KR20180059901A - METHOD FOR PRODUCING LAMINATE, METHOD FOR PRODUCING SEMICONDUCTOR DEVICE, AND LAMINATE - Google Patents

Abstract

A method for producing a laminated body, a method of manufacturing a semiconductor device, and a laminated body, which can be mechanically peeled off from a carrier substrate at room temperature, wherein the voids are reduced and the peeling force stability is excellent. A method of manufacturing a laminated body having a first member having a carrier substrate and a second member having a processed substrate, the method comprising the steps of: providing an adhesive layer on at least one surface of the first member and the second member, Pressing the two members under the air pressure P1 and further heating at a temperature T2 exceeding 40 deg. C under the air pressure P2, and then processing the processed substrate to form a laminate; and the adhesive layer has a storage elastic modulus G'1 of not more than 1,000,000 Pa, a storage elastic modulus G'2 at a temperature T2 of not more than 1,000,000 Pa, Log (P2 / P1)? 2.1, and a machine-peelable laminate.

Description

METHOD FOR PRODUCING LAMINATE, METHOD FOR PRODUCING SEMICONDUCTOR DEVICE, AND LAMINATE

The present invention relates to a method of manufacturing a laminate, a method of manufacturing a semiconductor device, and a laminate.

BACKGROUND ART [0002] In a manufacturing process of a semiconductor device such as an IC (integrated circuit) or an LSI (large-scale integrated circuit), a plurality of IC chips are formed on a device wafer and are separated by dicing.

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

Conventionally, a wire bonding method 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. However, 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 penetrate through the through hole. However, the method of forming the silicon through electrode alone can not sufficiently meet 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, in order to increase the thickness of the IC chip, it is necessary to reduce the thickness of the member constituting the IC chip. As for thinning of such a member, for example, the thinning of the device wafer is studied, leading to miniaturization of the IC chip, and the manufacturing process of the through-hole of the device wafer in the production of the silicon through- In terms of being able, it is becoming promising. In addition, in semiconductor devices such as power devices and image sensors, thinning has been attempted from the viewpoints of improvement of the degree of integration and freedom of device structure.

As device wafers, those having a thickness of about 700 to 900 mu m are widely known. However, in recent years, it has been attempted to reduce the thickness of device wafers to 200 mu m or less for the purpose of miniaturization of IC chips.

However, since a device wafer having a thickness of 200 占 퐉 or less is extremely thin and a semiconductor device manufacturing member using the same as a processed substrate is extremely thin, additional processing is performed on such a member, or when such a member is simply moved, It is difficult to stably support the member without damaging it.

In order to solve the above problems, there is known a technique of peeling a carrier substrate after adhering a processed substrate and a carrier substrate before thinning provided with a device on a surface thereof with an adhesive, grinding the back surface of the processed substrate to make it thinner .

Here, various methods have been studied to bond the carrier substrate and the processed substrate. For example, Patent Document 1 discloses a double-sided pressure-sensitive adhesive sheet for bonding two adherends to each other through a double-sided pressure-sensitive adhesive sheet, in which two adherends are bonded to a pressure-sensitive or heat-pressurized environment Sensitive adhesive sheet.

Patent Document 2 discloses a method of manufacturing a semiconductor device, which includes a pressing step of pressing a substrate and a support supporting the substrate through an adhesive layer and pressing the substrate with a pressing means, And a pressure adjusting step of placing the support under an environment of atmospheric pressure higher than the pressure of the environment in which the pressing process is performed.

Patent Document 1: JP-A-2002-332458 Patent Document 2: JP-A-2015-133465

As described above, when the processed substrate is processed, a step of forming a laminated body in which the processed substrate is adhered to the carrier substrate by using an adhesive is performed. However, since the processed substrate usually has a concave portion or a convex portion such as a circuit surface on its surface, voids may be generated when the carrier substrate, the adhesive layer and the processed substrate are squeezed in vacuum. Here, Patent Document 1 and Patent Document 2 disclose that voids are reduced by performing predetermined heating and pressurization. However, as a result of the inventors' study, it has been found that the voids can not necessarily be effectively reduced by the methods described in Patent Documents 1 and 2. In addition, when the carrier substrate can not be mechanically peeled from the laminate at room temperature Or peeled off at room temperature, it was found that the peel strength stability was inferior in some cases.

SUMMARY OF THE INVENTION The present invention has been made to solve these problems, and it is an object of the present invention to provide a method for producing a laminate, which is capable of mechanically peeling a carrier substrate at room temperature with voids reduced and excellent in peel strength stability, And to provide a laminate.

In view of the above-described problems, the inventors of the present invention have found that, by vacuum-bonding a carrier substrate and an adhesive agent and a processed substrate, heating at a temperature exceeding 40 캜 under atmospheric pressure can suppress generation of voids in the laminate, The present inventors have found that this excellent laminate can be obtained, and the present invention has been accomplished. Specifically, the above problem is solved by the following <1>, preferably by <2> to <17>.

&Lt; 1 > A manufacturing method of a laminate having a first member having a carrier substrate and a second member having a processed substrate,

Wherein at least one surface of the first member and the second member has an adhesive layer,

The first member and the second member are pressed together under the atmospheric pressure P1 so that the adhesive layer is inward and heated at a temperature T2 exceeding 40 占 폚 under the air pressure P2, Including sieving,

Wherein the adhesive layer has a storage elastic modulus G'1 at a measurement frequency of 10 Hz and a storage modulus G'2 at a measurement frequency of 10 Hz at a temperature T1 Lt; / RTI &gt;

When the atmospheric pressure P1 and the atmospheric pressure P2 satisfy Log (P2 / P1) &gt; = 2.1,

Wherein the carrier substrate and the processed substrate are peelable by a force of 10 to 80 N,

A method of producing a laminate;

Here, the force at the time of peeling was fixed on the horizontal plane with the processed substrate side of the laminate down, and the carrier substrate was moved vertically to the processed substrate at 25 DEG C at a speed of 50 mm / min It is the force when it is raised.

&Lt; 2 > The method for producing a laminate according to < 1 >, wherein the adhesive layer comprises a compound containing at least one of a fluorine atom and a silicon atom.

&Lt; 3 > The method for producing a laminate according to <1> or <2>, wherein the pressure P1 is less than 1013 Pa.

&Lt; 4 > The method for producing a laminated body according to any one of < 1 > to < 3 >, wherein the atmospheric pressure P2 is 10,000 Pa or more.

<5> The method for producing a laminated body according to any one of <1> to <4>, wherein the temperature T1 and the temperature T2 satisfy T1 <T2.

<6> The method for producing a laminated body according to any one of <1> to <4>, wherein the temperature T1 and the temperature T2 satisfy T1 + 20? T2.

<7> The method for producing a laminated body according to any one of <1> to <6>, wherein the first member and the second member each independently have an adhesive layer.

<8> The method for producing a laminated body according to any one of <1> to <7>, wherein heating is performed at the time of compression under the air pressure P1 and the heating temperature T1 is 110 ° C. or more.

<9> The method for producing a laminated body according to any one of <1> to <8>, wherein the temperature T2 is 130 ° C. or higher.

<10> The method according to any one of <1> to <9>, wherein the adhesive layer comprises at least one of a thermoplastic elastomer containing a styrene structure, a thermoplastic siloxane polymer, a cycloolefin polymer and an acrylic resin (2).

<11> The method for producing a laminated body according to any one of <1> to <10>, wherein the processing is a step of heating at a temperature of 160 ° C. to 300 ° C.

<12> The method for producing a laminate according to any one of <1> to <10>, wherein the processing is a step of thinning a surface of the processed substrate farther from the adhesive layer.

<13> A method for producing a laminate according to <12>, wherein the thickness of the processed substrate is made to be 100 μm or less by the thinning process.

&Lt; 14 > A method for manufacturing a laminated body according to any one of < 1 > to < 13 >, comprising a step of peeling at least a carrier substrate from the laminate at a temperature of 40 DEG C or lower. Gt;

<15> A laminate having a carrier substrate, an adhesive layer, and a processed substrate,

A void of not less than 1 mm in diameter and less than 150 pieces / m ² when observed under an ultrasonic microscope at a frequency of 140 MHz,

Wherein the carrier substrate and the processed substrate are peelable by a force of 10 to 80 N;

Here, the force at the time of peeling was fixed on the horizontal plane with the processed substrate side of the laminate down, and the carrier substrate was moved vertically to the processed substrate at 25 DEG C at a speed of 50 mm / min It is the force when it is raised.

<16> The laminate according to <15>, wherein the adhesive layer has a thickness of 10 to 150 μm.

<17> The laminate according to <15> or <16>, wherein the adhesive layer comprises at least one of a thermoplastic elastomer containing a styrene structure, a thermoplastic siloxane polymer, a cycloolefin polymer and an acrylic resin.

According to the present invention, it is possible to provide a method for producing a laminated body, a method for manufacturing a semiconductor device, and a laminated body, wherein the carrier substrate is mechanically peelable at room temperature and voids are reduced and the peel strength is excellent.

1 is a schematic view showing a first embodiment of a method for producing a laminate of the present invention.
Fig. 2 is a schematic view showing a third embodiment of the method for producing a laminate of the present invention. Fig.

Hereinafter, the contents of the present invention will be described in detail. In the present specification, "~" is used to mean that the numerical values described before and after the numerical value are included as the lower limit value and the upper limit value.

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 "active ray" or "radiation" in the present specification means, for example, visible ray, ultraviolet ray, far ultraviolet ray, electron ray, 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, exposure by X-rays and EUV light (Extreme Ultra-Violet) It also means drawing by particle lines.

As used herein, "(meth) acrylate" refers to acrylate and methacrylate, "(meth) acryl" refers to acrylic and methacryl, "(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) can be measured by using, for example, HLC-8220 (manufactured by TOSOH CORPORATION) as a column, TSKgel Super AWM- , 6.0 mm (inner diameter) × 15.0 cm) can be obtained by using a 10 mmol / L lithium bromide NMP (N-methylpyrrolidinone) solution as an eluent.

An oligomer is defined as a compound having a weight average molecular weight of 500 or more and less than 2000. The polymer is defined as a compound having a weight average molecular weight of 2000 or more.

The thickness and the like in the present invention mean the average thickness unless otherwise specified.

A method for producing a laminate according to the present invention is a method for producing a laminate having a first member having a carrier substrate and a second member having a processed substrate, characterized in that the surface of at least one of the first member and the second member , The first member and the second member are pressed together under the atmospheric pressure P1 so that the adhesive layer is inward and heated at a temperature T2 exceeding 40 占 폚 under the air pressure P2, And processing the processed substrate to form a laminate,

Wherein the adhesive layer has a storage elastic modulus G'1 at a measurement frequency of 10 Hz and a storage modulus G'2 at a measurement frequency of 10 Hz at a temperature T1 (P2 / P1) &gt; = 2.1, and the carrier substrate and the processed substrate can be peeled off with a force of 10 to 80 N. .

Here, the force (peeling force) at the time of peeling is fixed on a horizontal plane with the side of the processed substrate of the laminated body facing downward, and the carrier substrate is moved at a rate of 50 mm / It is the force when it is pulled up at the speed of the minute. The peel force is preferably 10 N or more and less than 50 N, and more preferably 10 N or less and 30 N or less.

With such a constitution, the generation of voids in the laminate can be effectively suppressed in the laminate which can be peeled off at 40 캜 or less, and the peel strength stability can be improved. That is, in the conventional method of producing a laminate, convex portions such as wirings, bumps, fillers, and pads, or concave portions such as scribe lines and conformer vias (hereinafter sometimes referred to as "convex portions" ) And the carrier substrate are pressed together through the adhesive layer, voids are likely to be generated in the obtained laminate. In the present invention, it has been found that voids confirmed after bonding can be reduced or eliminated by heating at a higher pressure than that at the time of bonding, after bonding. Although this mechanism is presumed, it is presumed that minute voids that are not filled even under a low atmospheric pressure such as a vacuum are heated under the above atmospheric pressure to generate a differential pressure inside and outside the voids, and voids are lost.

Further, in the present invention, it is possible to effectively improve the peel strength stability when the carrier substrate is peeled from the laminate by reducing the voids and by subjecting the heat pressing conditions at the time of producing the laminate as described above. It is also possible to peel off the machine at 40 ° C or lower.

Here, as described above, Patent Document 1 discloses that bubbles can be degassed by heating and pressurization. However, the storage elastic modulus of the adhesive layer used for bonding the processed substrate and the carrier substrate is not described. As a result of the present inventors' study, it has been found that the storage modulus at the time of pressing and at the time of heating after pressing greatly influences the peel strength stability. That is, in the present invention, the peel strength stability is greatly improved by setting the storage modulus at the time of pressing and heating after pressing to within the above range. By setting the storage elastic modulus, the peelability can also be improved.

On the other hand, Patent Document 2 also discloses that bubbles can be degassed by heating and pressurization. However, the adhesive used in Patent Document 2 can not be mechanically peeled off at a temperature of 40 占 폚 or lower. On the other hand, the present invention has succeeded in providing a method for producing a laminated body excellent in peel strength stability by bonding in the above-described configuration under a condition capable of mechanical peeling at 40 DEG C or lower.

The term "peeling off" refers to peeling of the carrier substrate from the laminate without chemical treatment by irradiation with light or heat, chemical treatment or the like. It is not always necessary to peel off the carrier substrate with a machine, It is intended to be included.

In the method of producing a laminate of the present invention, the adhesive layer is provided on at least one surface of a first member having a carrier substrate and a second member having a processed substrate, and the first member and the second member are bonded to the adhesive So that the layer is inward (bonding step).

As shown in Fig. 1, the first embodiment of the method for producing a laminate of the present invention comprises a carrier substrate 1 as a first member, a processed substrate 2 as a second member, And the adhesive layer 3 is pressed so that the adhesive layer is inward. The processed substrate 2 usually has a concavo-convex portion 4 such as a bump or a filler. The adhesive layer 3 may be a single layer or two or more layers, usually one layer. When the adhesive layer has two or more layers, the composition of each layer may be the same or different.

The second embodiment of the laminate of the present invention is characterized in that the carrier substrate 1 as the first member, the adhesive layer 3 provided on the surface of the carrier substrate and the processed substrate 2 as the second member So that the layer is inwardly pressed. The adhesive layer 3 may be a single layer or two or more layers, usually one layer. When the adhesive layer has two or more layers, the composition of each layer may be the same or different, and it is preferable to control the composition by the adhesive force of the substrate to be bonded.

As shown in Fig. 2, the third embodiment of the laminate according to the present invention comprises a carrier substrate 1 as a first member, an adhesive layer 3 provided on the surface of the carrier substrate, The substrate 2 and the adhesive layer 3 provided on the surface of the processed substrate are pressed so that the adhesive layer is inward. The adhesive layer (3) in the first member and the adhesive layer (3) in the second member may be the same composition or different from each other.

The method of the present invention is preferably the third embodiment. This is because in the case where the adhesive layer is provided on both surfaces of the carrier substrate and the processed substrate, the unevenness of the processed substrate can be flattened to some extent in advance, and as a result, to be.

Details of the composition of the adhesive layer, the manufacturing method and the like will be described later.

In the first to third embodiments, the first member and the second member may have other layers within a range not deviating from the spirit of the present invention. As another layer, a layer called a release layer, a release layer, and a separation layer is exemplified. As the release layer, reference may be made, for example, to paragraphs 0025 to 0055 of Japanese Laid-Open Patent Publication No. 2014-212292, the contents of which are incorporated herein by reference. As the separation layer, reference may be made to paragraphs 0069 to 0124 of the pamphlet of WO2013-065417, which contents are incorporated herein by reference.

In the present invention, the first member and the second member are pressed together under the atmospheric pressure P1 so that the adhesive layer is inward. The atmospheric pressure P1 is preferably less than 1013 Pa, more preferably 1000 Pa or less, more preferably 500 Pa or less, further preferably 300 Pa or less, more preferably 200 Pa or less, even more preferably 150 Pa or less, Especially 20 Pa or less, and more particularly 15 Pa or less. The lower limit value of the air pressure P1 may be 0 Pa, but the effect of the present invention can be sufficiently exhibited even when the pressure is 5 Pa or more.

The pressure at the time of pressing is preferably 0.01 to 1 MPa.

The temperature T1 at the time of compression is not particularly limited but is preferably 110 DEG C or higher, more preferably 130 DEG C or higher, more preferably 145 DEG C or higher, more preferably 155 DEG C or higher, And still more preferably 190 deg. C or higher. The upper limit value is preferably 240 占 폚 or lower, and more preferably 220 占 폚 or lower.

The heating at the time of pressing under the atmospheric pressure P1 may be multistage heating. For example, in the case of heating for a time of Y11 at a temperature (T11) of T11 and for a time of Y12 at a temperature of T12 (C) We will do as follows.

T1 = T11 x Y11 / (Y11 + Y12) + T12 x Y12 / (Y11 + Y12)

The same is applied to the heating after the third step. The same holds true for the temperatures T2 and T0 described later.

The storage elastic modulus G'1 at a measurement frequency of 10 Hz at a temperature T1 at the time of compression bonding is preferably 1,000,000 Pa or less, preferably 800,000 Pa or less, more preferably 600,000 Pa or less, and 400,000 Pa or less . The lower limit value is not specifically defined, but may be, for example, 100,000 Pa or more, and further 200,000 Pa or more. With such a range, it is possible to manufacture a laminate in which the adhesive is liquefied and does not flow out from the end face of the member and is easily deformed to smooth the adhesive layer.

The compression time at the atmospheric pressure P1 is not specifically defined, but may be, for example, 1 to 15 minutes.

The storage elastic modulus at a measurement frequency of 10 Hz in the present invention is measured by the method described in Examples to be described later. In the case where the measuring instrument used in the embodiment is a waste plate or the like, a device having another equivalent performance can be employed. Hereinafter, the measurement method is the same.

The method for producing a laminate of the present invention further includes a step of processing after heating at a temperature T2 exceeding 40 占 폚 under atmospheric pressure P2 (post-baking step). By heating the laminated body thus bonded (bonded), voids in the laminated body can be reduced.

The atmospheric pressure P2 is preferably 10,000 Pa or more, more preferably 15,000 Pa or more, and more preferably 100,000 Pa or more. The upper limit value of the atmospheric pressure 2 is not particularly limited, but may be 200,000 Pa or lower, for example, and is preferably 130,000 Pa or lower.

The temperature T2 at the time of pressing (heating) at the air pressure P2 is a temperature exceeding 40 占 폚, preferably 130 占 폚 or higher, more preferably 150 占 폚 or higher, more preferably 160 占 폚 or higher, More preferably at least 185 ° C, even more preferably at least 195 ° C, even more preferably at least 210 ° C. The upper limit value is not specifically defined, but may be 260 占 폚 or lower, and further 240 占 폚 or lower.

The storage elastic modulus G'2 at a measurement frequency of 10 Hz at a temperature T2 during compression (heating) at the atmospheric pressure P2 is preferably 1,000,000 Pa or less, preferably 800,000 Pa or less, and 600,000 Pa or less And more preferably 400,000 Pa or less. The lower limit value is not specifically defined, but may be, for example, 100,000 Pa or more, and further 200,000 Pa or more.

The pressing (heating) time at the atmospheric pressure P2 is not particularly defined, but may be, for example, 1 to 15 minutes.

In the present invention, the atmospheric pressure P1 and the atmospheric pressure P2 satisfy Log (P2 / P1)? 2.1. By providing the air pressure difference as described above, voids formed by the bonding process and the like can be effectively reduced. Log (P2 / P1) is preferably in the order of 2.2 or more, 2.3 or more, 2.5 or more, 2.8 or more, 2.9 or more, 3.1 or more, 3.4 or more, 3.6 or more, or 3.8 or more. The upper limit value of Log (P2 / P1) is not specifically defined, but may be 10 or less, for example, 6 or less, particularly 5 or less.

In the present invention, the temperature T1 and the temperature T2 preferably satisfy T1 < T2, more preferably satisfy T1 + 10? T2, more preferably satisfy T1 + 15? T2, T2 &lt; / RTI &gt; is satisfied, and it is more preferable that T1 + 20? T2 is satisfied. The upper limit of the temperature difference between the temperature T1 and the temperature T2 is not specifically defined, but may be set at, for example, 80 DEG C or less, and further, 40 DEG C or less.

As a preferable first embodiment of the method for producing a laminate of the present invention, Log (P2 / P1) &gt; = 2.3 and T1 + 15? T2, and the temperature T1 at the time of compression is 180 ° C or higher, preferably 190 ° C or higher Embodiments are exemplified.

As a second preferred embodiment of the method of producing the laminate of the present invention, Log (P2 / P1)? 2.5 and T1 + 15? T2, and the temperature T1 at the time of compression is 150 ° C or higher, preferably 170 ° C or higher Embodiments are exemplified.

As a third preferred embodiment of the method for producing a laminate of the present invention, Log (P2 / P1) ≥3.5, T1 + 10? T2, preferably T1 + 15? T2, Lt; 0 &gt; C or more, preferably 150 [deg.] C or more.

As a particularly preferable embodiment of the method for producing a laminated body of the present invention, it is preferable that the adhesive layer is a thermoplastic elastomer including a styrene structure, Log (P2 / P1)? 3.5, T1 + 15? T2, T1 is at least 170 DEG C as an example.

In the method of manufacturing a laminate of the present invention, the processed substrate is processed after the pressing. The term &quot; processing &quot; means performing a certain operation on a processed substrate, and includes processing such as heating as well as mechanical processing and chemical processing.

As a first embodiment of the above-mentioned processing, there is exemplified an embodiment in which the above processing is performed at a temperature of 160 캜 or more and 300 캜 or less.

In the second embodiment of the processing, the processing is such that the surface of the processed substrate farther from the adhesive layer is thinned.

The thinning may be performed mechanically, for example, by polishing or the like, or may be made thin by chemical treatment. The mechanical or chemical treatment is not particularly limited. For example, the mechanical treatment or the chemical treatment includes a thinning treatment such as gliding or chemical mechanical polishing (CMP), a treatment under high temperature and vacuum such as chemical vapor deposition (CVD) A treatment using a chemical such as a solvent, an acidic treatment solution or a basic treatment solution, a plating treatment, an irradiation with an actinic ray, and a heating and cooling treatment.

The thickness of the processed substrate after thinning by mechanical or chemical treatment is preferably, for example, less than 500 탆, more preferably 400 탆 or less, more preferably 300 탆 or less, more preferably 100 탆 or less, Is more preferable. The lower limit is preferably 1 m or more, for example, and more preferably 5 m or more. Here, the thickness of the processed substrate refers to the thickness of the substrate surface excluding the thickness of the concave-convex portion.

In the mechanical or chemical treatment, the maximum attainable temperature in the heat treatment is preferably 130 ° C to 400 ° C, more preferably 180 ° C to 350 ° C. It is preferable that the maximum attained temperature in the heat treatment is lower than the decomposition temperature of the adhesive layer. The heat treatment is preferably heating for 30 seconds to 30 minutes at the maximum attained temperature, and more preferably for 1 minute to 10 minutes at the maximum attained temperature.

After the thinning process, a process may be performed in which a through hole penetrating the silicon substrate is formed from the back surface of the thinned substrate to form a silicon through electrode in the through hole.

Further, in the present invention, it is preferable to manufacture the semiconductor device from the laminate produced by the above method by peeling the carrier substrate. That is, in the present invention, a method for manufacturing a semiconductor device is provided, which further comprises a step of peeling at least the carrier substrate from the laminate at a temperature of 40 ° C or lower. The peeling at this time is preferably a mechanical peeling. Upon peeling, only the carrier substrate may be peeled off from the laminate, or one or more adhesive layers may be peeled off together with the carrier substrate. The peeling position can be adjusted by controlling the compounding amount of one or more layers of the highly releasable component to be mixed in the adhesive layer. For example, when peeling is desired between the carrier substrate and the adhesive layer adjacent to the carrier substrate, a large amount of a highly releasable component may be added to the adhesive layer in contact with the carrier substrate. Particularly, when the component having a high releasability has a ubiquitous property, it is preferable to adjust the peeling position by blending a small amount of highly releasable components. The peeling at which position of the laminate can be appropriately determined depending on the use or the like. As the component having a high releasability and having a ubiquitous property, a compound containing at least one of a fluorine atom and a silicon atom to be described later is exemplified.

The peeling is preferably carried out by, for example, pulling up the end portion of the carrier substrate in a direction perpendicular to the processed substrate without performing any treatment. More specifically, it is preferable to fix the carrier substrate on the horizontal plane with the processed substrate side of the stacked body down and to pull the carrier substrate in the vertical direction with a force of 10 to 80 N, More preferably 10 N or more and 30 N or less. At this time, it is also preferable to insert a notch into the gap between the carrier substrate and the adhesive layer with a knife or the like, and peel off. The separation speed is preferably 30 to 70 mm / minute, more preferably 40 to 60 mm / minute.

The temperature at the time of peeling is preferably 40 占 폚 or less, more preferably 10 to 40 占 폚, and still more preferably 20 to 30 占 폚.

In addition to the above, the peeling liquid may be used to dissolve the adhesive layer, and the carrier substrate and the processed substrate may be separated. As the release liquid in this case, a release liquid used for removing the adhesive layer described later can be used.

When one or more adhesive layers remain in the layered product in which the carrier substrate is peeled together with the processed substrate, the adhesive layer is usually removed.

Is not particularly limited as a means for removing the adhesive layer, but the following method is preferable.

As a first embodiment of the adhesive layer removing means in the production method of the laminate of the present invention, in the laminate obtained by removing the carrier substrate, the adhesive layer is mechanically removed at a temperature of 40 DEG C or lower have. The temperature at which the adhesive layer is removed is preferably 40 占 폚 or less, more preferably 10 to 40 占 폚, and still more preferably 20 to 30 占 폚.

It is preferable that the removal is carried out by pulling up the adhesive layer so as to form an angle of 60 ° to 180 ° with respect to the substrate surface of the thinned substrate. By peeling at such an angle, it is possible to excellently peel off with a small force. In addition, it becomes easy to peel off the adhesive layer with the layer-like state. Examples of means for peeling include peeling by hand, peeling by means of a device, and the like. The peeling force varies depending on the bonding conditions and the like, but may be 10 to 135N, for example. It is preferable that the lower limit of the angle formed with respect to the substrate surface of the thinned processed substrate at the time of peeling is 90 DEG or more. The upper limit value of the angle is preferably 150 DEG or less.

As a second embodiment of the adhesive layer removing means in the production method of the laminate of the present invention, a method of removing the adhesive layer by contacting a solvent (release liquid) with the adhesive layer is exemplified.

Examples of the exfoliating solution include aliphatic hydrocarbons (such as hexane, heptane, isophora E, H and G (manufactured by Esso Chemical Co., Ltd.)), aromatic hydrocarbon (toluene, xylene and the like), halogenated hydrocarbons (Methylene dichloride, ethylene dichloride, trichlorethylene, monochlorobenzene, etc.) and polar solvents. Examples of the polar solvent include alcohols (such as methanol, ethanol, propanol, isopropanol, 1-butanol, 1-pentanol, 1-hexanol, 1-heptanol, But are not limited to, 1-hexanol, 1-nonanol, 1-decanol, benzyl alcohol, ethylene glycol monomethyl ether, 2-ethoxy ethanol, diethylene glycol monoethyl ether, diethylene glycol monohexyl Ether, triethylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether, polyethylene glycol monomethyl ether, polypropylene glycol, tetraethylene glycol Ethylene glycol monobutyl ether, ethylene glycol monophenyl ether, propylene glycol monophenyl ether, methylphenyl carbinol, n-amyl alcohol, methyl amyl alcohol Etc.), ketones (acetone, methyl ethyl ketone, ethyl butyl ketone, methyl isobutyl ketone, cyclohexanone, etc.) And the like, such as esters (ethyl acetate, propyl acetate, butyl acetate, amyl acetate, benzyl acetate, methyl lactate, butyl lactate, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, diethylene glycol acetate , Triethylphosphate, tricityl phosphate, N-phenylethanolamine, N-phenyldiethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine , 4- (2-hydroxyethyl) morpholine, N, N-dimethylacetamide, N-methylpyrrolidone and the like.

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

From the viewpoint of releasability, a mode of mixing two or more kinds of organic solvents and water, two or more kinds of alkali, acid and surfactant is also preferable. If necessary, additives such as a defoaming agent and a water softening agent may also be contained.

As the alkali, acid and surfactant, reference can be made to the disclosure of Japanese Laid-Open Patent Publication No. 2014-189696, paragraphs 0170 to 0176, which is incorporated herein by reference.

When the residue of the adhesive layer is adhered to the carrier substrate, the carrier substrate can be regenerated by removing the residue. Examples of the method for removing the residue include a method of physically removing the residue by spraying a brush, an ultrasonic wave, an ice particle, and an aerosol, a method of dissolving and removing the dissolution in the dissolution liquid, a method of decomposing and vaporizing by irradiation with actinic rays, And the like. Depending on the carrier substrate, conventionally known cleaning methods can be used.

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

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

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

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

&Lt; Adhesive layer >

The adhesive layer used in the present invention is usually formed using an adhesive composition.

The adhesive composition used in the present invention preferably contains a resin, and more preferably includes a resin and a solvent. The adhesive composition used in the present invention preferably contains a compound containing at least one of a fluorine atom and a silicon atom.

<< Resin >>

The resin used in the present invention is preferably a resin which achieves the storage elastic modulus of the above-mentioned pressure-sensitive adhesive layer, and is usually an elastomer. By using an elastomer, it is possible to form an adhesive layer having excellent adhesiveness by an appropriate anchor effect following the fine unevenness of the carrier substrate and the processed substrate. Further, when peeling the carrier substrate from the processed substrate, the carrier substrate can be peeled off from the processed substrate without stress on the processed substrate, and breakage or peeling of devices on the processed substrate can be prevented.

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

Examples of the resin included in the adhesive layer include thermoplastic elastomers including styrene structure, olefin elastomer, vinyl chloride elastomer, urethane elastomer, amide elastomer, thermoplastic siloxane polymer, cycloolefin polymer, Block copolymers are exemplified and it is preferable to include at least one of a thermoplastic elastomer containing a styrene structure, a thermoplastic siloxane polymer, a cycloolefin-based polymer and an acrylic resin, and it is preferable to use a thermoplastic elastomer containing a styrene structure, More preferably a thermoplastic elastomer containing a styrene structure, and still more preferably a thermoplastic elastomer containing at least one of a styrene polymer and a cycloolefin polymer.

<<< Thermoplastic Elastomer Containing Styrene Structure >>>

The adhesive composition preferably contains a thermoplastic elastomer containing a styrene structure. The thermoplastic elastomer containing a styrene structure is an elastomer containing repeating units derived from styrene in the total repeating units.

The thermoplastic elastomer containing a styrene structure 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 (SEEPS), and the like.

The weight average molecular weight of the thermoplastic elastomer including the styrene structure is preferably 2,000 to 200,000, more preferably 10,000 to 200,000, and still more preferably 50,000 to 100,000. Within this range, the solubility of the thermoplastic elastomer containing the styrene structure to the solvent is improved, and the coating property is improved. Further, even when the processed substrate is peeled off from the carrier substrate and the remaining tacky adhesive layer is removed, there is an advantage that the residue is not left on the processed substrate or the carrier substrate because the solvent is excellent in solubility.

In the present invention, examples of the thermoplastic elastomer containing a styrene structure include a block copolymer, a random copolymer and a graft copolymer, and a block copolymer is preferable, and a styrene block copolymer And it is particularly preferable that both ends are block copolymers of styrene. When the both ends of a thermoplastic elastomer containing a styrene structure is a block copolymer of styrene (a repeating unit 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 phase separation contributes to suppression of the generation of irregularities on the surface of the processed substrate 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 the present invention, the thermoplastic elastomer containing a styrene structure is preferably a hydrogenated product. If the thermoplastic elastomer containing the styrene structure is a hydrogenated material, the thermal stability and the storage stability are improved. Further, the peelability and the removability of the adhesive layer after peeling can be improved. Further, the hydrogenated substance means a polymer in which the elastomer is hydrogenated.

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

The thermoplastic elastomer containing a styrene structure can be deformed to 200% at a room temperature (25 DEG C) at a room temperature (25 DEG C) at an original size of 100%. When the external force is removed, the thermoplastic elastomer It is preferable to have the property of returning to

The amount of the unsaturated double bond of the thermoplastic elastomer containing a styrene structure is preferably less than 15 mmol / g, more preferably 7 mmol / g or less, still more preferably less than 5 mmol / g, more preferably 0.5 mmol / mmol / g. The lower limit value is not specifically defined, but may be 0.001 mmol / g or more, for example.

The amount of the unsaturated double bond referred to herein does not include the amount of the unsaturated double bond in the benzene ring derived from styrene. The amount of unsaturated double bond can be calculated by nuclear magnetic resonance (NMR) measurement.

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

Examples of commercially available thermoplastic elastomers containing a styrene structure include toughprene A, toughprene 125, toughprene 126S, solfrene T, asaprene T-411, asaprene T-432, asaprene T- Toughtech H1052, Tuftec H1052, Tuftec H1062, Tuftec M1943, Tuftec M1911, Tuftec H1041, Tuftec MP10, Tuftec M1913, Tuftec H1051 Elastomer AR-860C, elastomer AR-840C, elastomer AR-830C, elastomer AR-860C, elastomer AR-850C, elastomer AR- Elastomer AR-SC-0, elastomer AR-SC-5, elastomer AR-710, elastomer AR-SC-65, elastomer AR-SC-30, elastomer AR- Elastomer AR-SC-75, elastomer AR-SC-45, elastomer AR-720, elastomer AR-741, elastomer AR- Elastomer AR-FL-85N, elastomer AR-FL-60N, elastomer AR-750, elastomer AR-760, elastomer AR-760, elastomer AR- , Kraton D1113, Kraton D1114, Kraton D1117, Kraton D1119, Kraton D1124, Kraton D1126, Kraton &lt; (R) &gt; D1161, Craton D1162, Craton D1163, Craton D1163, Craton D1164, Craton D1165, Craton D1183, Craton D1193, Craton DX406, Craton D4141, Kraton D4271, Kraton D4433, Kraton D1170, Kraton D1171, Kraton D1173, Cariflex IR0307, Cariflex IR0310, Cariflex IR0401, Kraton D0242, Kraton D1101, Kraton D1102, Kraton D1116, Kraton D1118, Kraton D1133, Leighton D1152,

Kraton D1153, Kraton D1155, Kraton D1184, Kraton D1186, Kraton D1189, Kraton D1191, Kraton D1192, Kraton DX405, Kraton DX408, Kraton DX410, Kraton DX414, Kraton DX415, Kraton Kleiton G1650, Craton G1651, Craton G1652, Craton G1643, Craton G1643, Craton G1645, Craton G1633, Craton G1650, Craton G1651, Craton G1652, Craton G1641, Craton G1510, Craton A1536, Craton FG1901, Craton FG1924, Kraton G1654, Kraton G1657, Kraton G1660, Kraton G1726, Kraton G1701, Kraton G1702, Kraton G1730, Kraton G1750, Kraton G1765, Kraton G4609, Kraton G4610 ), TR2000, TR2001, TR2003, TR2250, TR2500, TR2601, TR2630, TR2787, TR2827, TR1086, TR1600, SIS5002, SIS5200, SIS5250, SIS5405, SIS5505, Dynalon 6100P, Dynalon 4600P, Dynalon 6200P, Dynalon 4630P, Dynalon 8601P, Dynalon (Trade name, manufactured by JSR Corporation), Denka STR series (trade name, Denki Kagaku Co., Ltd., trade name, manufactured by JSR Corporation), DENARON 8600P, DYNARON 8903P, DYNARON 6201B, DYNARON 1321P, DYNARON 1320P, DYNARON 2324P, (Manufactured by Sumitomo Chemical Co., Ltd.), Quaternary 3520, Quintex 3433N, Quintax 3421, Quintax 3620, Quintax 3450, Quintax 3460 (manufactured by Nippon Zeon), TPE- (Manufactured by Mitsubishi Kagaku Co., Ltd.), Septon 1001, Septon 1020, Septon 2002, Septon 2004, Septon 2005, Septon 2006, Septon 2007, Septon 2063, Septon 2104, Septon 4033, Septon 4044, Septon 4055, (Trade names, trade names, trade names, trade names, trade names, trade names, trade names, trade names, trade names, (Trade name, manufactured by Sumitomo Bakelite Co., Ltd.), rheostomer, Manufactured by Nihon Kohyo Co., Ltd.).

In the present invention, a thermoplastic elastomer containing a styrene structure, which comprises an elastomer X containing repeating units derived from styrene at a ratio of 50% by mass or more and 95% by mass or less in the total repeating units, An embodiment in which the elastomer Y is contained in the repeating units in a proportion of 10% by mass or more and less than 50% by mass is also preferable.

When the elastomer X and the elastomer Y are used in combination, the flatness of the polished surface of the substrate (hereinafter also referred to as flat polishability) is good and the occurrence of warpage of the polished substrate can be effectively suppressed while having excellent releasability. The mechanism by which such an effect can be obtained is presumed to be as follows.

That is, since the elastomer X is a comparatively hard material, by including the elastomer X, a tacky adhesive layer having excellent peelability can be produced. Further, since the elastomer Y is a relatively soft material, it is easy to form an adhesive layer having elasticity. Therefore, when the laminated body of the processed substrate and the carrier substrate is manufactured by using the above adhesive composition and the processed substrate is polished to be thinned, even if the pressure at the time of polishing is locally applied, It is easy to return to the shape of. As a result, excellent flat polishing performance can be obtained. Also, even if the laminated body after the polishing is subjected to heat treatment and then cooled, the internal stress generated at the time of cooling can be alleviated by the adhesive layer, and occurrence of warpage can be effectively suppressed.

Further, even when the elastomer Y is blended with the elastomer X, the region where the elastomer X is phase-separated exists, and the like, and the excellent releasability by the elastomer X is sufficiently achieved.

The elastomer X is an elastomer containing repeating units derived from styrene in a proportion of 50% by mass or more and 95% by mass or less in the total repeating units. The content of the repeating unit derived from styrene is more preferably 50 to 90% by mass , More preferably from 50 to 80 mass%, still more preferably from 55 to 75 mass%, still more preferably from 56 to 70 mass%.

The hardness of the elastomer X is preferably 83 or more, more preferably 85 or more, and even more preferably 90 or more. The upper limit value is not particularly limited, but is, for example, 99 or less. The hardness is a value measured by a Type A durometer according to the method of JIS (Japanese Industrial Standard) K6253.

The elastomer Y is an elastomer containing repeating units derived from styrene in a proportion of 10% by mass or more and less than 50% by mass in the total repeating units, and the content of the repeating unit derived from styrene is preferably 10 to 45% by mass, More preferably 10 to 40% by mass, still more preferably 12 to 35% by mass, and particularly preferably 13 to 33% by mass.

The hardness of the elastomer Y is preferably 82 or less, more preferably 80 or less, and even more preferably 78 or less. The lower limit value is not particularly limited but is 1 or more.

The difference between the hardness of the elastomer X and the hardness of the elastomer Y is preferably 5 to 40, more preferably 10 to 35, more preferably 15 to 33, and most preferably 17 to 29. By setting this range, the effect of the present invention can be exerted more effectively.

In the present invention, elastomers other than the elastomer X and the elastomer Y may be blended. As the other elastomer, a polyester elastomer, a polyolefin elastomer, a polyurethane elastomer, a polyamide elastomer, a polyacrylic elastomer, a silicone elastomer, a polyimide elastomer, a rubber-modified epoxy resin and the like can be used.

In the above embodiment, the total amount of the elastomer X and the elastomer Y preferably accounts for 90 mass% or more, more preferably 95 mass% or more, of the total amount of the elastomer X, the elastomer Y and the other elastomer % Or more by mass.

The mass ratio of the elastomer X to the elastomer Y is preferably 5:95 to 95: 5, more preferably 20:80 to 90:10, and even more preferably 40:60 to 85:15, in terms of the mass ratio of the elastomer X to the elastomer Y. Particularly preferred. Within the above range, warpage suppression and peelability are more effectively achieved.

<<< Thermoplastic Siloxane Polymers >>>

In the adhesive composition of the present invention, a thermoplastic siloxane polymer can be used as the resin component.

Thermoplastic siloxane ^{polymers, R 21 R 22 R 23 SiO} 1/2 unit ^{(R 21, R 22, R} 23 is Im, respectively, unsubstituted or monovalent hydrocarbon group or hydroxyl group of carbon atoms of the substituted 1-10) and SiO _4/2 containing units, wherein _{^{R 21 R 22 R 23 SiO 1}} /2 units _/ SiO ₄ / a molar ratio of ₂ units of 0.6 ~ 1.7 in the organo polysiloxane-to-old and, organosilane represented by the general formula (1) The proportion of the organopolysiloxane to be subjected to the dehydration condensation and the organopolysiloxane is from 99: 1 to 50:50 and the weight average molecular weight is preferably from 200,000 to 1,500,000 .

[Chemical Formula 1]

(Wherein R ¹¹ and R ¹² each represent an unsubstituted or substituted monovalent hydrocarbon group of 1 to 10 carbon atoms, and n is 5000 to 10000)

Such a thermoplastic siloxane is preferable because it is excellent in adhesiveness and heat resistance.

In the general formula (1), the organic substituent groups R ¹¹ and R ¹² are each an unsubstituted or substituted monovalent hydrocarbon group of 1 to 10 carbon atoms, specifically, a methyl group, ethyl group, n-propyl group, An alkyl group such as an isopropyl group, an n-butyl group, a t-butyl group, an n-pentyl group, a cyclopentyl group and an n- hexyl group, a cycloalkyl group such as a cyclohexyl group, an aryl group such as a phenyl group, A hydrogen group, a group in which a part or all of the hydrogen atoms of these hydrocarbon groups are substituted with a halogen atom, preferably a methyl group and a phenyl group.

The weight average molecular weight of the thermoplastic organopolysiloxane is 200,000 or more, more preferably 350,000 or more, and 1,500,000 or less, and more preferably 1,000,000 or less. Further, the content of the low molecular weight component having a molecular weight of 740 or less is preferably 0.5% by mass or less, more preferably 0.1% by mass or less.

As a commercially available product, SILRES 604 (Asahi Kasei Barker Silicon) is exemplified.

<<< Cycloolefin Polymer >>>

Examples of the cycloolefin-based polymer include norbornene-based polymers, monocyclic cycloolefin polymers, cyclic conjugated diene polymers, vinyl alicyclic hydrocarbon polymers, and hydrides of these polymers. Preferred examples of the cycloolefin-based polymer include an addition (co) polymer containing at least one repeating unit represented by the following general formula (II) and at least one repeating unit represented by the general formula (I) (Co) polymers obtained by copolymerization. Another preferred example of the cycloolefin-based polymer is a ring-opened (co) polymer containing at least one cyclic repeating unit represented by the general formula (III).

(2)

In the general formulas (I) to (III), m represents an integer of 0 to 4. R ¹ to R ⁶ each represent a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms; X ¹ to X ³ and Y ¹ to Y ³ each represent a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, (CH ₂ ) _n COOR ¹¹ , - (CH ₂ ) _n OCOR ¹² , - (CH ₂ ) _n NCO, - (CH ₂ ) _n NO _{2 , - (CH 2) n CN} , - (CH 2) n CONR 13 R 14, - (CH 2) n NR 15 R 16, - (CH 2) n OZ, - (CH 2) n W, or X ¹ (-CO) ₂ O, (-CO) ₂ NR ¹⁷ which is composed of Y ¹ , X ² and Y ² or X ³ and Y ³ . Each of R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ and R ¹⁷ is a hydrogen atom or a hydrocarbon group (preferably a hydrocarbon group having 1 to 20 carbon atoms), Z is a hydrocarbon group W represents SiR ¹⁸ pD3-p (wherein R ¹⁸ represents a hydrocarbon group of 1 to 10 carbon atoms, D represents a halogen atom, -OCOR ¹⁸ or -OR ¹⁸⁾ , or a halogen atom substituted by halogen, And p represents an integer of 0 to 3). n represents an integer of 0 to 10;

The norbornene polymer is disclosed in, for example, Japanese Unexamined Patent Application Publication No. 10-7732, Japanese Unexamined Patent Publication No. 2002-504184, US2004 / 229157A1, and WO2004 / 070463A1. The norbornene polymer can be obtained by addition polymerization of norbornene polycyclic unsaturated compounds. If necessary, norbornene polycyclic unsaturated compounds and ethylene, propylene, butene; Conjugated dienes such as butadiene, isoprene; And non-conjugated dienes such as ethylidene norbornene may be addition polymerized. The norbornene polymer is commercially available from Mitsui Chemicals, Inc. under the trade name of APEL, and APL8008T (Tg 70 DEG C), APL6013T (Tg 125 DEG C) or APL6015T (Tg 145 DEG C) having different glass transition temperatures ° C) and the like. Pellets such as TOPAS8007, 5013, 6013 and 6015 are commercially available from Polyplastics.

Appear3000 is also available from Ferrania.

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

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

The weight average molecular weight of the cycloolefin-based polymer in terms of polystyrene according to gel permeation chromatography (GPC) is preferably 10,000 to 1,000,000, more preferably 50,000 to 500,000, and even more preferably 100,000 to 300,000.

As the cycloolefin-based polymer used in the present invention, the cycloolefin-based polymers described in paragraphs 0039 to 0052 of Japanese Patent Application Laid-Open No. 2013-241568 are also exemplified.

<<< Acrylic resin >>>

The acrylic resin in the present invention is preferably a resin obtained by polymerizing a (meth) acrylate monomer.

Examples of the (meth) acrylate monomer include 2-ethylhexyl (meth) acrylate, ethyl (meth) acrylate, methyl (meth) acrylate, n- (Meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, isononyl (Meth) acrylate, n-nonyl (meth) acrylate, isoamyl (meth) acrylate, n-decyl Benzyl (meth) acrylate, cyclohexyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate and 2-methylbutyl (meth) acrylate.

Further, other monomers may be copolymerized within the range not departing from the gist of the present invention. When other monomers are copolymerized, 10 mol% or less of the total monomers is preferable.

In the present invention, an acrylic resin having an organopolysiloxane as a side chain of the resin component is also preferable. Examples of the acrylic resin having an organopolysiloxane in the side chain include those represented by the following general formula (2).

In general formula (2)

(3)

In the formula (2), R ¹ may be the same or different when a plurality of R ^{1 s} exist, and represent CH ₃ , C ₂ H ₅ , CH ₃ (CH ₂ ) ₂ or CH ₃ (CH ₂ ) ₃ . When a plurality of R ^{2 s} exist, they may be the same or different and represent H, CH ₃ , C ₂ H ₅ , CH ₃ (CH ₂ ) ₂ or CH ₃ (CH ₂ ) ₃ . When a plurality of R ^{3 s} exist, they may be the same or different and represent H or CH ₃ . R ⁴ may be the same or different when a plurality of R ⁴ are present and may be H, CH ₃ , C ₂ H ₅ , CH ₃ (CH ₂ ) ₂ , CH ₃ (CH ₂ ) ₃ or an epoxy group, a hydroxyl group, Represents an alkyl group having 1 to 6 carbon atoms substituted with at least one functional group selected from the group consisting of an alkoxy group, a vinyl group, a silanol group and an isocyanate group.

a is from 50 to 150, b is from 50 to 150, and c is from 80 to 600. M is from 1 to 10;

Organo Specific examples of the acrylic resin having a polysiloxane side chain, Shin-Etsu Kagaku Kogyo (Co., Ltd.), a silicone graft acrylic resin, product name: X-24-798A, X-22-8004 (R 4: C 2 H 4 OH, functional group equivalent weight: 3250 (g / mol)) , X-22-8009 (R 4: Si (OCH 3) 3 containing an alkyl group, a functional group equivalent weight: 6200 (g / mol)) , X-22-8053 (R 4 : H, a functional group equivalent weight: 900 (g / mol)) , X-22-8084, X-22-8084EM, X-22-8195 (R 4: H, a functional group equivalent weight: 2700 (g / mol)) , doah Gosei GS-1000 series (GS-1015, GS-1302, and the like), GS-1000 series (US-270, US-350, US-352, US- And the like.

In addition to the above, acrylate MF 001 manufactured by Mitsubishi Rayon Co., Ltd. and the like are exemplified.

The adhesive composition used in the present invention is preferably a resin in an amount of 50 to 100% by mass of the solid content, more preferably 70 to 100% by mass of the resin.

The adhesive composition used in the present invention may contain only one kind of resin, or two or more kinds of resins. When two or more of them are contained, it is preferable that the total amount is in the above range.

<< Solvent >>

The adhesive composition used in the present invention preferably contains a solvent. In the case of forming the adhesive layer by applying the adhesive composition used in the present invention, it is preferable to add a solvent. As the solvent, any of known solvents can be used without limitation, and organic solvents are preferable.

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

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

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

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

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

Of these, methylethylene, tert-butylbenzene, 1,2,4-trimethylbenzene, p-menthane,? -Butyrolactone, anisole, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl But are not limited to, cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, ethylcarbitol acetate, butylcarbitol acetate, propylene glycol And propylene glycol methyl ether acetate are preferable, and tert-butylbenzene and mesitylene are more preferable.

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

The boiling point of the solvent contained in the adhesive composition at 1013.25 hPa is preferably from 110 to 250 캜, more preferably from 140 to 190 캜. By using such a solvent, it is possible to obtain an adhesive layer having better in-plane uniformity. When two or more kinds of solvents are used, the boiling point of the solvent having the highest boiling point is set to the boiling point.

When the adhesive composition has a solvent, the content of the solvent in the adhesive composition is preferably such that the total solid content of the adhesive composition is 5 to 80% by mass, more preferably 10 to 50% by mass , And particularly preferably from 15 to 40 mass%.

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

The content of the solvent in the adhesive layer is preferably 1% by mass or less, more preferably 0.1% by mass or less, and particularly preferably not contained.

&Lt; Compound containing at least one of fluorine atom and silicon atom &gt; >

The adhesive composition used in the present invention preferably contains a compound containing at least one of a fluorine atom and a silicon atom. Such a compound usually functions as a release agent and is fixed on a horizontal plane with the side of the processed substrate of the laminate facing downward. The carrier substrate is moved vertically to the processed substrate at 25 DEG C at a rate of 50 mm / min The laminate can be peeled off with a force of 10 to 80 N when pulled up. The compound containing at least one of the fluorine atom and the silicon atom is a compound in which the amount of the silicon atom or the fluorine atom is such that the amount of the silicon atom or the fluorine atom is unevenly distributed in the surface layer of the adhesive layer and in the interface between the substrate and the adhesive layer, It is possible to form at least the adhesive layer having excellent releasability to the processed substrate or the carrier substrate.

<<< Compounds Having Fluorine Atoms >>>

As a first embodiment of the compound having a fluorine atom, a liquid form compound is exemplified. The liquid-like compound means a compound having fluidity at 25 ° C, for example, a compound having a viscosity at 25 ° C of 1 to 100,000 mPa · s.

The viscosity of the fluorine atom-containing compound at 25 占 폚 is more preferably 10 to 20,000 mPa 占 퐏, and more preferably 100 to 15,000 mPa 占 퐏. When the viscosity of the fluorine atom-containing compound is within the above range, the compound having a fluorine atom is prone to localization on the surface of the adhesive layer.

In the present invention, the fluorine atom-containing compound can be preferably used in any form of monomer, oligomer or polymer. It may also be a mixture of an oligomer and a polymer. Also, a mixture of an oligomer and / or a polymer and a monomer may be used.

The fluorine atom-containing compound is preferably an oligomer, a polymer and a mixture thereof in terms of heat resistance and the like.

Examples of the oligomer and the polymer include a radical polymer, a cationic polymer, and an anionic polymer, all of which can be preferably used. Among them, a (meth) acrylic polymer is particularly preferable. By using a (meth) acryl-based polymer as the compound having a fluorine atom, the effect of the compound having a fluorine atom on the surface of the adhesive layer is liable to be uniformalized and excellent in peelability.

The weight average molecular weight of the fluorine atom-containing compound is preferably 500 to 100,000, more preferably 1,000 to 50,000, and still more preferably 2,000 to 20,000.

In the present invention, the fluorine atom-containing compound is preferably a compound which is not denatured during the treatment of the substrate to be provided for adhesion. For example, a compound which can be present in liquid form even after heating at 250 DEG C or higher or after processing the processed substrate with various chemical solutions is preferable. As a specific example, it is preferable that the viscosity at 25 ° C after heating from 250 ° C to 25 ° C at a temperature elevation condition of 10 ° C / min from 25 ° C and then at 25 ° C is 1 to 100,000 mPa · s, mPa · s is more preferable, and 100 to 15,000 mPa · s is more preferable.

The fluorine atom-containing compound having such characteristics is preferably a non-thermosetting compound having no reactive group. The term reactive group as used herein refers to the whole period of the reaction in the heating at 250 ° C, and includes a polymerizable group and a hydrolyzable group. Specific examples thereof include a (meth) acryl group, an epoxy group, and an isocyanate group.

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

As the non-thermosetting compound, a (meth) acrylic copolymer containing a perfluoroalkyl group which can be synthesized from a perfluoroalkyl group-containing (meth) acrylic acid ester is preferable.

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

More specifically, acrylic acid esters such as alkyl acrylate (the number of carbon atoms of the alkyl group is preferably 1 to 20) (e.g., methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, , Ethylhexyl acrylate, octyl acrylate, t-octyl acrylate, chloroethyl acrylate, 2,2-dimethylhydroxypropyl acrylate, 5-hydroxypentyl acrylate, trimethylolpropane monoacrylate, (For example, phenyl acrylate), alkyl (meth) acrylates such as methyl acrylate, ethyl acrylate, butyl acrylate, Methacrylic acid esters such as methacrylate (the number of carbon atoms of the alkyl group is preferably 1 to 20) (for example, methyl methacrylate Acrylate, isobutyl methacrylate, ethyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, amyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, chlorobenzyl methacrylate, , 4-hydroxybutyl methacrylate, 5-hydroxypentyl methacrylate, 2,2-dimethyl-3-hydroxypropyl methacrylate, trimethylolpropane monomethacrylate, pentaerythritol monomethacrylate (Methacrylic acid, methacrylic acid, methacrylic acid, methacrylic acid, methacrylic acid, methacrylic acid, methacrylic acid, And the like), styrenes such as styrene and alkylstyrene (e.g., methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, Butylene styrene, isoprene styrene, isoprene, styrene, butylene, diene, styrene, isobutylene, styrene, , Acetoxymethylstyrene, etc.), alkoxystyrene (e.g., methoxystyrene, 4-methoxy-3-methylstyrene, dimethoxystyrene and the like), halogensilane (e.g., But are not limited to, chlorostyrene, chlorostyrene, dichlorostyrene, dichlorostyrene, trichlorostyrene, tetrachlorostyrene, pentachlorostyrene, bromostyrene, dibromostyrene, iodostyrene, fluorostyrene, 2-bromo-4-trifluoromethylstyrene, 4-fluoro-3-trifluoromethylstyrene, etc.), acrylonitrile, methacrylonitrile acrylic acid, and carboxylic acid There may be mentioned water (acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, p- carboxyl styrene, and the metal salt, ammonium salt compounds of these acid groups, etc.). (Meth) acrylic acid esters having a hydrocarbon group of 1 to 24 carbon atoms are particularly preferred from the viewpoint of releasability, and examples thereof include methyl, butyl, 2-ethylhexyl, lauryl, stearyl, glycidyl And (meth) acrylates of higher alcohols such as 2-ethylhexyl, lauryl, stearyl and the like, especially acrylates, are preferred.

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

In the present invention, the compound having a fluorine atom is preferably a compound containing a mineral oil. Examples of the organic group include an alkyl group and an aromatic group.

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

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

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

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

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

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

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

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

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

The aromatic group may be monocyclic or polycyclic. The carbon number of the aromatic group is preferably from 6 to 20, more preferably from 6 to 14, and most preferably from 6 to 10. It is preferable that the aromatic group does not contain a hetero atom (for example, a nitrogen atom, an oxygen atom, a sulfur atom, etc.) in the element constituting the ring. Specific examples of the aromatic group include a benzene ring, a naphthalene ring, a pentane ring, an indane ring, an azole ring, a heptane ring, an indane ring, a perylene ring, a pentacene ring, an acenaphthene ring, a phenanthrene ring, an anthracene ring, a naphthacene ring, A thiophene ring, an imidazole ring, an oxazole ring, a thiazole ring, a pyridine ring, a pyrazine ring, a pyrimidine ring, a pyridazin ring, an indolizine ring, A benzofuran ring, an isobenzofuran ring, a quinoline ring, a quinoline ring, a phthalazine ring, a naphthyridine ring, a quinoxaline ring, a quinoxazoline ring, an isoquinoline ring, a carbazole ring, a phenanthrene ring, Pyran, acridine, phenanthroline, thianthrene, chroman, zenthene, phenoxathiine, phenothiazine, and phenanthrene.

The aromatic group may have the substituent described above.

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

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

The fluorine atom-containing compound preferably has 2 to 100, more preferably 6 to 80, groups having at least one hydrophilic group in one molecule.

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

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

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

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

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

As the compound having a fluorine atom, a commercially available product may be used. Examples of commercially available non-thermosetting compounds include Teflon (registered trademark) (DuPont), Teflon (DuPont), Fluon (Asahi Glass), Hyler (SolvaySolexis), Haier (SolvaySolexis) Fluorine resins such as Flon (Asahi Glass Co.), Aplas (Asahi Glass Co., Ltd.), Sephrase Soft (Central Glass Co., Ltd.), and Cefalcoat (Central Glass Co., Ltd.), Viton (DuPont), Caleth (Manufactured by Shin-Etsu Chemical Co., Ltd.), SIFEL (manufactured by Shin-Etsu Chemical Co., Ltd.), etc., chlorotox (DuPont Company), Pombuline (Daitoku Tech Co., Ltd.) , Surfron S243 and the like, manufactured by AGC SEIYAKU CHEMICAL Co., Ltd.), and various fluorine oils including perfluoropolyether oils such as DAFREE FB-962 (Daikin Kogyo Co., Ltd., Daikin Kogyo Co., DIC), and the like.

F-251, F-281, F-477, F-553, F-554 and F-555 of Megapark series manufactured by DIC Co. are commercially available as a compound having a fluorine atom having a hydrophilic group. F-556, F-557, F-558, F-559, F-560, F-561, F-563, F- 710F, 710FS, 710FL, 730FL, and 730LM of the Fotogen series manufactured by NEOS.

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

<<< Compound Containing Silicon Atoms >>>

In the present invention, the compound containing a silicon atom may be preferably used in any form of oligomer or polymer. It may also be a mixture of an oligomer and a polymer. Such a mixture may further contain a monomer. The compound containing a silicon atom may be a monomer.

From the viewpoint of heat resistance and the like, a compound containing a silicon atom is preferably an oligomer, a polymer and a mixture thereof.

As the oligomer and polymer, for example, an addition polymer, a polycondensation product, an addition condensation product and the like can be used without particular limitation, but polycondensation is particularly preferable.

The weight average molecular weight of the compound containing a silicon atom is preferably 500 to 100,000, more preferably 1,000 to 50,000, and still more preferably 2,000 to 20,000.

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

The liquid compound containing silicon atoms having such characteristics is preferably an uncured compound having no reactive group. The term "reactive group" as used herein refers to a group which reacts by heating or irradiation with radiation, and includes other polymerizable groups and hydrolyzable groups in addition to ethylenically unsaturated bonds. Specific examples thereof include a (meth) acryl group, an epoxy group, and an isocyanate group.

It is preferable that the 10% thermal mass reduction temperature of the compound containing a silicon atom which is raised from 25 占 폚 to 20 占 폚 / min is 250 占 폚 or higher, more preferably 280 占 폚 or higher. The upper limit value is not particularly limited, but is preferably 1000 占 폚 or lower, for example, and more preferably 800 占 폚 or lower. According to this embodiment, it is easy to form an adhesive layer having excellent heat resistance. The thermal mass reduction temperature is a value measured under the above-mentioned temperature increasing condition under a nitrogen stream by a thermogravimetric analyzer (TGA).

The compound containing a silicon atom used in the present invention preferably contains a mineral oil. Examples of the lipophilic group include a linear or branched alkyl group, a cycloalkyl group, and an aromatic group.

The number of carbon atoms in the alkyl group is preferably from 1 to 30, more preferably from 1 to 10, and still more preferably from 1 to 3. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a dodecyl group, a tetradecyl group, , Isobutyl group, sec-butyl group, tert-butyl group, 1-ethylpentyl group and 2-ethylhexyl group.

The alkyl group may have a substituent. Examples of the substituent include a halogen atom, an alkoxy group, and an aromatic group. Examples of the halogen atom include a chlorine atom, a fluorine atom, a bromine atom, and an iodine atom, and a fluorine atom is preferable.

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

The cycloalkyl group may be monocyclic or polycyclic. The number of carbon atoms of the cycloalkyl group is preferably from 3 to 30, more preferably from 4 to 30, still more preferably from 6 to 30, and particularly preferably from 6 to 20. Examples of the monocyclic cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group and a cyclooctyl group. Examples of the polycyclic cycloalkyl group include an adamantyl group, a norbornyl group, a vinyl group, a camphanyl group, a decahydronaphthyl group, a tricyclodecanyl group, a tetracyclodecanyl group, a camphoryl group, a dicyclohexyl group, .

The cycloalkyl group may have the substituent described above.

The aromatic group may be monocyclic or polycyclic. The carbon number of the aromatic group is preferably from 6 to 20, more preferably from 6 to 14, and particularly preferably from 6 to 10. It is preferable that the aromatic group does not contain a hetero atom (for example, a nitrogen atom, an oxygen atom, a sulfur atom, etc.) in the element constituting the ring. Specific examples of the aromatic group include a benzene ring, a naphthalene ring, a pentane ring, an indane ring, an azole ring, a heptane ring, an indane ring, a perylene ring, a pentacene ring, an acenaphthene ring, a phenanthrene ring, an anthracene ring, a naphthacene ring, A thiophene ring, an imidazole ring, an oxazole ring, a thiazole ring, a pyridine ring, a pyrazine ring, a pyrimidine ring, a pyridazin ring, an indolizine ring, A benzofuran ring, an isobenzofuran ring, a quinoline ring, a quinoline ring, a phthalazine ring, a naphthyridine ring, a quinoxaline ring, a quinoxazoline ring, an isoquinoline ring, a carbazole ring, a phenanthrene ring, A thiophene ring, a phenanthrene ring, a phenanthrene ring, a phenanthroline ring, a phenanthroline ring, a thianthrene ring, a chroman ring, a zenthene ring, a phenoxathiine ring, a phenothiazine ring and a phenanthrene ring.

The aromatic group may have the substituent described above. As the substituent, a straight-chain alkyl group is preferable.

The compound containing a silicon atom is preferably a compound represented by the following general formula (4).

In general formula (4)

[Chemical Formula 4]

R ¹ and R ² in the general formula (4) are each independently a linear or branched alkyl group, cycloalkyl group or aromatic group, and one of R ¹ and R ² may be an organic group containing a polyether chain.

L ¹ represents -O- or a linking group containing a polyether chain.

The preferable range of the linear or branched alkyl group, cycloalkyl group or aromatic group as R ¹ and R ² in the above general formula is the same as that of the alkyl group, cycloalkyl group or aromatic group of a straight chain or branched chain described in the section of the above-mentioned organic group, .

In the above general formulas, one of R ¹ and R ² is preferably an organic group containing a polyether chain. The polyether structure in the organic group including the polyether chain may be any structure having a plurality of ether bonds and is not particularly limited. Examples of the polyether structure include a polyethylene glycol structure (polyethylene oxide structure), polypropylene glycol (Polypropylene oxide structure), a polybutylene glycol structure (polytetramethylene glycol structure), a polyether structure derived from plural kinds of alkylene glycol (or alkylene oxide) (for example, Poly (propylene glycol / ethylene glycol) structure), and other polyoxyalkylene structures. The addition form of each alkylene glycol in the polyether structure derived from plural kinds of alkylene glycol may be a block type (block copolymerization type) or a random type (random copolymerization type) .

The organic group containing the polyether chain may be an organic group composed of only the polyether structure, and one or more of the polyether structure and one or more linking groups (a bivalent group having one or more atoms) are connected Organic &lt; / RTI &gt; Examples of the linking group in the organic group containing a polyether chain include a divalent hydrocarbon group (particularly, a linear or branched alkylene group), a thioether group (-S-), an ester group (-COO-) , An amide group (-CONH-), a carbonyl group (-CO-), a carbonate group (-OCOO-), and groups in which two or more thereof are bonded.

The polyether chain of L &lt; ¹ &gt; in the above general formula is not particularly limited as long as it has a structure having a plurality of the above-described ether bonds, but a structure having a plurality of the above-described ether bonds can be preferably used. The polyether chain may be an organic group composed of only a polyether structure, an organic group having a structure in which one or more of the polyether structures and one or more linking groups (a bivalent group having at least one atom) Contributing. Examples of the linking group in the organic group containing a polyether chain include a divalent hydrocarbon group (particularly, a linear or branched alkylene group), a thioether group (-S-), an ester group (-COO-) , An amide group (-CONH-), a carbonyl group (-CO-), a carbonate group (-OCOO-), and groups in which two or more thereof are bonded.

The compound containing silicon atoms in the present invention is more preferably at least one selected from dimethyl polysiloxane, methylphenyl polysiloxane, diphenyl polysiloxane and polyether modified polysiloxane.

Compounds containing silicon atoms are disclosed, for example, in JP-A-62-36663, JP-A-61-226746, JP-A-61-226745, JP-A-62-170950 , Japanese Unexamined Patent Publications Nos. 63-34540, 7-230165, 8-62834, 9-54432, 9-5988 , And JP-A-2001-330953, liquid form at 25 占 폚.

BYK-315, BYK-313, BYK-313, BYK-307, BYK-310, BYK- BYK-331 "," BYK-332 "," BYK-323 "," BYK-325 "," BYK- BYK-345 "," BYK-345 "," BYK-346 "," BYK-348 "," BYK- BYK-SILCLEAN 3720 "," BYK-UV3500 "," BYK-UV3510 "," BYK-UV3570 "," BYK- (Trade name, manufactured by Big Chemical Japan Co., Ltd.), "AC FS 180", "AC FS 360", "AC S 20" (manufactured by Algin Chemie), "POLYFLOW KL- Quot; Polyflow KL-404 ", "Polyflow KL-400 ", Kyoeisha Gagaku Co., KP-310 "," KP-323 "," KP-326 "," KP-301 "," KP- KP-351 "," KP-355 "," KP-341 "," KP-104 "," KP- KP-369 "," KP-368 "," KP-369 "," KP- , "KP-330 ", " "KP-650", "KP-651", "KP-390", "KP-391" and "KP-392" (manufactured by Shin-Etsu Chemical Co., "FZ-2105", "67 ADDITIVE", "8618 ADDITIVE", "3 ADDITIVE", "57 ADDITIVE", "L-7604" ADDITIVE ", "56 ADDITIVE" (manufactured by Toray Dow Corning Co., Ltd.), TEGO WET 270 (manufactured by Evonik Degussa Japan), and NBX- ), ADVALON FA33, FLUID L03, FLUID L033, FLUID L051, FLUID L053, FLUID L060, FLUID L066, IM22, WACKER-Belsil DMC 6038 (manufactured by Asahi Kasei Barker Silicone Co., Ltd.), KF- , KF-615A, KP-112, KP-341, X-22-4515, KF-354L, KF-355A, KF-6004, KF-6011, KF-6011P, KF-6012, , KF-6016, KF-6017, KF-6017P, KF-6020, KF-6028, KF-6028P, KF-6038, KF-6043, KF-6048, KF-6123, KF- K-642, KF-643, KF-644, KF-945, KP-110, KP-355, KP-369, KS-604, Polon SR-Conc, X-22-4272, (Manufactured by Shin-Etsu Chemical Co., Ltd.), 8526 ADDITIVE, FZ-2203, FZ-5609, L-7001, SF 8410, 2501 COSMETIC WA FZ-2123, FZ-2162, FZ-2162, FZ-2106, FZ-2108, FZ-2112, FZ- 2164, FZ-2191, FZ-2207, FZ-2208, FZ-2222, FZ-7001, FZ-77, L-7002, L-7604, SF8427, SF8428, SH 28 PAINR ADDITIVE, SH3749, SH3773M, SH8400, SH8700 Silwet L-7220, Silwet L-7230, Silwet L-7220, Silwet L-7210, Silwet L-7210, Silwet L-7220, Silwet L-7604, Silwet L-7604, Silwet L-7260, Silwet L-7500, Silwet L-7550, Silwet L-7600, Silwet L-7602, Silwet L-7604, Silwet L-722, Silwet L-722, TSW4445, TSF4446, TSF4452, Silwet Hydrostable 68 Silwet L-7607, Silwet L-7608, Silwet L-7622, Silwet L-7650, Silwet L-7657, Silwet L-77, Silwet L-8500, Silwet L-8610, TSF4440, TSF4441, TSF4450, TSF4460 Performance Materials ", manufactured by Japan Advanced Technology Co., Ltd.).

The total content of the compound containing at least one of the fluorine atom and the silicon atom in the adhesive composition (or the adhesive layer) used in the present invention is preferably such that the total content of the compounds contained in the adhesive composition (or the adhesive layer) Is preferably 0.001 mass% or more, more preferably 0.005 mass% or more, further preferably 0.01 mass% or more, particularly preferably 0.1 mass% or more, and still more preferably 0.2 mass% or more. The upper limit value is preferably 10 mass% or less, more preferably 5 mass% or less, more preferably less than 2.5 mass%, and most preferably 1 mass% or less.

When the total content of the compound containing at least one of the fluorine atom and the silicon atom is within the above range, the coating property and the peeling property are more excellent. In particular, in the present invention, the amount of the compound containing at least one of fluorine atoms and silicon atoms in the adhesive composition (or the adhesive layer) is at least high in that the effect of the present invention can be achieved.

The compound containing at least one of a fluorine atom and a silicon atom may be used singly or in combination of two or more. When two or more kinds are used in combination, it is preferable that the total content is in the above range.

In the case where the adhesive layer of the present invention has multiple layers, the compound containing at least one of the fluorine atom and the silicon atom may be included in either or both of them. The preferable range of the content of each layer is the same as the above-mentioned range. In addition, it is preferable to contain different amounts of the layers, and particularly to increase the peeling force in the adhesive layer.

<< Antioxidants >>

The adhesive composition used in the present invention may contain an antioxidant from the viewpoint of preventing the elastomer from becoming low in 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 phenolic antioxidant include para-methoxyphenol, 2,6-di-tert-butyl-4-methylphenol, Irganox1010, Irganox1330, Irganox3114, Irganox1035, Sumilizer MDP-S "and" Sumilizer GA-80 "manufactured by Sumitomo Chemical Co.,

Examples of the sulfur-based antioxidant include 3,3'-thiodipropionate di-stearyl, Sumilizer TPM, Sumilizer TPS, Sumilizer TP-D and the like available from Sumitomo Chemical Co., .

Examples of the phosphorus antioxidant include tris (2,4-di-tert-butylphenyl) phosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, poly Dialkyldiphenylphosphite, triphenylphosphite, "Irgafos 168", "Irgafos 38" manufactured by BASF Co., Ltd., and the like.

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

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

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

Among the above-mentioned antioxidants, it is preferable to use a phenolic antioxidant in combination with a sulfur-based antioxidant or a phosphorus-based antioxidant, and it is particularly preferable to use a phenolic antioxidant in combination with a sulfur-based antioxidant. Particularly when a thermoplastic elastomer containing a styrene structure is used as the elastomer, it is preferable to use a phenolic antioxidant and a sulfur-based antioxidant in combination. By using such a combination, it is expected that the deterioration of the elastomer by the oxidation reaction can be effectively suppressed. When the phenolic antioxidant and the sulfur antioxidant are used in combination, the mass ratio of the phenol antioxidant to the sulfur antioxidant is preferably 95: 5 to 5:95, : 25 is more preferable.

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

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

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

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

<< Radical Polymerizable Compound >>

The adhesive composition used in the present invention preferably contains a radically polymerizable compound. By using the adhesive composition containing a radical polymerizable compound, it is easy to suppress the flow deformation of the adhesive layer during heating. This makes it possible to suppress the flow deformation of the adhesive layer during heating, for example, when the laminate after polishing the processed substrate is heat-treated, and the occurrence of warpage can be effectively suppressed. Further, since the hardened adhesive layer can be formed, the adhesive layer is hardly deformed even when the pressure is locally applied at the time of polishing the processed substrate, and the flat polishing property is excellent.

In the present invention, the radical polymerizable compound is a compound having a radical polymerizable group, and a known radical polymerizable compound capable of being polymerized by a radical can be used. Such compounds are widely known in the technical field of the present invention, and they can be used without any particular limitation in the present invention. These may be, for example, monomers, prepolymers, oligomers or mixtures thereof and chemical forms thereof such as their multimers. As the radical polymerizing compound, reference can be made to the description in paragraphs 0099 to 0180 of Japanese Laid-Open Patent Publication No. 2015-087611, the contents of which are incorporated herein by reference.

The radically polymerizable compounds are described in Japanese Patent Publication Nos. 48-41708, 51-37193, 2-32293, and 2-16765, Such as urethane acrylates as described in JP-A-58-49860, JP-A-56-17654, JP-A-62-39417, and JP-A-62-39418 Also suitable are urethane compounds having the ethylene oxide skeleton described therein. As radically polymerizable compounds described in JP-A-63-277653, JP-A-63-260909, and JP-A-1-105238, a compound having an amino or sulfide structure in the molecule Polymerizable monomers may also be used.

Examples of commercially available radically polymerizable compounds include urethane oligomers UAS-10, UAB-140 (manufactured by Sanyo Kogaku Pulp), NK Ester M-40G, NK Ester 4G, NK Ester A-9300, NK Ester M- NK Ester A-BPE-4, UA-7200 (manufactured by Shin Nakamura Kagaku), DPHA-40H (manufactured by Nippon Kayaku), UA-306H, UA-306T, UA- 306I, AH-600, T-600, AI-600 (manufactured by Kyoeisha Chemical Co., Ltd.) and Blemmer PME400 (manufactured by Nichiyu Corporation).

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

[Chemical Formula 5]

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

In the adhesive composition used in the present invention, the content of the radical polymerizable compound in the adhesive composition is preferably in the range of from 0.1 to 5 parts by mass, , Preferably 1 to 50 mass%, more preferably 1 to 30 mass%, and still more preferably 5 to 30 mass%. The radical polymerizing compound may be used singly or in combination of two or more kinds.

In the adhesive composition used in the present invention, the mass ratio of the elastomer and the radically polymerizable compound in the case of adding the radically polymerizable compound is preferably from 98: 2 to 10:90 as the ratio of the elastomer to the radically polymerizable compound, More preferably from 95: 5 to 30:70, and particularly preferably from 90:10 to 50:50. When the mass ratio of the elastomer to the radical polymerizable compound is within the above range, the adhesive layer having excellent adhesion, flat abrasion resistance, peelability and flexural restraint can be formed.

<< Other Ingredients >>

The adhesive composition used in the present invention may contain various additives such as a surfactant, a plasticizer, a curing agent, a catalyst other than the above, a filler, an adhesion promoter, an ultraviolet absorber, An anti-aggregation agent, an elastomer or other polymer compound. When these additives are blended, the blending amount thereof is preferably 3% by mass or less, more preferably 1% by mass or less, of the total solid content of the adhesive composition. The lower limit value in the case of blending is preferably 0.0001 mass% or more. The total amount of these additives is preferably 10 mass% or less, more preferably 3 mass% or less, of the total solid content of the adhesive composition. The lower limit of the total amount of these components to be blended is preferably 0.0001 mass% or more.

The adhesive composition used in the present invention preferably does not contain impurities such as metals. The content of the impurities contained in these materials is preferably 1 ppm or less, more preferably 1 ppb or less, more preferably 100 ppt or less, even more preferably 10 ppt or less, Or less) is particularly preferable.

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

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

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

<< Preparation of Adhesive Composition >>

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

The filter can be used without particular limitation as far as it is conventionally used for filtration applications and the like. Examples of the resin include fluororesins such as polytetrafluoroethylene (PTFE), polyamide resins such as nylon-6 and nylon-6,6, polyolefin resins such as polyethylene and polypropylene (PP) And the like). Among these materials, polytetrafluoroethylene (PTFE) is preferable.

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

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

<< Formation of Adhesive Layer >>

The adhesive layer is formed on at least one surface of the carrier substrate and the processing substrate, as described above. An adhesive layer may be formed only on the carrier substrate and then bonded to the processed substrate. Alternatively, an adhesive layer may be formed only on the processed substrate, and may be laminated with the carrier substrate. It is preferable that an adhesive layer is provided on both the carrier substrate and the processed substrate so that both are adhered to each other. The adhesive layer can be formed by a conventionally known spin coating method, a spraying method, a slit coating method, a roller coating method, a float coating method, a doctor coating method, a dipping method, or the like. Subsequently, since the adhesive composition usually contains a solvent, heating is performed to volatilize the solvent. The heating temperature T0 is preferably higher than the boiling point of the solvent, more preferably 110 deg. C or higher, more preferably 130 deg. C to 200 deg. C, and particularly preferably 160 deg.

The adhesive agent layer in the present invention is a layer in which the adhesive agent composition has a boiling point X1 (unit: 캜) of the solvent contained in the adhesive composition, a thickness X2 (unit: (Unit: 占 폚), preferably satisfies the following relationship.

(X1-X2)? T0? (X1-X2 + 55)

It is more preferable to satisfy the following relationship.

(X1-X2 + 5)? T1? (X1-X2 + 45)

With such a range, it is possible to achieve a good flatness of the adhesive layer and further suppress the occurrence of voids. Particularly, when the resin contained in the adhesive layer is a thermoplastic elastomer containing a styrene structure, the effect is remarkable.

In particular, the in-plane uniformity of the adhesive layer as expressed by the following formula can be made less than 33%.

Of the thickness of the adhesive layer = (average value of the thickness of the adhesive layer) x 100 (unit:%)

It is preferable that the adhesive layer is thermally cured before press bonding, for example, under the conditions of a temperature of 110 to 250 DEG C and a time of 1 to 120 minutes.

The ultraviolet rays such as the g line and i line are preferably used (particularly preferably i line) as the radiation (light) usable at the time of exposure. Irradiation dose (exposure dose) is appropriate can be set according to the kind of the polymerizable compound, for example, 30 ~ 1500mJ / cm ² are preferred, and 50 ~ 1000mJ / cm ² is more preferably, 80 ~ 500mJ / cm ² is more desirable.

The adhesive layer is preferably formed so as to completely cover the device chip on the processed substrate, and when the height of the device chip is X m, and the thickness of the adhesive layer is Y m, the relationship of "X + 100 & .

The thickness of the adhesive layer in the present invention is preferably 1 to 150 탆, more preferably 10 to 100 탆, more preferably 10 to 60 탆, even more preferably 10 to 50 탆, more preferably 15 to 45 탆 Do. In the case where a plurality of adhesive layers are provided, it is preferable that each layer has the above thickness.

&Lt; Process substrate &

In the present invention, the processed substrate is preferably a device wafer. The device wafer can be a known one without limitation, and examples thereof include a silicon substrate, a compound semiconductor substrate, and a glass 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 a mechanical structure and a circuit are formed include semiconductors such as memories and logic devices, microelectromechanical systems (MEMS), power devices, image sensors, micro sensors, light emitting diodes (LEDs) Devices, micro devices, and the like.

It is preferable that the device wafer has a concave-convex portion. According to the present invention, it is possible to stably adhere to a device wafer having a structure on its surface, and to easily release adherence to a device wafer. The height of the structure is not particularly limited, but is preferably 0.1 to 150 占 퐉, more preferably 0.5 to 100 占 퐉, for example.

The thickness of the processed substrate is preferably 500 占 퐉 or more, more preferably 600 占 퐉 or more, and more preferably 700 占 퐉 or more. The upper limit is preferably, for example, 2000 占 퐉 or less, more preferably 1500 占 퐉 or less.

<Carrier Substrate>

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

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

<Laminate>

An example of the laminate of the present invention is a laminate having a carrier substrate, an adhesive layer, and a processed substrate, wherein the voids having a diameter of 1 mm or more and less than 150 pieces / m ² when observed under an ultrasonic microscope at a frequency of 140 MHz, The carrier substrate and the processed substrate are laminated bodies which can be peeled off with a force of 10 to 80 N.

The thickness of the adhesive layer of the laminate of the present invention can be referred to the description of the thickness of the adhesive layer described above, and is the same as the preferred range. The adhesive layer of the laminate of the present invention preferably comprises at least one of a thermoplastic elastomer, a thermoplastic siloxane polymer and a cycloolefin polymer containing a styrene structure. The details of these can be referred to the description of the resin used for the above-mentioned adhesive layer, and the preferable range is also the same.

In the laminate, after the processed substrate is usually subjected to any processing, the carrier substrate is peeled off to remove the adhesive layer. The obtained processed substrate is diced for each semiconductor chip, for example, and inserted into the semiconductor device. That is, the present invention discloses a method of manufacturing a semiconductor device, which includes the above-described method for producing a laminate or the above-mentioned method for producing a laminate. Further, a semiconductor device including the above-described laminate is disclosed.

<Other configurations>

As the jig for processing, attaching, carrying, and peeling the carrier substrate and the processed substrate, any emboss carrier tape or dicing frame may be used. In particular, when handling thin wafers, it is preferable to use TWSS disk type, ring type (manufactured by Shin-Etsu Polymer Co., Ltd.) or the like.

In addition, in the present invention, reference may be made to the contents of Japanese Laid-Open Patent Publication Nos. 2014-189731 and 2014-189696, the contents of which are incorporated herein by reference, without departing from the spirit of the present invention .

Example

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

[Example 1]

The following components were mixed to prepare a homogeneous solution, which was then filtered using a polytetrafluoroethylene filter having a pore size of 5 mu m to prepare compositions of Examples and Comparative Examples.

&Lt; Composition of Adhesive Composition >

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

The additives shown in Table 1: the mass parts shown in Table 1

Irganox 1010 (made by BASF): 2 parts by mass

Sumilizer TP-D (manufactured by Sumitomo Chemical Co., Ltd.): 2 parts by mass

Solvent (tert-butylbenzene, boiling point 169 ° C, manufactured by Toyo Kosei Kogyo Co., Ltd.): The amount to be the solid content concentration shown in Table 1

[Table 1]

The compounds listed in Table 1 are as follows.

[Table 2]

<Compound>

A-5: TSF4445 (Momentive Performance Materials, Japan Kogyo Co., Ltd.)

A-6: KF-6017 (manufactured by Shin-Etsu Chemical Co., Ltd.)

&Lt; Formation of laminate (Examples 1 to 10, 12 to 21 and Comparative Examples 1 to 3, 5, 6 and 8)

A silicon wafer having a diameter of 12 inches (1 inch is 2.54 cm) was used as a carrier substrate, and the adhesive composition shown in Table 1 was applied to the surface of the carrier substrate using a wafer bonding apparatus (Synapse V, Tokyo Electron) did. A hot plate was used to heat at a distance of 0.2 mm from the heat source to the carrier substrate at 160 캜 for 3 minutes and further heated at 190 캜 for 3 minutes to form an adhesive layer on the surface of the carrier substrate. At this time, the thickness of the adhesive layer was 40 탆.

The carrier substrate and the processed substrate (silicon wafer having a diameter of 12 inches) were thermocompression bonded by a wafer bonding apparatus (manufactured by EVG 805, manufactured by EVG) for 3 minutes under the atmospheric pressure P1 shown in Table 3 at a temperature of T1 and a pressure of 0.11 MPa , Thereby obtaining a laminate (bonding).

The bonded laminated body was heated for 5 minutes under the atmospheric pressure P2 shown in Table 3, using a wafer bonding apparatus (EVG 805, manufactured by EVG) for 5 minutes (post-baking).

&Lt; Formation of laminate (Example 11, Comparative Example 4)

A silicon wafer having a diameter of 12 inches (1 inch is 2.54 cm) was used as a carrier substrate, and the adhesive composition shown in Table 1 was applied to the surface of the carrier substrate using a wafer bonding apparatus (Synapse V, Tokyo Electron) did. A hot plate was used to heat at a distance of 0.2 mm from the heat source to the carrier substrate at 160 캜 for 3 minutes and further heated at 190 캜 for 3 minutes to form an adhesive layer on the surface of the carrier substrate. At this time, the thickness of the adhesive layer was 20 탆.

As a processed substrate, a processed substrate having a plurality of copper fillers each having a height of 10 占 퐉 and a diameter of 50 占 퐉 was used on a silicon wafer having a diameter of 12 inches. The adhesive composition shown in Table 1 was applied onto the surface of the processed substrate by a wafer bonding apparatus (Tokyo Electron, Synapse V). A hot plate was used to heat at a distance of 0.2 mm from the heat source to the processed substrate at 160 캜 for 3 minutes and further heated at 190 캜 for 3 minutes to form an adhesive layer on the surface of the processed substrate. At this time, the thickness of the adhesive was 20 탆.

The carrier substrate on which the adhesive layer was formed and the processed substrate on which the adhesive layer was formed were bonded by a wafer bonding apparatus (made by EVG 805, manufactured by EVG) at a pressure T1 of 0.11 MPa and a pressure T1 of 3 Followed by thermocompression for a minute to obtain a laminate.

The bonded laminate was heated (post-baked) for 5 minutes at a temperature T2 under the atmospheric pressure P2 shown in Table 3 using a wafer bonding apparatus (EVG 805, manufactured by EVG).

&Lt; Comparative Example 7 &

In Example 2, the bonded laminated body was formed in the same manner as above except that the laminated body was not post-baked.

&Lt; Measurement of storage elastic modulus &

By the method described in Example 1, an adhesive layer was prepared so that the thickness of the adhesive layer became 100 m. The resultant adhesive layer was sandwiched between parallel plates having a diameter of 10 mm and measured with a dynamic viscoelasticity measuring apparatus (Rheosol-G3000, UBM, Co., Ltd.) at a frequency of 10 Hz and a temperature raising rate of 5 deg. . &Lt; / RTI &gt; The storage elastic modulus at a measurement frequency of 10 Hz at a temperature T1 is G'1 and the storage elastic modulus at a measurement frequency of 10 Hz at a temperature T2 is G'2.

[Table 3]

&Lt; void evaluation of laminated body after bonding >

The voids in the bonded laminate were observed using a probe having a frequency of 140 MHz using an ultrasound imaging apparatus (FineSAT II, Hitachi Power Solutions Co., Ltd.), and evaluated according to the following criteria.

A: voids having a diameter of 1 mm or more were not observed.

B: Less than 150 voids / m ^{2 of} voids having a diameter of at least 1 mm were observed.

C: voids having a diameter of 1 mm or more were observed at 150 pieces / m ² and less than 300 pieces / m ² .

D: More than 300 voids / m &lt; ² &gt;

&Lt; Evaluation of voids in laminated body after post-baking &

The voids of the post-baked laminate were observed using a probe with a frequency of 140 MHz using an ultrasound imaging apparatus (FineSAT II, Hitachi Power Solutions Co., Ltd.) and evaluated according to the following criteria.

A: voids having a diameter of 1 mm or more were not observed.

B: Less than 150 voids / m ^{2 of} voids having a diameter of at least 1 mm were observed.

C: voids having a diameter of 1 mm or more were observed at 150 pieces / m ² and less than 300 pieces / m ² .

D: More than 300 voids / m &lt; ² &gt;

<Evaluation of peelability>

The back surface of the processed substrate of the laminate was polished to a thickness of 20 mu m using a back grinder DFG8540 (Disco) to obtain a thin laminated product.

The polished surface of the thinned laminate was placed on the lower side and the lower silicon wafer (processed substrate) was fixed together with the dicing frame in the center of the dicing tape using a dicing tape mounter. Subsequently, the upper silicon wafer (carrier substrate) was pulled up at a rate of 50 mm / min in a direction perpendicular to the lower silicon wafer at 25 占 폚 using a wafer debonding device (Synapse Z manufactured by Tokyo Electron Co., Ltd.) , It was confirmed whether or not the lower silicon wafer could be peeled without being cracked, and the evaluation was made based on the following criteria. In addition, the force was measured with a force gauge (ZTS-100N manufactured by Imada Co., Ltd.).

A: Peelable from 10N to less than 30N

B: Peelable from 30N to less than 50N

C: Peelable from 50N to less than 80N

D: Can be peeled off at 80N or more

E: During the peeling, the silicon wafer (processed substrate)

F: Peelable under 10N

<Peel strength stability evaluation>

At the time of peeling off, the machining substrate was evaluated by evaluating the fluctuation of the peeling force from 50 mm to 250 mm on the line passing through the center of the processed substrate from the point of 0 mm on the cross section, did.

A: The maximum value and the minimum value of the peeling force are within ± 25%

B: The maximum value and the minimum value of the peeling force are ± 25% or more and less than ± 35%

C: The maximum value and the minimum value of the peeling force are ± 35% or more and less than ± 45%

D: The maximum value and the minimum value of the peeling force are ± 45% or more

[Table 4]

As apparent from the above results, voids were generated in the laminated body after bonding in all the examples and comparative examples. However, in the laminated body manufactured by the manufacturing method of the present invention, after post-baking, Could. Further, it was found that the laminate produced by the production method of the present invention required a peeling force of 10 N or more at the time of peeling off the silicon wafer, so that it was properly adhered.

On the other hand, when at least one of the storage elastic moduli at the time of compression and heating after compression was over 1,000,000 Pa (Comparative Examples 1, 2, 4 and 6), the voids did not decrease even after post-baking and the peel strength stability was inferior . Also, in the case where the pressures P1 and P2 did not satisfy Log (P2 / P1) &gt; = 2.1 (Comparative Examples 3, 5 and 6), voids did not decrease even after post-baking, and the peel strength stability was also inferior.

Further, in the case where the post-baking was not performed (Comparative Example 7), void reduction was not possible, and the peel strength stability was also inferior.

Even when the relationship between the storage elastic modulus and the atmospheric pressure P1 and P2 was satisfied, when peeling was not possible with a force of 10 to 80 N (Comparative Example 8) when pulled up at a rate of 50 mm / min at 25 ° C, The silicon wafer is cracked.

In Examples 1 to 21, the adhesive layer was slowly peeled from the laminate of the lower silicon wafer (processed substrate) and the backing adhesive layer at 25 占 폚 after the removal test after the heat resistance test, Also, the adhesive layer was peeled off neatly.

1 carrier substrate
2 processed substrate
The trivalent adhesive layer
4 uneven portion

Claims (17)

A method of manufacturing a laminate having a first member having a carrier substrate and a second member having a processed substrate,
Wherein at least one surface of the first member and the second member has an adhesive layer,
The first member and the second member are pressed together under the atmospheric pressure P1 so that the adhesive layer is inward and heated at a temperature T2 exceeding 40 占 폚 under the air pressure P2, Including sieving,
Wherein the adhesive layer has a storage elastic modulus G'1 at a measurement frequency of 10 Hz and a storage modulus G'2 at a measurement frequency of 10 Hz at a temperature T1 Lt; / RTI &gt;
When the atmospheric pressure P1 and the atmospheric pressure P2 satisfy Log (P2 / P1) &gt; = 2.1,
Wherein the carrier substrate and the processed substrate are peelable by a force of 10 to 80 N,
A method of producing a laminate;
Here, the force at the time of peeling was fixed on the horizontal plane with the processed substrate side of the laminate down, and the carrier substrate was moved vertically to the processed substrate at 25 DEG C at a speed of 50 mm / min It is the force when it is raised. The method according to claim 1,
Wherein the adhesive layer comprises a compound containing at least one of a fluorine atom and a silicon atom. The method according to claim 1 or 2,
Wherein the atmospheric pressure P1 is less than 1013 Pa. The method according to any one of claims 1 to 3,
Wherein the atmospheric pressure P2 is 10,000 Pa or more. The method according to any one of claims 1 to 4,
Wherein the temperature T1 and the temperature T2 satisfy T1 < T2. The method according to any one of claims 1 to 4,
And the temperature T1 and the temperature T2 satisfy T1 + 20? T2. The method according to any one of claims 1 to 6,
Wherein the first member and the second member each independently have a backing adhesive layer. The method according to any one of claims 1 to 7,
Wherein the heating is performed at the time of compression under the air pressure P1, and the heating temperature T1 is 110 DEG C or more. The method according to any one of claims 1 to 8,
And the temperature T2 is 130 DEG C or higher. The method according to any one of claims 1 to 9,
Wherein the adhesive layer comprises at least one of a thermoplastic elastomer containing a styrene structure, a thermoplastic siloxane polymer, a cycloolefin polymer and an acrylic resin. The method according to any one of claims 1 to 10,
Wherein the processing is a step of heating at a temperature of 160 ° C or higher and 300 ° C or lower. The method according to any one of claims 1 to 10,
Wherein the processing is a step of thinning the surface of the processed substrate farther from the adhesive layer. The method of claim 12,
And the thickness of the processed substrate is made to be 100 占 퐉 or less by the thinning processing. A manufacturing method of a semiconductor device, comprising the method of manufacturing a laminate according to any one of claims 1 to 13, and further comprising a step of peeling at least the carrier substrate from the laminate at a temperature of 40 ° C or lower. 1. A laminate having a carrier substrate, an adhesive layer, and a processed substrate,
A void of not less than 1 mm in diameter and less than 150 pieces / m ² when observed under an ultrasonic microscope at a frequency of 140 MHz,
Wherein the carrier substrate and the processed substrate are peelable by a force of 10 to 80 N;
Here, the force at the time of peeling was fixed on the horizontal plane with the processed substrate side of the laminate down, and the carrier substrate was moved vertically to the processed substrate at 25 DEG C at a speed of 50 mm / min It is the force when it is raised. 16. The method of claim 15,
Wherein the adhesive layer has a thickness of 10 to 150 占 퐉. The method according to claim 15 or 16,
Wherein the adhesive layer comprises at least one of a thermoplastic elastomer containing a styrene structure, a thermoplastic siloxane polymer, a cycloolefin-based polymer and an acrylic resin.

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