film, and the surface of the thermoplastic resin film is excellent in flatness, so that the release layer can be formed with a substantially uniform film thickness. That is, if a layered product for adhesion is formed by spin coating, outgas caused by the residual solvent, wrinkles due to drying and shrinking, and peripheral shrinkage due to edge beads occur. However, By using it as a laminate for adhesion, the above problems can be suppressed. As a result, when the device wafer and the support are adhered to each other, the thermoplastic resin film is hardly brought into direct contact with the device surface, and more excellent peelability can be achieved. As a result, when the support is peeled from the device surface of the device wafer after the device wafer and the support adhere to each other, a laminate including at least the support and the thermoplastic resin film is peeled off from the device. Thus, a thermoplastic resin film It is possible to simplify the labor of cleaning the device wafer after the adhesion between the device wafer and the support is released.

Further, since the thermoplastic resin film is used, the thermoplastic resin is softened by the heating at the time of pressing the device wafer and the support. As a result, excellent adhesion can be achieved without causing voids to follow the fine irregularities of the device wafer.

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

In the present specification, "the area corresponding to the device surface as the surface of the device side of the thermoplastic resin film" means a region corresponding to the device wafer side of the adhesive layer Is a region in contact with the device surface of the device wafer.

The adhesive laminate of the present invention is such that, when the support is peeled from the device surface of the device wafer after the device wafer and the support are bonded, the laminate including at least the support and the thermoplastic resin film is peeled from the device. The peeling may be peeling at the interface between the device surface and the release layer, peeling at the interface between the release layer and the thermoplastic resin film, or peeling inside the release layer.

That is, the release surface of the release layer may be attached to the device surface of the device wafer after the support is peeled from the device wafer. 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 device surface. It is preferable that the entire surface of the thermoplastic resin film is laminated on the support, but a part of the thermoplastic resin film (preferably 10% or more of the surface area of the thermoplastic resin film) Or less, more preferably 5% or less) may be peeled from the support.

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

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

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

<< Thermoplastic Resin Film >>

In the adhesive laminate of the present invention, the thermoplastic resin film may be a film obtained by processing a thermoplastic resin into a film shape by a method such as injection molding, extrusion molding, or coating. By using a thermoplastic resin film, since it follows the shape of a chip or the like on a device wafer and is deformed, the adhesion between the device wafer and the support is good. Further, the support and the device wafer can be adhered without causing voids.

The average thickness of the thermoplastic resin film is not particularly limited, but is preferably 0.1 to 500 탆, more preferably 0.1 to 300 탆, and more preferably 1 to 150 탆. When 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 device surface of the device wafer. Further, it is difficult to increase the outgassing at the time of processing after the adhesion, and the deviation at the time of bonding.

Further, in the present invention, the average thickness of the thermoplastic resin film is preferably in the range from one end face to the other end face in the section along the one direction of the thermoplastic resin film at five places at regular intervals Is defined as the average value of the values measured by the micrometer.

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

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

The 1% weight reduction temperature of the thermoplastic resin film which has been raised from 25 占 폚 to 20 占 폚 / min is preferably 250 占 폚 or higher, more preferably 300 占 폚 or higher, and still more preferably 350 占 폚 or higher. If the 1% weight reduction temperature of the thermoplastic resin film is 250 DEG C or higher, decomposition of the thermoplastic resin can be suppressed even when exposed to high temperatures during mechanical or chemical treatment of the device wafer, effectively suppressing the generation of voids . The weight reduction temperature is a value measured under the above-mentioned elevated temperature condition under a nitrogen stream by a thermogravimetric analyzer (TGA).

The content of the solvent in the thermoplastic resin film is preferably 5% by mass or less, more preferably 1% by mass or less, and particularly preferably not contained. According to this embodiment, outgas can be suppressed, and voids can be prevented from being generated when the substrate is heated in a bonded state. The solvent content of the thermoplastic resin film can be measured by gas chromatography (GC).

<<< Thermoplastic Resin >>>

In the adhesive laminate of the present invention, the thermoplastic resin film preferably includes a thermoplastic resin. Examples of the thermoplastic resin include thermoplastic polyimide, polystyrene elastomer, polyester elastomer, polyamide elastomer, polyetheretherketone, polyphenylene ether, modified polyphenylene ether, polyethersulfone, polyacetal resin And a cycloolefin polymer. From the viewpoint of heat resistance, it is also possible to use a polystyrene elastomer, a polyester elastomer, a polyamide elastomer, a polyetheretherketone, a polyphenylene ether, a modified polyphenylene ether and a polyether sulfone, Cycloolefin polymer, and more preferably at least one thermoplastic polyimide. The thermoplastic resin may be used singly or in a mixture of two or more kinds.

The thermoplastic resin film containing the thermoplastic resin can follow the fine irregularities of the device wafer and can achieve excellent adhesion without generating voids. Further, when the support is peeled from the device wafer, the support can be peeled off (preferably, machine peeled off) from the device wafer without stressing the device wafer or the like, and breakage or peeling of the device or the like can be prevented.

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

The glass transition temperature (hereinafter also referred to as Tg) of the thermoplastic resin is preferably 50 to 400 ° C, more preferably 75 to 400 ° C, and further preferably 110 to 350 ° C. When the Tg is in the above range, the thermoplastic resin film is softened at the time of adhesion between the device wafer and the support, and even after the fine unevenness of the device wafer, voids are not generated, and excellent adhesion can be achieved. When the thermoplastic resin has two or more types of Tg, the value of Tg means the lower glass transition point.

The melting point of the thermoplastic resin is preferably 100 to 450 占 폚, more preferably 120 to 400 占 폚. When the melting point is in the above-mentioned range, it follows the fine irregularities of the device wafer and excellent adhesion can be achieved without generating voids. When the thermoplastic resin has two or more kinds of melting points, the melting point means a lower melting point.

The weight average molecular weight of the thermoplastic resin is preferably from 2,000 to 200,000, more preferably from 10,000 to 200,000, and most preferably from 50,000 to 100,000. Within this range, the heat resistance can be improved.

<<<< Thermoplastic Polyimide >>>>

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

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

As the thermoplastic polyimide resin, those having a repeating structural unit represented by the following general formula (1) can be cited.

[Chemical Formula 1]

In the general formula (1), X is a direct bond, -SO ₂ -, -CO-, -C (CH ₃ ) ₂ -, -C (CF ₃ ) ₂ - or -S- and R ¹ and R ² , R ³ and R ⁴ each independently represent 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, Y is a group consisting of the following formula (2) Lt; / RTI &gt;

(2)

The thermoplastic polyimide resin having a repeating structural unit represented by the general formula (1) is obtained by reacting an etheral amine represented by the following general formula (3) and a tetracarboxylic acid dianhydride represented by the following general formula (4) as raw materials in the presence of an organic solvent Or in the absence of a solvent, and chemically or thermally imidizing the resulting polyamic acid.

(3)

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 in the general formula (1).

Specific examples of R ¹ , R ² , R ³ and R ^{4 in} the general formulas (1) and (3) include alkyl groups such as a hydrogen atom, methyl group and ethyl group, alkoxy groups such as methoxy group and ethoxy group, A halogenated alkyl group such as a methyl group and a trifluoromethyl group, a halogenated alkoxy group such as a fluoromethoxy group, and a halogen atom such as a chlorine atom and a fluorine atom. Preferably, it is a hydrogen atom. X 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 formulas (1) and (4), Y is represented by the formula (2), and pyromellitic dianhydride is preferably used as the acid dianhydride.

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

[Chemical Formula 4]

As the thermoplastic polyimide resin, thermoplastic polyimide resins having repeating structural units represented by the following formulas (6) and (7) are also preferable.

[Chemical Formula 5]

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

The thermoplastic polyimide resin having the repeating structural units represented by the formulas (6) and (7) can be obtained by reacting the corresponding etheral amine and tetracarboxylic acid dianhydride as raw materials in the presence or absence of an organic solvent, The polyamide acid can be prepared by chemically or thermally imidizing the polyamide acid. As a concrete production method of these, known conditions of the production method of polyimide can be used.

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

[Chemical Formula 6]

The thermoplastic polyimide resin having a repeating structural unit represented by the formula (8) can be prepared by reacting the obtained polyamic acid with a corresponding etheralamine and tetracarboxylic acid dianhydride in the presence or absence of an organic solvent as a raw material, Or thermally imidized. As a concrete production method of these, known conditions of the production method of polyimide can be used.

The thermoplastic polyimide resin is excellent in heat resistance. The 1% weight reduction temperature of the thermoplastic polyimide resin which has been raised from 25 占 폚 to 20 占 폚 / min is preferably 250 占 폚 or higher, more preferably 300 占 폚 or higher, and still more preferably 350 占 폚 or higher.

The Tg of the thermoplastic polyimide resin is preferably 200 to 400 占 폚, more preferably 250 to 375 占 폚, and still more preferably 300 to 350 占 폚. When the Tg is within the above range, it follows the fine irregularities of the device wafer, and excellent adhesion can be achieved without generating voids.

Examples of commercially available products of the thermoplastic polyimide include "Aurum (registered trademark)" manufactured by Mitsui Chemicals, Ltd., "Midfil (registered trademark)" manufactured by Kurashiki Boshiki Co., Spel (registered trademark) TP "or the like may be used.

<<<< Polystyrene based elastomer >>>>

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

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

The polystyrene-based elastomer is preferably a block copolymer of styrene and another resin. More preferably, the polystyrene-based elastomer is a block polymer of styrene at one terminal or both terminals, and particularly preferably a block polymer of styrene at both terminals. When the both ends of the polystyrene-based elastomer are styrene block polymers (repeating units derived from styrene), the thermal stability tends to be further improved. This is because the repeating unit derived from styrene having high heat resistance is present at the terminal. Particularly, since the block portion of the repeating unit derived from styrene is a reactive polystyrene-based hard block, it is preferable because heat resistance and chemical resistance tend to be better. When these are used as a block copolymer, it is considered that phase separation is performed between the hard block and the soft block at 200 캜 or higher. It is believed that the shape of the phase separation contributes to suppressing the generation of irregularities on the substrate surface of the device wafer. Such a resin is more preferable from the viewpoint of solubility in a solvent and resistance to a resist solvent.

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

In the present specification, the "repeating unit derived from styrene" is a structural unit derived from styrene contained in the polymer when the styrene or styrene derivative is polymerized, and may have a substituent. Examples of the styrene derivative include? -Methylstyrene, 3-methylstyrene, 4-propylstyrene and 4-cyclohexylstyrene. Examples of the substituent include an alkyl group of 1 to 5 carbon atoms, an alkoxy group of 1 to 5 carbon atoms, an alkoxyalkyl group of 1 to 5 carbon atoms, an acetoxy group, and a carboxyl group.

Examples of commercially available polystyrenic elastomers include commercially available products such as "Gastronet" (Septon S2104, etc.), "Hiabra" by Kuraray Co., Ltd., "TurfecT" by Asahi Kasei Chemicals Co., Ron. "

<<<< Polyester elastomer >>>>

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

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

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

(7)

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

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

As the polyester elastomer, an aromatic polyester (e.g., polybutylene terephthalate) portion as a hard segment component and an aliphatic polyester (e.g., a polytetramethylene glycol) portion as a soft segment component One multi-block copolymer may be used. As the multi-block copolymer, various grades may be cited depending on the kind, ratio, and molecular weight of the hard segment and the soft segment. Specific examples thereof include "pre-maloi" manufactured by Mitsubishi Kagaku Co., Ltd., "Pelprene" manufactured by Toyo Boseki Co., Ltd., and "Hitrell" manufactured by Toray DuPont Co.,

<<<< Polyamide elastomer >>>>

The polyamide-based elastomer is not particularly limited and may be appropriately selected depending on the purpose. For example, a polyamide such as polyamide-6, 11, 12 or the like may be used for a hard segment and a polyether and / or polyester such as polyoxyethylene, polyoxypropylene, and polytetramethylene glycol may be used as a soft segment And the like. This elastomer is roughly classified into two types, a polyether block amide type and a polyetherester block amide type. Commercially available products include "diamide" and "besamide E" manufactured by Daicel-Ebonics Co., Ltd. and "TPAE" manufactured by T & K TOKA Co., Ltd.

<<<< Polyetherketone >>>>

Examples of the polyether ketone include, but are not limited to, "VICTREX PEEK" manufactured by VICTREX Japan Co., Ltd., "X-Peak" manufactured by Kurashiki Boshoku Co., "Vesta Kip" manufactured by Nick Co., Ltd., and the like.

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

The polyphenylene ether or the modified polyphenylene ether can be used without particular limitation. For example, "NORYL" manufactured by SABIC Innovative Plastics Japan, "Zairon" manufactured by Asahi Kasei Chemicals Co., Ltd., "Yepia Ace", "Remalloy" manufactured by Mitsubishi Engineering Plastics Co., And "Besostran" produced by Ebonic Co., Ltd. and the like.

<<< Polyether sulfone >>>

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

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

[Chemical Formula 8]

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

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

[Chemical Formula 9]

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

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

As the polyethersulfone, a commercially available product may be used. Examples thereof include "Ultrason E series" (Ultrason E6020P etc.) manufactured by BASF, "Radel A series" manufactured by Solvay Advanced Polymer, "Sumika Excel PES series" manufactured by Sumitomo Chemical Co., Ltd .; and Solvay Specialty Polymers Japan Quot; Verdel "and the like. Examples of the "Sumika Excel series" include Sumika Excel (registered trademark) PES3600P, Sumika Excel (registered trademark) PES4100P, Sumika Excel (registered trademark) PES4100MP, Sumika Excel (registered trademark) PES4800P, Sumika Excel (registered trademark) , Sumika Excel (registered trademark) PES5200P, and Sumika Excel (registered trademark) PES5400P.

<<<< Polyacetal resin >>>>

The polyacetal resin may be used without particular limitation. For example, "Delrin" manufactured by DuPont Co., "DURACON" manufactured by Polyplastics Co., Ltd., "Tenak" manufactured by Asahi Gas Chemical Co., Ltd., "Yuplatel" manufactured by Mitsubishi Engineering Plastics Co., .

<<<< Cycloolefin Polymer >>>>

The cycloolefin polymer may be used without particular limitation. "TOPAS" manufactured by TOPAS ADVANCED POLYMERS GmbH, "APEL" manufactured by Mitsui Kagaku Co., Ltd., "ZEONEX" manufactured by JSR Corporation, "Zeonex" manufactured by Nippon Zeon Co., ARTON "and the like.

The thermoplastic resin film preferably contains the thermoplastic resin in an amount of 50 to 100 mass%, more preferably 70 to 100 mass%, and particularly preferably 88 to 100 mass%, based on the total solid content of the thermoplastic resin film. According to this embodiment, it is easy to obtain a laminate for adhesion with excellent adhesion and peelability.

The thermoplastic resin may be a single type or two or more types. When the number of the thermoplastic resins is two or more, the total is preferably in the above range.

<<< Antioxidants >>>

The thermoplastic resin film may contain an antioxidant from the viewpoint of preventing the polymer component from becoming low molecular weight or gelation due to oxidation at the time of heating. As the antioxidant, phenol antioxidants, sulfur antioxidants, phosphorus antioxidants, quinone antioxidants, amine antioxidants and the like can be used.

Examples of the phenol antioxidant include p-methoxyphenol, 2,6-di-tert-butyl-4-methylphenol, Irganox (registered trademark) 1010, Irganox (registered trademark) "Sumilizer (registered trademark) MDP-S" and "Sumilizer (registered trademark) GA-80" manufactured by Sumitomo Chemical Co., Ltd. have.

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

Examples of the phosphorus antioxidant include tris (2,4-di-tert-butylphenyl) phosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, poly Irgafos (registered trademark) 168, Irgafos (registered trademark) 38, etc., manufactured by BASF, and the like can be given as examples of the organic phosphine phosphite, dialkyl phosphite, diphenyl isodecyl phosphite, 2-ethylhexyl diphenyl phosphite, have.

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

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

The antioxidant is preferably Irganox (registered trademark) 1010, Irganox (registered trademark) 1330, 3,3'-thiodipropionate distearyl, Sumilizer (registered trademark) TP- , Irganox (registered trademark) 1330 is more preferable, and Irganox (registered trademark) 1010 is particularly preferable.

Among the above-mentioned antioxidants, phenol-based antioxidants and sulfur-based antioxidants or phosphorus-based antioxidants are preferably used in combination, and phenol-based antioxidants and sulfur-based antioxidants are most preferably used in combination. Particularly, it is preferable to use a combination of a phenol-based antioxidant and a sulfur-based antioxidant. With such a combination, it is possible to expect an synergistic effect of converting the hydroperoxide (ROOH), which is a decomposition product, into a stable ROH group, while supplementing the peroxy radical generated in the course of thermal oxidation. When the phenol-based antioxidant and the sulfur-based antioxidant are used in combination, the mass ratio of the phenol-based antioxidant to the sulfur-based antioxidant is preferably from 1:10 to 10: 1, more preferably from 1: 5 to 5: : 1 is more preferable.

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

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

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

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

<<< Surfactant >>>

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

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

Examples of the fluorochemical surfactant include Megapak F-251, F-281, F-430, F-444, F-477, F-510 and F-552 , F-553, F-554, F-555, F-556, F-557, F-558, F-559, , F-563, F-565, F-567, same F-568, same F-569, same F-570, same F-571, same R-40, same R-41, same R-43 , S-242, S-243, S-386, S-651 (trade name) manufactured by AGC SEIMI CHEMICAL CO., LTD. S-611, S-420, and PF-636, PF-656, PF-6320, PF-6520 and PF-7002 manufactured by OMNOVA.

Examples of the nonionic surfactant include glycerol, trimethylol propane, trimethylol ethane, and their ethoxylates and propoxylates (for example, glycerol propoxylate, glycerin ethoxylate and the like), polyoxyethylene Polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol di-laurate, polyethylene glycol di Stearate and the like.

Examples of the cationic surfactant include EFKA-745 manufactured by Morishita Sangyo Co., Ltd., and Polyflur No. 7 manufactured by Kyoeisha Kagaku Co., 75, No. 90, No. 95 &lt; / RTI &gt;

TSF-4445, TSF-4460, TSF-4452, Shin-Etsu Silicone Co., Ltd. KP-341, KF- 6001, KF-6002, BYK-307, BYK-323 and BYK-330 manufactured by BICKEMI CO., LTD.

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

The surfactant may be one kind or two or more kinds. When two or more kinds of surfactants are used, the total amount is preferably in the above range.

<< Other additives >>

The thermoplastic resin film may contain various additives such as a plasticizer, a compatibilizing agent, a filler, an adhesion promoter, an ultraviolet absorber, an anti-aggregation agent, a silane coupling agent, and the like in a range that does not impair the effects of the present invention can do. When these additives are compounded, the total amount is preferably 3% by mass or less of the total solid content of the thermoplastic resin film.

<< Disclaimer >>

The adherence laminate of the present invention is a laminate for adhe- sive comprising a releasing agent selected from a compound having a siloxane bond and a compound having a silicon atom and a fluorine atom in a region corresponding to a device surface, Layer (release layer). The releasing agent is preferably a compound having a silicon atom and a fluorine atom. According to this embodiment, more excellent peelability can be achieved.

The film thickness of the release layer is not particularly limited as it is effective even if it is a thin film. For example, it is preferably 0.001 to 1000 nm, more preferably 0.1 to 500 nm, and further preferably 1 to 100 nm. Within this range, it is possible to prevent direct contact of the thermoplastic resin film with the device wafer at the time of adhesion between the device wafer and the support, thereby achieving more satisfactory releasability.

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

When the releasing layer contains a compound having a silicon atom and a fluorine atom, the releasing layer is a layer containing a compound containing at least one selected from a fluorine atom and a silicon atom in an amount of 5 to 100 mass %, More preferably from 50 to 100 mass%, still more preferably from 90 to 100 mass%.

When the releasing layer contains a compound having a siloxane bond, the releasing layer preferably contains a compound having a siloxane bond in an amount of 5 to 100 mass% with respect to the total solid content of the releasing layer, more preferably 50 to 100 mass% %, More preferably from 90 to 100 mass%.

When the releasing layer contains a compound having a silicon atom and a fluorine atom and a compound having a siloxane bond, the releasing layer preferably contains 30 to 95 mass% of a compound having silicon atoms and fluorine atoms relative to the total solid content of the releasing layer, , A compound having a siloxane bond is preferably contained in an amount of 5 to 70 mass%, more preferably 40 to 90 mass% of a compound having a silicon atom and a fluorine atom, and 10 to 60 mass% of a compound having a siloxane bond desirable.

There may be only one type of release agent, or two or more types of release agents. When the release agent is two or more kinds, it is preferable that the total amount is in the above range.

The release layer preferably has a water contact angle of 30 DEG or more, more preferably 40 DEG or more, and more preferably 50 DEG or more, as measured at 250 DEG C for 2 hours and then at 25 DEG C. The upper limit is not particularly limited, but is preferably 140 DEG or less, more preferably 130 DEG or less, and more preferably 120 DEG or less. When the water contact angle is 30 DEG or more, excellent peelability is obtained.

Further, in the present invention, the water contact angle was measured by using various kinds of release layers formed on a 100 mm thick Si wafer. A contact angle meter (product number: CA-D) manufactured by Kyowa Kaimengagaku Co., Ltd. was used as the contact angle measuring apparatus. At a room temperature of 25 占 폚 and a humidity of 50%, a water droplet of 70 pL was dropped and contact angles at five sites were measured. Five contact angles were averaged to obtain the contact angle of each sample.

<<< Compound with siloxane bond >>>

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

Silicone resins can be suitably used in both solventless, oil, solution, emulsion and baking forms.

The silicone resin is preferably capable of being baked on the surface of the thermoplastic resin film by heating at 150 占 폚 or higher (more preferably 200 占 폚 or higher, more preferably 250 占 폚 or higher, particularly preferably 300 占 폚 or higher) . The upper limit is preferably 450 占 폚 or lower, more preferably 400 占 폚 or lower, and still more preferably 350 占 폚 or lower. If the baking at such a temperature is feasible, the release layer is hardly decomposed during mechanical or chemical treatment at a high temperature, and the heat resistance is excellent. Further, generation of voids can be effectively suppressed.

The phrase "stickable to the surface of the thermoplastic resin film" means a state in which the silicone resin is strongly bonded to the thermoplastic resin and does not easily peel off by reacting by heating after the film formation.

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

As the silicone resin, a linear organopolysiloxane and / or an organopolysiloxane having a branched structure are preferable. As the organopolysiloxane, for example, an organopolysiloxane represented by the following general formula (1) can be used.

[Chemical formula 10]

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

(11)

The alkenyl group represented by R ¹ includes, for example, vinyl, allyl, propenyl, and the like.

Examples of the monovalent organic group represented by R ² include alkyl groups such as methyl, ethyl, propyl, butyl and the like; Cycloalkyl groups such as cyclohexyl group; Alkenyl groups such as vinyl, allyl and propenyl; An aryl group such as phenyl or tolyl, or a chloromethyl group, a trifluoropropyl group or a cyanoethyl group substituted with a halogen atom, a cyano group, an amino group or the like in a part or all of hydrogen atoms bonded to the carbon atoms of these groups A substituted or unsubstituted monovalent hydrocarbon group or an alkoxy group such as methoxy, ethoxy, propoxy or methoxyethoxy group, a hydroxyl group, or an epoxy group.

R ¹ is preferably a vinyl group industrially, and R ² is preferably a methyl group at least 80 mol%, both industrially and in terms of characteristics.

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

a and d are numbers of siloxane units located at the molecular end of the organopolysiloxane, a is 2 or more, d is 0 or a positive integer, and from the relationship between the number of branches and the number of molecular terminals, a + d = b + 2.

The structural unit having an alkenyl group alone is only M ^1, and when a is 2 or more, the number of alkenyl groups in one molecule is 2 or more, and the alkenyl group is preferentially arranged at the molecular chain terminal. Even if d = 0, if d + d = b + 2 can be satisfied, d = 0 is more preferable in order to achieve good curability.

The range of the degree of polymerization of the organopolysiloxane is limited by the combined value of a, b, c, and d, but practical indication is visually useful. The viscosity of the polymer having a high degree of polymerization is generally expressed as a limiting viscosity? R, but the limiting viscosity? R of the organopolysiloxane is particularly preferably in the range of 1.0 to 3.0.

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

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

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

KM-9737A, KM-9738A, KM-9739, KM-722T, KM-740T, KM-742T, and KM-780 (manufactured by Shin-Etsu Chemical Co., , KF-965, KF-96, KF-965, KF-965, KF-965, KF-962, KM-782, KM-785, KM-797, KM-9705, KM-860A, KM-862T, KS-7201, KS-7200, SEPA-COAT, Toray, Dow Corning Co., Ltd., SM 7036 EX, KS-704, KM-244F, KS-61, KS-702, KS-725, KS-707, KS- , 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 TSF4600, TSF4420, TSM620, TSM621, YSR3022, TSM6281, YSR6209, YSR6209B, YSR6209B, Momentive Performance Materials, Japan Advanced Technology Corporation, 230 FLUID, SF 8416, SH 550, PRX 308, SH 7020, SR 2472, TSM630, TSM630NF, TSM631, TSM632, TSM637, YMR7212, TSM6341, TSM6343, TSM647, TSM6344, TSM6345, TSM6362, TSM6363, TSM650 and YG6144.

<<< Compound having silicon atom and fluorine atom >>>

The compound having a silicon atom and a fluorine atom is preferably a silane coupling agent. The content of fluorine atoms in the silicon-fluorine-containing compound is preferably 20 to 80%, more preferably 24 to 80%. Here, the content of fluorine atoms was measured by an ICP emission spectrochemical analyzer (product number: ICPS-8100) of Shimazu Seisakusho Co., Ltd. for each compound.

As the silane coupling agent, there may be mentioned a group having at least one fluorine atom and a compound having at least one silyl group.

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

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

[Chemical Formula 12]

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

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

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

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

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

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

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

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

Examples of the compound having a silicon atom and a fluorine atom include KBM-7103 manufactured by Shin-Etsu Chemical Co., Ltd., Optol DSX manufactured by Daikin Kogyo Co., Ltd., F-Top manufactured by Mitsubishi Materials Denshi Kasei Co., Perfluorooctyl trimethoxysilane, perfluorooctyl trimethoxysilane, trifluoropropyl triethoxysilane, perfluorooctyl trimethoxysilane, perfluorooctyl tin, perfluorooctyl trimethoxysilane, perfluorooctyl trimethoxysilane, Perfluorododecyltrimethoxysilane, perfluorododecyltriethoxysilane, perfluoropentyltriethoxysilane, perfluoropentyltrimethoxysilane, and the like, and the like. And these can be preferably used.

<<< Other Ingredients >>>

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

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

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

The production method of the adhesive laminate of the present invention includes a step of forming a layer (release layer) containing the above-described releasing agent on the surface of the above-mentioned thermoplastic resin film.

&Lt; Production method of thermoplastic resin film &gt;

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

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

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

As the solvent, any of known solvents can be used without limitation, and organic solvents are preferable.

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

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

Such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone, N-methyl-2-pyrrolidone (NMP) Ketones;

Halogens such as methylene chloride, chloroform, 1,2-dichloroethane, 1,2-dibromoethane and chlorobenzene;

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

And hydrocarbons such as limonene and p-menthane.

These solvents are also preferably mixed with two or more kinds in view of improving the application surface shape and the like. In this case, it is particularly preferable to use at least one selected from the group consisting of mesitylene, p-mentine, gamma butyrolactone, anisole, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethylcellosolve acetate, Cyclohexanone, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether, and propylene glycol methyl ether, and the like. Ether acetate, and mixtures thereof.

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

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

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

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

In the laminating method, a composition including at least the releasing agent is applied to a releasing film to form a releasing layer (releasing layer film) in a film form, and a surface of the releasing film of the releasing film of the thermoplastic resin film, This is a method of laminating by contacting a film-free surface.

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

The coating method is a method in which a solution for forming a release layer is applied to a surface of the thermoplastic resin film on which no release film is formed and then dried. As the composition for forming a release layer, it is preferable to use a solution containing the above-described release agent and a solvent. Any solvent can be preferably used as long as the solvent can dissolve the release agent. When the releasing agent contains a compound having a silicon atom and a fluorine atom, a solvent having a fluorine atom is preferable because of high solubility. As an example, Fluorinert FC-40 (manufactured by Sumitomo 3M Co., Ltd.) can be mentioned.

When a thermoplastic resin film is produced by a solution casting method, the solution for forming a release layer may be applied and dried in-line without applying a solution for film formation, drying, and winding. When the physical properties of the solution are designed so that the solution for forming a film and the solution for forming a release layer are not compatible with each other, they may be simultaneously applied and dried at the same time.

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

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

The release layer can be provided on both surfaces of the thermoplastic resin film by applying a solution for forming a release layer on both surfaces of the thermoplastic resin film.

The co-extrusion method is a method of obtaining a sheet in which the thermoplastic resin film and the release layer are integrated with each other by thermally melting the material for forming the film and the material for forming the release layer and simultaneously molding them by extrusion molding. The release layer can be provided on both surfaces of the thermoplastic resin film by extruding the material for forming the release layer on both surfaces of the material for film formation.

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

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

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

<Adhesive Support>

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

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

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

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

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

The thickness of the support is not particularly limited, but is preferably 300 占 퐉 to 100 mm, more preferably 350 占 퐉 to 10 mm, for example.

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

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

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

&Lt; Device Wafer Laminate &gt;

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

The device wafer stacking laminate of the present invention has the above-described adhesive laminate of the present invention between the device wafer and the support, and the side of the release layer side of the adhesive laminate is in contact with the device surface of the device wafer, And the other side is in contact with the surface of the support.

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

A mechanical structure or a circuit may be formed on the surface of the device wafer. Examples of the device wafer on which the mechanical structure and the circuit are formed include MEMS (Micro Electro Mechanical Systems), a power device, an image sensor, a microsensor, an LED, an optical device, an interposer, a buried device and a microdevice.

The device wafer preferably has a structure such as a metal bump, a pad, and a via. The adhesive film of the present invention can stably adhere to a device wafer having a structure on the surface, and the device wafer can be easily peeled off. The height of the structure is not particularly limited, but is preferably 1 to 100 占 퐉, for example. The structure may be buried up to the inside of the device wafer.

The thickness of the device wafer before mechanical or chemical treatment is preferably 500 탆 or more, more preferably 600 탆 or more, and more preferably 700 탆 or more. The upper limit is, for example, preferably 1000 占 퐉 or less, more preferably 900 占 퐉 or less.

The thickness of the device wafer after thinning by mechanical or chemical treatment is preferably, for example, less than 500 mu m, more preferably 400 mu m or less, and further preferably 300 mu m or less. The lower limit is, for example, preferably 5 占 퐉 or more, more preferably 10 占 퐉 or more.

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

The device wafer laminate of the present invention can be produced by heat-pressing a surface of the above-described adhesive support on the side where the adhesive laminate is formed and a device wafer. The pressure bonding conditions are, for example, a temperature of 100 to 400 DEG C, a pressure of 0.01 to 1 MPa, and a time of 1 to 15 minutes.

It is also possible to arrange the above-described adhesive laminate according to the present invention between the support and the device wafer, followed by hot pressing.

<Method of Manufacturing Semiconductor Device>

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

1 (A) to 1 (F) are schematic cross-sectional views (Figs. 1 (A) to 1 (D)) for explaining adherence between a support and a device wafer, a state in which a device wafer adhered to a support is thin 1 (E)), and a state in which the support and the device wafer are separated (Fig. 1 (F)).

1 (A) and 1 (B), a laminate 11 for adhesion, in which a release layer 110 is laminated on the surface of a thermoplastic resin film 111, is laminated on a support 12 ), And an adhesive supporting body 100 having the release layer 110 disposed on the outermost surface thereof is manufactured. The adhesive support 100 can be manufactured by the above-described method.

In the adhesive supporting member 100 of this embodiment, the entire surface of one side of the supporting member 12 is covered with the adhesive layer 11. Such an adhesive support is effective when it is desired to lower the TTV (Total Thickness Variation) of the thinning device wafer (that is, to further improve the flatness of the thin device wafer).

That is, in the case of thinning a device wafer adhered by the adhesive layer, the structure of the device wafer is first protected by the adhesive film, so that the roughness derived from the structure at the time of thinning is substantially eliminated It is possible. As a result, the TTV of the finally obtained thin device wafer can be lowered further.

As shown in Fig. 1 (C), the device wafer 60 is formed by providing a plurality of device chips 62 on the surface (device surface) 61a of the silicon substrate 61.

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

Subsequently, as shown in Figs. 1C to 2D, the adhesive supporting body 100 and the device surface 61a of the device wafer 60 are pressed to bond the supporting body 12 and the device wafer 60 .

Subsequently, the back surface 61b of the silicon substrate 61 is subjected to a mechanical or chemical treatment (not particularly limited, for example, a thinning treatment such as gliding or chemical mechanical polishing (CMP), chemical vapor deposition A treatment using a chemical such as an organic solvent, an acidic treatment solution or a basic treatment solution, a plating treatment, an irradiation with an actinic ray, a heating / cooling treatment, etc.) are carried out at a high temperature and a vacuum such as physical vapor deposition (PVD) The thickness of the silicon substrate 61 is preferably reduced (for example, the average thickness is preferably less than 500 탆, more preferably 1 to 200 탆, and more preferably 1 to 100 탆) A thin device wafer 60a is obtained.

As a mechanical or chemical treatment, a through hole (not shown) that penetrates the silicon substrate from the back surface 61b1 of the thin device wafer 60a is formed after the thinning process, and a silicon penetration electrode (Not shown) may be formed. The maximum attained temperature in the heat treatment is, for example, preferably 130 to 450 ° C, more preferably 180 to 400 ° C. The heat treatment is preferably, for example, heating for 30 seconds to 5 hours at the maximum attained temperature, more preferably for 1 minute to 3 hours at the maximum attained temperature.

Subsequently, as shown in Fig. 1 (F), the support 12 is removed from the thin device wafer 60a. The method of desorption is not particularly limited, but it is preferable to pull up the end portion of the thin device wafer 60a in the vertical direction with respect to the thin device wafer 60a and peel it off without any treatment. That is, machine separation is preferable.

The peeling interface may be the interface between the device surface 61a and the release layer 110 or may be the interface between the release layer 110 and the thermoplastic resin film 111 or may be the inside of the release layer 110. [ That is, the release surface of the release layer 110 may be attached to the device surface 61a1. A is the peel strength between the adhesive laminate 11 and the thin device wafer, and B is the peeling strength between the thermoplastic resin film 111 and the release layer 110, it is preferable that the following formula is satisfied.

A <B (1)

The peel strength was measured five times by peeling off the end of the thin device wafer 60a in the vertical direction with respect to the device wafer using a digital force gauge manufactured by Imada Co., Ltd., .

After the peeling liquid is brought into contact with the laminating adhesive layer 11 and then the thin device wafer 60a is slid with respect to the support 12 as required, the thin film device wafer 60a is peeled from the end of the thin device wafer 60a It may be pulled up in the vertical direction with respect to the device wafer and peeled off. As the exfoliation liquid, for example, the exfoliation liquid described in paragraphs 0203 to 0212 of Japanese Laid-Open Patent Publication No. 2014-80570 can be used. Further, the present invention does not necessarily require treatment with a peeling liquid or the like. It is possible to simultaneously remove the thermoplastic resin film 111 together with the support 12 from the device surface 61a of the thin device wafer 60a without generating peeling residue or the like by only mechanical separation.

After the support is peeled from the thin device wafer 60a, the device surface 61a may be cleaned by bringing it into contact with a cleaning liquid to be described later. If necessary, the thin device wafer 60a is subjected to various known processes to manufacture a semiconductor device having the thin device wafer 60a.

<Washing solution>

Hereinafter, the cleaning liquid will be described in detail.

As the cleaning liquid, an organic solvent dissolving the thermoplastic resin and the releasing agent is preferable. Examples of the organic solvent include aliphatic hydrocarbons (such as hexane, heptane, Eisophor E, H and G manufactured by Esso Chemical Co., Ltd., aromatic hydrocarbons such as toluene and xylene) Examples of the polar solvent include alcohols (such as methanol, ethanol, propanol, isopropanol, 1-butanol, 1-pentane Butanol, 1-hexanol, 1-heptanol, 1-octanol, 2-octanol, 2-ethyl-1-hexanol, Ether, 2-ethoxyethanol, diethylene glycol monoethyl ether, diethylene glycol monohexyl ether, triethylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol Polyethylene glycol monomethyl ether, polypropylene glycol, tetraethylene glycol Ethylene glycol monobutyl ether, ethylene glycol monophenyl ether, propylene glycol monophenyl ether, methylphenyl carbinol, n-amyl alcohol, methyl amyl alcohol Etc.), ketones (acetone, methyl ethyl ketone, ethyl butyl ketone, methyl isobutyl ketone and cyclohexanone), esters (ethyl acetate, Ethylene glycol monobutyl acetate, propylene glycol monomethyl ether acetate, diethylene glycol acetate, diethyl phthalate, butyl levulinate, etc.), others (triethyl phosphate, tricresyl phosphate, N- Phenylethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, 4- (2-hydroxyethyl) morpholine, N, N-dimethylacetamide, N- Tilpi pyrrolidone, etc.), and the like.

In addition, by removing the thermoplastic resin film 111 on the support 12, the support 12 can be regenerated. Examples of the method for removing the thermoplastic resin film 111 include a method of physically removing the thermoplastic resin film 111 by spraying brushes, ultrasonic waves, ice particles, and aerosols while remaining in a film form, a method of dissolving and removing them in an aqueous solution or an organic solvent, , A method of chemical decomposition by decomposition or vaporization by irradiation of heat, etc. Depending on the support, conventionally known cleaning methods can be used.

For example, in the case of using a silicon substrate as a support, a conventionally known silicon wafer cleaning method can be used. For example, as an aqueous solution or an organic solvent that can be used for chemical removal, a strong acid, a strong base, And specific examples thereof include acids such as sulfuric acid, hydrochloric acid, hydrofluoric acid, nitric acid and organic acids, bases such as tetramethylammonium, ammonia and organic bases, oxidizing agents such as hydrogen peroxide, A mixture of hydrochloric acid and hydrogen peroxide, a mixture of sulfuric acid and hydrogen peroxide, a mixture of hydrofluoric acid and hydrogen peroxide, and a mixture of hydrofluoric acid and ammonium fluoride.

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

The support cleaning liquid preferably contains an acid having a pKa of less than 0 and hydrogen peroxide. The acid having a pKa of less than 0 is selected from an inorganic acid such as hydrogen iodide, perchloric acid, hydrogen bromide, hydrogen chloride, nitric acid, sulfuric acid, or an organic acid such as alkylsulfonic acid or arylsulfonic acid. From the viewpoint of the cleaning property of the adhesive layer on the support, it is preferably an inorganic acid, most preferably sulfuric acid.

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

<< Conventional Embodiment >>

Next, a conventional embodiment will be described.

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

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

However, according to the conventional adhesive, it is difficult to easily adhere the support to the device wafer without damaging the device wafer after the device wafer is adhered by a high adhesive force. For example, if a high adhesion property is employed among conventional adhesive agents in order to sufficiently bond the device wafer and the support, adhesion between the device wafer and the support tends to be too strong. Therefore, as shown in Fig. 2, a tape (e.g., a dicing tape) 70 is attached to the back surface of the thin device wafer 60a, The thin film device wafer 60a is peeled off from the supporting substrate 100a and the device 63 is detached from the device chip 62 provided with the structure 63 to break the device chip 62 Defects are likely to occur.

On the other hand, among conventional pastes, if a low adhesive property is employed, the adhesion of the device wafer to the device wafer can be easily released. However, since the adhesion between the device wafer and the support is too weak, It is easy for defects to occur.

On the other hand, the self-adhesive laminate of the present invention exhibits sufficient adhesiveness and can easily release adhesion between the device wafer 60 and the support 12. That is, according to the adhesive laminate of the present invention, the device wafer 60 can be adhered to the thin device wafer 60a with high adhesive force, and the device wafer 60 can be adhered to the thin device wafer 60a without damaging the thin device wafer 60a The adhesive can be easily released.

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

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

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

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

Example

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to the following examples unless it is beyond the ordinary knowledge. Unless otherwise specified, "part" and "%" are based on mass.

&Lt; Production method of adhesive laminate from thermoplastic resin film &gt; (Examples 1, 3, 8 to 12, Comparative Examples 1 to 4)

The following coating liquid for forming a release layer was applied on the thermoplastic resin film described below and dried in an oven at 120 DEG C for 1 minute to prepare a laminate for adhesion as a release layer having a release layer on one side of the thermoplastic resin film did.

[Application liquid for forming release layer]

The release agent described in Table 1: The mass part

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

&Lt; Production method of adhesive laminate from thermoplastic resin solution &gt; (Examples 2 and 4 to 7)

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

Subsequently, the following coating solution for forming a release layer was applied on a thermoplastic resin film, and oven-dried at 120 DEG C for 1 minute to prepare a laminate for adhesion, which had a release layer on one side of the thermoplastic resin film did.

[Composition for film production]

The thermoplastic resins shown in Table 1: The mass parts 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: The mass parts shown in Table 1

[Application liquid for forming release layer]

The release agent described in Table 1: The mass part

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

[Table 1]

The compounds listed in Table 1 are as follows.

&Lt; Thermoplastic resin &

(thermoplastic polyimide resin, 1% weight reduction temperature = 520 占 폚, melting point = 388 占 폚, Tg = 320 占 폚, manufactured by Kurashiki Boshiki Co.,

(a-2) Ultrason E6020P (polyether sulfone, 1% weight reduction temperature = 510 占 폚, melting point = 225 占 폚, Tg = 225 占 폚,

(polyetheretherketone, 1% weight reduction temperature = 480 占 폚, melting point = 343 占 폚, Tg = 320 占 폚, manufactured by Kurashiki Boshiki Co.,

(a-4) Septon S2104 (polystyrene type elastomer, 1% weight reduction temperature = 370 占 폚, melting point = 170 占 폚, Tg = 120 占 폚,

(a-5) NORYL APS130 resin (modified polyphenylene ether, 1% weight reduction temperature = 360 DEG C, melting point = 132 DEG C, Tg = 120 DEG C, SABIC Innovative Plastics Japan)

(a-6) Septon S2002 (polystyrene type elastomer, 1% weight reduction temperature = 310 占 폚, melting point = 150 占 폚, Tg = 100 占 폚,

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

<Release Agent>

(b-1) Optol DSX (a compound having a silicon atom and a fluorine atom (fluorine-based silane coupling agent), Daikin Kogyo Co., Ltd.)

(b-2) KS-700 (compound having siloxane bond (silicone resin), baking temperature = 250 캜, manufactured by Shin-Etsu Chemical Co.,

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

(b-4) KS-7201 (compound having siloxane bond (silicone resin), baking temperature = 200 캜, manufactured by Shin-Etsu Chemical Co.,

(b-5) KS-7200 (compound having siloxane bond (silicone resin), firing temperature = 230 캜, manufactured by Shin-Etsu Chemical Co.,

(b-6) Optu HD-1100 (a compound having a fluorine atom and no silicon element, manufactured by Daikin Industries, Ltd.)

(a compound having a silicon atom and no fluorine atom, manufactured by Tokyo Kasei Kogyo Co., Ltd.) (b-7) trimethoxy (3- (phenylamino)

(b-8) SEPA-COAT (compound having siloxane bond (silicone resin), baking temperature = 150 캜, manufactured by Shin-Etsu Chemical Co.,

(a compound having a silicon atom and a fluorine atom, fluorine content = 22%, manufactured by Shanghai Fuluda Rubber &amp; plastic Materials Technology Co., Ltd.) (b-9) Trifluoropropyltriethoxysilane

The 1% weight reduction temperature of the thermoplastic resin is a value measured by raising the temperature from 25 占 폚 to 20 占 폚 / min under a nitrogen stream by a thermogravimetric analyzer (TGA).

&Lt; Fabrication of Adhesive Support &gt;

The laminate for adhesive bonding produced by the above method was set in a vacuum laminator. Then, in this apparatus, the adhesive layer was placed on a 100 mm Si wafer, and the Si wafer and the face (the thermoplastic resin film side) opposite to the release layer of the adhesive layer laminate were brought into contact with each other under a vacuum, The adhesive laminate and the Si wafer were fixed to produce an adhesive support.

&Lt; Preparation of test piece &

The side of the adhesive support on which the adhesive laminate was formed and the device surface of the device wafer were pressed under vacuum at a pressure of Tg + 50 deg. C and 0.11 MPa for 3 minutes to prepare a test piece. As the device wafer, a bump made of copper having a diameter of 80 mu m and a height of 40 mu m was formed at a pitch of 200 mu m on a 100 mm Si wafer.

&Lt; Comparative Example 3 &

0.5 part by mass of Optol DSX (manufactured by Daikin Industries, Ltd.) and 99.5 parts by mass of Fluorinert FC-40 (manufactured by Sumitomo 3M Co., Ltd.) were applied to the device surface of the device wafer, And dried to form a release layer having a thickness of 10 nm.

Next, the thermoplastic resin film and the device surface of the device wafer were pressed under vacuum at 370 DEG C and 0.11 MPa for 3 minutes using a midfil (manufactured by Kurashiki Boshiki Co., Ltd.) as a thermoplastic resin film , And a test piece was produced.

&Lt; Comparative Example 4 &

0.5 part by mass of Optol DSX (manufactured by Daikin Industries, Ltd.) and 99.5 parts by mass of Fluorinert FC-40 (manufactured by Sumitomo 3M Co., Ltd.) were applied on a 100 mm Si wafer, Followed by drying to form a releasing layer of 10 nm. Thus, a support was produced.

Next, the thermoplastic resin film and the side of the support on which the release layer was formed were pressed under vacuum at 370 占 폚 under a pressure of 0.11 MPa using a midfil (manufactured by Kurashiki Boshiki Co., Ltd.) as the thermoplastic resin film Followed by compression for 3 minutes to prepare an adhesive support.

Next, the device surface of the adhesive support and the device wafer was pressed under vacuum at 370 DEG C and 0.11 MPa for 3 minutes to produce a test piece.

<Water contact angle of the release layer>

The water contact angle of the release layer was such that the composition for forming a release layer in which a release layer of various test pieces was formed on a 100 mm thick Si wafer was formed under the same conditions as the film formation conditions in which the release layers of various test pieces were formed, To form a release layer having the same film thickness as that of the test piece.

Next, the test piece was heated at 250 占 폚 for 2 hours, cooled to 25 占 폚, and the contact angle of water was measured using a contact angle meter (product number: CA-D) manufactured by Kyowa Gaimengagaku Co., Ltd. . The measurement was carried out by dropping 70 pL of water on the surface of the release layer of each test piece at a room temperature of 25 캜 and a humidity of 50%, and the contact angle at five points was measured.

<Peelability>

<< Evaluation of peel strength >>

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

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

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

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

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

D: Peeling force at the maximum was 20 N or more, or the Si wafer was damaged, and peeling could not be performed.

<< Evaluation of device surface >>

The appearance of the device surface of the device wafer after peeling of the Si wafer was visually observed and evaluated according to the following criteria.

A: Residual of thermoplastic resin film is not confirmed

B: Residues of some of the release layer are identified

C: Remains of release layer and thermoplastic resin film are confirmed

<Heat resistance>

The test piece was heated in a vacuum of 300 캜 or 400 캜 and observed with an ultrasonic microscope (Hitachi Power Solutions, type: FineSAT), and evaluated according to the following criteria.

A: No voids are found in the adhesive laminate

B: Several voids having a diameter of less than 3 mm are confirmed in the adhesive laminate

C: voids having a diameter of 3 mm or more were identified in the laminate for adhesion, or voids were confirmed on the entire surface

[Table 2]

From the above results, in Examples 1 to 14, the peelability was good.

On the other hand, in Comparative Examples 1 to 4, peeling residue of the thermoplastic resin was present on the device surface, and the peelability was poor.

11: Adhesive laminate
11a:
12: Support
60: device wafer
60a: thin device wafer
61: silicon substrate
61a, 61a1: Device face
61b, 61b1:
62: Device chip
63: structure
100: Adhesive support
100a: Adhesive support
110:
111: thermoplastic resin film

Claims (11)

A laminate for adhesive bonding, which is used for releasably adhering a device surface of a device wafer and a support,
In the adhesive layer,
A thermoplastic resin film,
(B-1) a silicone resin having a silicon atom and a fluorine atom and being capable of being bonded to the thermoplastic resin film by heating at 150 DEG C or higher and being a silicone resin in an amount of 50 to 100 mass% relative to the total solid content of the release layer, And a release layer comprising a releasing agent selected from a silane coupling agent in an amount of 5 to 100 mass% with respect to the total solid content of the release layer,
In the group represented by the following formula (B-1), three hydrolysable groups are bonded to the silicon atom,
Wherein the device-side surface of the thermoplastic resin film has at least the release layer in an area corresponding to the device surface,
Wherein the adhesive layer laminate has a laminate including at least the support and the thermoplastic resin film peeled off from the device when peeling the support from the device surface of the device wafer after the device wafer adheres to the support, Wherein the adhesive layer is a laminate.

^Wherein R ^h1 to R ^h3 are each independently selected from the group consisting of an alkoxy group, a mercapto group, a halogen atom, an amide group, an acetoxy group, an amino group, and an isopropenoxy group Hydrolyzable group.] The method according to claim 1,
Wherein the thermoplastic resin film comprises a thermoplastic resin having a glass transition point of 50 to 400 占 폚. The method according to claim 1 or 2,
Wherein the thermoplastic resin film is at least one of thermoplastic polyimide, polystyrene elastomer, polyester elastomer, polyamide elastomer, polyetheretherketone, polyphenylene ether, modified polyphenylene ether, polyether sulfone, poly And at least one thermoplastic resin selected from an acetal resin and a cycloolefin polymer. The method according to claim 1 or 2,
Wherein the 1% weight reduction temperature of the thermoplastic resin film heated at 25 占 폚 to 20 占 폚 / min is 250 占 폚 or higher. The method according to claim 1 or 2,
Wherein the release layer has a thickness of 0.001 to 1000 nm. The method according to claim 1 or 2,
Wherein the release layer has a water contact angle of 30 DEG or more as measured at a temperature of 250 DEG C for 2 hours and then cooled to 25 DEG C. delete The method according to claim 1 or 2,
Wherein the releasing agent is a silane coupling agent having a silicon atom and a fluorine atom and containing a group represented by the formula (B-1) and being in an amount of 5 to 100 mass% with respect to the total solid content of the releasing layer and having a fluorine atom content of 20 To 80% by weight of the adhesive layer. delete The method according to claim 1 or 2,
Which is capable of being bonded to the thermoplastic resin film by heating at 150 DEG C or more to the surface of the thermoplastic resin film and which has a silicon atom and a fluorine atom in an amount of 50 to 100% by mass based on the total solid content of the release layer, Comprising the step of forming a release layer comprising a release agent selected from a silane coupling agent containing a group represented by the formula (B-1) and being present in an amount of 5 to 100 mass% with respect to the total solid content of the release layer, Wherein the adhesive layer is an adhesive layer. A method of manufacturing a semiconductor device, comprising the steps of: providing a laminate for adhering according to claim 1 or claim 2 between a device wafer and a support, wherein a surface of a release layer side of the adherent laminate is in contact with a device surface of the device wafer, Wherein the device wafer adheres to the surface of the device wafer.

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