JP6615722B2 - Laminate manufacturing method, temporary bonding composition, and temporary adhesive film - Google Patents

Description

  The present invention relates to a laminate manufacturing method, a temporary bonding composition, and a temporary adhesive film.

In a manufacturing process of a semiconductor device such as an integrated circuit (IC) or a large-scale integrated circuit (LSI), a large number of IC chips are formed on a device wafer and separated by dicing.
With the need for further downsizing and higher performance of electronic equipment, further downsizing and higher integration are required for IC chips mounted on electronic equipment, but integrated circuits in the in-plane direction of device wafers High integration is approaching its limit.

  As an electrical connection method from an integrated circuit in an IC chip to an external terminal of the IC chip, a wire bonding method has been widely known. However, in recent years, in order to reduce the size of an IC chip, a device wafer is used. A method is known in which a through hole is provided in a metal plug, and a metal plug as an external terminal is connected to an integrated circuit so as to penetrate through the through hole (so-called silicon through electrode (TSV) formation method). However, only the method of forming the through silicon vias cannot sufficiently meet the above-described needs for higher integration of the recent IC chip.

  In view of the above, a technique is known in which the degree of integration per unit area of a device wafer is improved by multilayering integrated circuits in an IC chip. However, since the multilayered integrated circuit increases the thickness of the IC chip, it is necessary to reduce the thickness of the members constituting the IC chip. For example, thinning of a device wafer is being considered as a thinning of such a member, which not only leads to the miniaturization of an IC chip, but also saves the manufacturing process of a through hole of a device wafer in the production of a silicon through electrode. Because it is possible, it is considered promising. Also, thinning of semiconductor devices such as power devices and image sensors has been attempted from the viewpoint of improving the degree of integration and improving the degree of freedom of the device structure.

As a device wafer, one having a thickness of about 700 to 900 μm is widely known. However, in recent years, for the purpose of reducing the size of an IC chip or the like, the thickness of the device wafer can be reduced to 200 μm or less. Has been tried.
However, since a device wafer having a thickness of 200 μm or less is very thin and a semiconductor device manufacturing member using the device wafer as a substrate is also very thin, such a member is subjected to further processing or such a member. It is difficult to support the member stably and without damaging the member when, for example, it is simply moved.

  In order to solve the above problems, the device wafer before thinning and the carrier substrate are temporarily fixed with the temporary bonding composition (temporary bonding), and the back surface of the device wafer is ground and thinned. A technique for peeling (detaching) a carrier substrate from a device wafer is known.

  For example, Patent Document 1 discloses the manufacture of a semiconductor device that at least seals a semiconductor element connected to a conductor with a sealing resin on the adhesive layer in an adhesive sheet having a base material layer and an adhesive layer. A semiconductor device manufacturing adhesive sheet used in a process, wherein the adhesive layer of the adhesive sheet has an aromatic vinyl compound polymer block and a conjugated diene compound polymer block and / or water thereof An adhesive sheet for manufacturing a semiconductor device is disclosed that contains an additive and is crosslinked so that the gel fraction is 50% by mass or more.

JP 2004-75853 A

Here, in Patent Document 1, a composition for temporary bonding is prepared as an adhesive solution. Liquid temporary bonding compositions have various advantages and are widely used. However, when a liquid temporary bonding composition is used, for example, the temporary bonding composition is applied in a layered manner on the surface of the carrier wafer, the solvent component is dried, and then cured to form a temporary bonding film. A process for bonding the device wafers is required. Therefore, further improvement in work efficiency is required. Moreover, when a liquid temporary bonding composition is applied in a layered manner on the surface of a carrier wafer or the like, an edge bead may be formed at the end of the layered temporary bonding composition film.
The present invention aims to solve such a problem, and when a laminate is manufactured by bonding two substrates together with a temporary adhesive film, a uniform temporary adhesive film having excellent work efficiency is formed. An object of the present invention is to provide a method for producing a laminate, and a temporary bonding composition and a temporary bonding film.

As a result of investigation by the present inventor under the above problems, the above problems have been solved by the following means <1>, preferably <2> to <18>.
<1> A method for manufacturing a laminate having a structure in which a first substrate, a temporary adhesive film, and a second substrate are adjacent to each other in the above order, and temporarily bonded to one surface of the first substrate or a mold Applying a mold composition, applying a mold or a second substrate to the surface of the temporary bonding composition, applying energy to the temporary bonding composition, and forming a temporary adhesive film; In the above order, the temporary adhering composition contains a release agent, and is a powdery or granular method at 25 ° C. and 101,300 Pa.
<2> The method for producing a laminate according to <1>, wherein the application of energy includes heating.
<3> The method for producing a laminate according to <1> or <2>, wherein the application of energy includes application of pressure.
<4> The method for producing a laminate according to any one of <1> to <3>, wherein the temporary bonding composition includes a resin.
<5> The method for producing a laminate according to any one of <1> to <4>, wherein the release agent includes at least one of a fluorine atom and a silicon atom.
<6> The method for producing a laminate according to any one of <1> to <5>, wherein the temporary bonding composition includes an antioxidant.
<7> After applying the temporary bonding composition to the surface of the first substrate and applying the second substrate to the surface of the temporary bonding composition, energy is applied to the temporary bonding composition. The method for producing a laminate according to any one of <1> to <6>, wherein a temporary adhesive film is formed.
<8> The method for producing a laminated body according to <7>, wherein the formation of the temporary adhesive film and the temporary adhesion between the first substrate and the second substrate are performed in the same process using a bonder device.
<9> Apply the temporary bonding composition to the surface of the first substrate and apply the mold to the surface of the temporary bonding composition, or apply the temporary bonding composition to the surface of the mold. Applying and applying the second substrate to the surface of the temporary bonding composition, and further forming the temporary adhesive film, and then peeling the mold and removing the mold The method for manufacturing a laminate according to any one of <1> to <6>, wherein the second substrate or the first substrate is applied to a surface of the temporary adhesive film.
<10> The method for producing a laminate according to <9>, wherein the mold has at least one of a concave portion and a convex portion on a surface in contact with the temporary bonding composition.
<11> A composition for temporary bonding which contains a release agent and is powdery or granular at 25 ° C. and 101,300 Pa.
<12> The temporary bonding composition according to <11>, wherein the temporary bonding composition further includes a resin.
<13> The temporary bonding composition according to <12>, wherein the resin includes a styrene-based elastomer.
<14> The temporary bonding composition according to any one of <11> to <13>, wherein the release agent includes at least one of a fluorine atom and a silicon atom.
<15> The temporary bonding composition according to any one of <11> to <14>, wherein the temporary bonding composition includes an antioxidant.
<16> A temporary adhesive film containing a release agent and a resin, wherein the temporary adhesive film has at least one of a concave portion and a convex portion on the surface, and has an average thickness of 5 to 500 μm. .
<17> The temporary adhesive film according to <16>, wherein the temporary adhesive film is formed by curing the temporary adhesive composition according to any one of <11> to <15>.
<18> A method for manufacturing a semiconductor device, including the method for manufacturing a laminated body according to any one of <1> to <10>.

  According to the present invention, when manufacturing a laminate by bonding two substrates together with a temporary adhesive film, a method for manufacturing a laminate that is excellent in work efficiency and can form a uniform temporary adhesive film, and a composition for temporary adhesion Products and temporary adhesive films can be provided.

It is the schematic which shows 1st Embodiment of the manufacturing method of the laminated body of this invention. It is the schematic which shows 2nd Embodiment of the manufacturing method of the laminated body of this invention.

Hereinafter, the contents of the present invention will be described in detail. In the present specification, “to” is used to mean that the numerical values described before and after it are included as a lower limit and an upper limit.
In the description of the group (atomic group) in this specification, the description which does not describe substitution and non-substitution includes what does not have a substituent and what has a substituent. For example, the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
“Actinic light” or “radiation” in the present specification means, for example, those including visible light, ultraviolet rays, far ultraviolet rays, electron beams, X-rays and the like.
In this specification, unless otherwise specified, “exposure” includes not only exposure using light but also drawing using particle beams such as electron beams and ion beams. The light used for the exposure generally includes an active ray or radiation such as an emission line spectrum of a mercury lamp, far ultraviolet rays represented by an excimer laser, extreme ultraviolet rays (EUV light), X-rays, or electron beams.
In the present specification, the total solid content refers to the total mass of the components excluding the solvent from all the components of the composition.
In the present specification, “(meth) acrylate” represents acrylate and methacrylate, “(meth) acryl” represents acrylic and methacryl, and “(meth) acryloyl” represents “acryloyl” and “methacryloyl”. .
In this specification, a weight average molecular weight and a number average molecular weight are defined as a polystyrene conversion value by gel permeation chromatography (GPC) measurement. In this specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are, for example, using HLC-8220 (manufactured by Tosoh Corporation), and TSKgel Super AWM-H (manufactured by Tosoh Corporation, inner diameter) as a column. (ID) 6.0 mm × 15.0 cm) and a 10 mmol / L lithium bromide NMP (N-methylpyrrolidone) solution as an eluent.
In the embodiments described below, the members and the like described in the drawings already referred to are denoted by the same or corresponding reference numerals in the drawings, and the description is simplified or omitted.

Manufacturing method of laminated body The manufacturing method of the laminated body of the present invention is a manufacturing method of a laminated body having a structure in which a first substrate, a temporary adhesive film, and a second substrate are adjacent to each other in the above order. Applying a temporary bonding composition to one surface of the substrate or mold, applying a mold or second substrate to the surface of the temporary bonding composition, and applying energy to the temporary bonding composition. And a step of forming a temporary adhesive film in the order described above, wherein the temporary adhesive composition contains a release agent and is powdery or granular at 25 ° C. and 101,300 Pa. And
Thus, by using the powdery or granular temporary bonding composition, unlike the temporary bonding composition containing a solvent as a main component, it is not necessary to apply and dry to form a temporary bonding film. Furthermore, when the temporary adhesive film is produced by coating, edge beads can be easily formed at the edge portion, but the use of a powdery or granular temporary adhesive composition can suppress the occurrence of edge beads.
Furthermore, in the manufacturing method of the laminated body of this invention, since a recessed part or a convex part can be easily formed in the surface of a temporary adhesion film, it is preferable when temporarily fixing the device wafer which has an uneven part to a carrier substrate.
As an energy provision means, what is mentioned in 1st Embodiment or 2nd Embodiment mentioned later is illustrated.
Hereinafter, preferred embodiments of the present invention will be described with reference to the drawings. It goes without saying that the present invention is not limited to the embodiments described in the drawings.

<First Embodiment>
In the manufacturing method according to the first embodiment of the present invention, the temporary bonding composition is applied to the surface of the first substrate, and the second substrate is applied to the surface of the temporary bonding composition. Energy is imparted to the composition to form a temporary adhesive film. Furthermore, it is preferable to form the temporary adhesive film and temporarily bond the first substrate and the second substrate in the same process using a bonder device.
Hereinafter, the first embodiment will be described in detail with reference to FIG.
1 (1) to 1 (4) show a process of manufacturing a laminated body by temporarily bonding (bonding) a first substrate and a second substrate with a temporary adhesive film. 1 (5) to (8) show a process of processing the obtained laminate.

<< Bonding >>
In FIG. 1 (1), a first substrate 2 is provided in a bonder device (only part of which is shown below) 1, and a temporary bonding composition 3 is placed on the first substrate 2. The temporary bonding composition 3 is preferably placed on the surface of the first substrate 2 after providing an enclosure with a frame 4 or the like. In order to place the temporary bonding composition 3 on the surface of the first substrate, it is preferable to spray the temporary bonding composition 3 with a uniform thickness using a sieve or the like. By placing the temporary bonding composition 3 so as to have a uniform thickness, a more uniform temporary bonding film can be easily obtained. The average thickness of the temporary bonding composition 3 (powder or granular material applied to the layer) varies depending on the shape of the temporary bonding composition, but the gap (void) in the state where the composition is placed on the substrate surface. ) And the solid volume ratio of 50%: 50%, 0.02 to 0.4 mm is preferable, and 0.06 to 0.30 mm is more preferable. The method of this embodiment is particularly useful when the average thickness of the temporary bonding composition 3 is about 0.1 to 0.2 mm.
The first substrate 2 may be a carrier substrate or a device wafer, but is preferably a carrier substrate. Moreover, the other board | substrate whose detail is mentioned later may be sufficient. By using the first substrate as a carrier substrate (the probability of damaging devices on the device wafer can be more effectively reduced.
As shown in FIG. 1 (1), after layering the temporary bonding composition 3, the frame 4 is removed, and as shown in FIG. 1 (2), at least the edge portion at a position higher than the temporary bonding composition is removed. It is preferable to insert a spacer (not shown) in a part. By setting it as such a structure, since it can prevent that the composition for temporary adhesion on the 1st board | substrate and the 2nd board | substrate 6 contact before pressurization, a part of composition for temporary adhesion is from an edge. It is possible to more effectively suppress spilling and scattering, and part of the temporary bonding composition adhering to the second substrate before pressurization and causing unevenness in film thickness.
In the above description, the frame 4 is removed. However, if the height of the frame 4 is set lower than the thickness of the temporary adhesive film after bonding, it may not be removed.

Next, as shown in FIG. 1 (3), the second substrate 6 is provided on the surface of the temporary bonding composition 3. The second substrate 6 is preferably a device wafer when the first substrate 2 is a carrier substrate. When a device wafer is provided as the second substrate 6, a concave portion or a convex portion such as a bump on the surface of the device wafer is provided in contact with the temporary bonding composition 3. In addition, the recessed part in this invention means that the depth of the deepest part of a hollow is 5 micrometers or more, for example. Moreover, a convex part means that the height of the highest part of a protrusion part is 5 micrometers or more, for example.
Next, energy is applied as shown in FIG. Examples of energy include heating and application of pressure, and both heating and application of pressure are preferably performed. Although heating temperature is based also on the component contained in the composition for temporary attachment, it is 100-300 degreeC, for example, and heating time is 30 seconds-30 minutes, for example. The pressure is, for example, 5 to 50 kN, and the pressure application time is, for example, 30 seconds to 30 minutes. The pressure is preferably applied by applying pressure from the first substrate 2 side and the second substrate 6 side.
By applying energy, for example, the powdery or granular component in the temporary bonding composition 3 is deformed, and most of the voids are eliminated, and the flat temporary bonding film 33 is formed.
The average thickness of the temporary adhesive film 33 is preferably 0.01 to 0.2 mm, and more preferably 0.03 to 0.15 mm. The method of this embodiment is particularly beneficial when the average thickness of the temporary adhesive film 33 is about 0.05 to 0.1 mm.

  The application of energy is preferably performed in the bonder apparatus 1 as shown in FIG. In the conventional liquid temporary bonding composition, bonding was performed after the coating film was dried. However, in the present invention, the temporary bonding composition 3 is in the form of powder or particles, so Formation and temporary bonding of the first substrate 2 and the second substrate 6 can be performed in the bonder apparatus 1. Furthermore, the temporary adhesion film 33 and the temporary adhesion of the first substrate 2 and the second substrate 6 can be performed in the same process. “Within the same process” means, for example, what can be done within the same energy application step. However, the formation of the temporary adhesive film 33 and the temporary adhesion between the first substrate 2 and the second substrate 6 do not need to proceed completely simultaneously. Actually, when energy is applied in FIG. 1 (4), the formation of the temporary adhesive film 33 proceeds preferentially at the beginning, and at the stage where the formation of the temporary adhesive film 33 has progressed to some extent, In many cases, the temporary bonding between the substrate 2 and the second substrate 6 proceeds.

<< Processing >>
The laminate obtained as described above is preferably processed. Processing is usually performed on the surface of the second substrate such as a device wafer that is not in contact with the temporary adhesive film. The processing is exemplified by mechanical or chemical processing. More specifically, thinning processing such as grinding or chemical mechanical polishing (CMP), chemical vapor deposition (CVD) or physical vapor deposition (PVD). And treatment under high temperature and vacuum such as, treatment with chemicals such as organic solvent, acidic treatment liquid and basic treatment liquid, plating treatment, irradiation with actinic rays, heat treatment and cooling treatment.
In FIG. 1 (5), the laminated body is moved to a grinder, and the back surface of the device wafer (the surface on which the concave portion or the convex portion is not provided) is thinned by the grinder. The thickness of the base material portion (portion serving as a base not having a concave portion or a convex portion) of the device wafer (processed second substrate 66) after being thinned is preferably 50 μm or less, and more preferably 20 μm or less. . As a lower limit, it can be set as 10 micrometers, for example.

<< Debonding >>
In the present invention, after the second substrate 6 is processed, a step of cleaning the temporary adhesive film protruding outside the area of the substrate surface of the processed second substrate 66 with a peeling solution may be provided. In this embodiment, after thinning the device wafer, the temporary adhesive film that protrudes is removed by using a stripping solution, whereby temporary adhesion is performed by directly applying the treatment under high temperature and vacuum to the temporary adhesive film. Deformation and alteration of the film can be prevented.
Next, as shown in FIG. 1 (6), the processed second substrate is moved to the debonder apparatus. Usually, it arrange | positions so that the processed 2nd board | substrate may become a lower side (fixed side). Next, as shown in FIG. 1 (7), one of the first substrate 2 and the processed second substrate 66 is peeled from the processed (thinned) laminate. The substrate to be peeled is preferably the substrate that has not been processed (thinned). In FIG. 1 (7), the first substrate 2 that is the carrier substrate is peeled off at the interface with the temporary adhesive film 33. However, it may be peeled off at the interface between the temporary adhesive film 33 and the processed second substrate 66.

  The peeling method is not particularly limited, but it is preferable that the processed device wafer is fixed, and the carrier substrate is pulled up from the end in a direction perpendicular to the processed device wafer to be peeled off. At this time, the peeling interface is preferably the interface between the carrier substrate and the temporary adhesive film.

Next, as shown in FIG. 1 (8), the processed second substrate 66 can be obtained by removing the temporary adhesive film 33 from the processed second substrate 66.
The removal method of the temporary adhesive film 33 is, for example, a method of peeling the temporary adhesive film 33 in a film state, a method of removing using the peeling liquid (a method of peeling and removing the temporary adhesive film after swelling with the peeling liquid) , A method of destroying and removing the temporary adhesive film by spraying the peeling liquid, a method of dissolving and removing the temporary adhesive film in the peeling liquid, etc.), decomposing the temporary adhesive film by irradiation with active light, radiation or heat, or For example, a method of removing by evaporation.
From the viewpoint of reducing the amount of solvent used, a method of peeling the temporary adhesive film 33 in a film state (peel off) is preferable. The method of peeling and removing the temporary adhesive film 33 while it is in a film state means that the temporary adhesive film is peeled and removed by applying a physical force without performing chemical treatment such as using a peeling liquid ( A method of peeling off. When the temporary adhesive film is peeled and removed in the film state, peeling by hand or mechanical peeling is preferable.

  Moreover, as a peeling liquid, the organic solvent which melt | dissolves a temporary adhesive film is preferable. Details of the stripping solution can be referred to the descriptions in paragraphs 0231 to 0241 of JP-A-2015-191940, and the contents thereof are incorporated in the present specification.

<< Cleaning >>
The first substrate 2 may be cleaned after being peeled from the processed second substrate 66. For cleaning, an organic solvent or the above stripping solution is preferably used.

<< Manufacture of semiconductor devices >>
Various known processes may be performed on the processed second substrate 66. For example, the semiconductor device can be manufactured by performing various processes on the thinned device wafer.

<Second Embodiment>
In the manufacturing method of the second embodiment of the present invention, the temporary adhesion composition is applied to the surface of the first substrate, and the mold is applied to the surface of the temporary adhesion composition, or the surface of the mold And applying the second substrate to the surface of the temporary bonding composition, further forming a temporary adhesive film, peeling the mold, and peeling the mold The second substrate or the first substrate is applied to the surface of the temporary adhesive film on the processed side.
In the second embodiment, since the temporary adhesive film is formed using a mold, it is possible to easily manufacture a temporary adhesive film having at least one of a concave portion and a convex portion.
Hereinafter, the second embodiment will be described in detail with reference to FIG.
FIG. 2 shows a case where a temporary bonding composition is applied to the surface of the first substrate, a mold is applied to the surface of the temporary bonding composition, a temporary adhesive film is formed, the mold is peeled off, It is the schematic which shows the process of applying the said 2nd board | substrate to the surface of the temporary adhesive film of the side which peeled the mold type | mold.
2 (1) to 2 (6) show a process of manufacturing a laminated body by temporarily bonding (bonding) the first substrate and the second substrate with a temporary adhesive film. 2 (7) to 2 (10) show a process of processing the obtained laminate.
Common reference numerals are assigned to common reference numerals with FIG.

<< Compression mold >>
In FIG. 2 (1), the 1st board | substrate 2 is installed in the compression mold apparatus 7 (only one part is shown), and the composition 3 for temporary attachment is put on it. It is preferable that the temporary bonding composition 3 is placed on the surface of the first substrate after providing an enclosure with a frame 4 or the like. When placing the temporary bonding composition 3 on the surface of the first substrate, it is preferable to use a sieve or the like to make the temporary bonding composition 3 have a uniform thickness. By placing the temporary bonding composition 3 so as to have a uniform thickness, a more uniform temporary bonding film can be easily obtained. In this state, the average thickness of the temporary bonding composition 3 varies depending on the shape of the temporary bonding composition, but the ratio of the gap (void) and the solid content when the composition is placed on the substrate surface is about 50%: In the case of 50%, 0.02 to 0.4 mm is preferable, and 0.04 to 0.3 mm is more preferable. The method of this embodiment is particularly effective when the average thickness of the temporary bonding composition 3 is about 0.1 to 0.2 mm.
The first substrate may be a carrier substrate or a device wafer, but is preferably a carrier substrate. Moreover, the other board | substrate whose detail is mentioned later may be sufficient. By using the first substrate as a carrier substrate, the probability of damaging devices on the device wafer can be more effectively reduced.
As shown in FIG. 2 (1), the temporary bonding composition 3 is applied in layers on the first substrate placed in the compression mold apparatus 7, and then the frame 4 is removed as necessary.
Thereafter, the mold 8 is provided on the surface of the temporary bonding composition 3. At this time, the mold 8 may have at least one of a concave portion and a convex portion on the surface in contact with the temporary bonding composition 3. In the present invention, the concave and convex portions of the mold can be set so as to correspond to the concave and convex portions on the surface of the device wafer or the like. With such a configuration, the first substrate 2 and the second substrate 6 can be temporarily bonded to each other more uniformly, and the final bonded body (carrier wafer / temporary adhesive film / device wafer) can be bonded. Thickness uniformity can be further improved.

Next, energy is applied as shown in FIG. Examples of energy include heating and application of pressure, and both heating and application of pressure are preferably performed. Although heating temperature is based also on the component contained in the composition 3 for temporary bonding, it is 100-300 degreeC, for example, and heating time is 30 seconds-30 minutes, for example. The pressure is, for example, 5 to 50 kN, and the pressure application time is, for example, 30 seconds to 30 minutes. It is preferable to apply the pressure by applying pressure from the first substrate 2 side and the mold die 8 side.
By applying energy, for example, the powdery or granular component in the temporary bonding composition 3 is deformed to form the temporary bonding film 33.
Application of energy is performed through the mold 8 and the first substrate 2 in the compression mold apparatus 7. The compression mold apparatus 7 has a heating function and a pressurizing function in both the upper and lower sides. By setting it as such a structure, the temporary adhesive film which has at least one of a recessed part and a convex part on the surface of the temporary adhesive film 33 is obtained.
In addition, when using a thermoplastic resin as a main component of the composition 3 for temporary adhesion | attachment, it is preferable to cool, after heating and melting a thermoplastic resin and forming the temporary adhesion film | membrane 33 corresponding to a mold.
The average thickness of the temporary adhesive film 33 is preferably 0.01 to 0.2 mm, and more preferably 0.02 to 0.15 mm. The method of this embodiment is particularly beneficial when the average thickness of the temporary adhesive film 33 is about 0.05 to 0.1 mm.

  After the temporary adhesive film 33 is formed, the mold 8 is peeled off as shown in FIG. The obtained temporary adhesive film 33 has, on its surface, convex portions or concave portions to which the mold concave portions or convex portions are transferred.

<< Bonding >>
Next, as shown in FIGS. 2 (5) and (6), a device wafer as the second substrate 6 is provided on the surface of the temporary adhesive film 33. Further, the carrier substrate as the first substrate 2 and the device wafer as the second substrate 6 are temporarily bonded via the temporary bonding film 33. The temporary bonding is preferably performed in the bonder apparatus 1. The temporary adhesion is preferably performed by applying energy. Examples of energy include heating and application of pressure, and both heating and application of pressure are preferably performed. Although heating temperature is based also on the component contained in the composition 3 for temporary bonding, it is 100-300 degreeC, for example, and heating time is 30 seconds-30 minutes, for example. The pressure is, for example, 5 to 50 kN, and the pressure application time is, for example, 30 seconds to 30 minutes. The pressure is preferably applied by applying pressure from the first substrate 2 side and the second substrate 6 side.
In addition, it is preferable that a spacer is inserted into at least a part of the edge before the second substrate 6 is provided on the stacked body of the first substrate 2 and the temporary adhesive film 33. Moreover, it is desirable to evacuate the inside of the bonder apparatus 1 before pressurization. Furthermore, when a spacer is inserted, it is necessary to pull out the spacer before pressurization. By these steps, it is difficult for air to remain between the temporary adhesive film 33 and the second substrate 6, and voids (air) remain between the temporary adhesive film 33 and the second substrate 6 during heating and pressurization. It can be effectively suppressed.

<< Processing, Debonding, Cleaning, Manufacturing of Semiconductor Device >>
The laminate obtained as described above is preferably processed. The processing is performed by the steps shown in (7) to (10) of FIG. 2, but these details are the same as the explanations corresponding to (5) to (8) of FIG. 1, and the preferred ranges are also the same. is there.

  Next, after peeling the carrier substrate from the processed device wafer, various known processes can be performed on the processed device wafer to manufacture a semiconductor device having the processed device wafer.

  The second embodiment also includes applying the temporary bonding composition to the surface of the mold, applying the second substrate to the surface of the temporary bonding composition, and further forming the temporary bonding film. Then, a method of peeling the mold mold and applying the first substrate to the surface of the temporary adhesive film on the side where the mold mold is peeled is also disclosed. In this case, a mold mold is placed in the compression mold apparatus instead of the first substrate, and a laminate of mold mold / temporary adhesive film / second substrate is manufactured. After peeling off the mold from the laminate, the first substrate is applied at the position where the mold was laminated. Others are the same as the above-mentioned embodiment.

<Board>
Next, the first substrate and the second substrate will be described. An example of a preferred embodiment of the first substrate and the second substrate is one device wafer, and the other is a carrier substrate that holds the device wafer when processing the device wafer.
Examples of the carrier substrate that supports the device wafer include a substrate including a silicon substrate and a glass substrate.
When a carrier substrate including a silicon substrate or a glass substrate is used, as the other substrate, a memory device, a fanout device (logic, discrete, etc.), a MEMS device (Micro Electro Mechanical Systems device), a power device, an image sensor, A flexible device (communication, display, etc.) can also be used.
On the other hand, metal substrates (for example, aluminum substrates, copper substrates, stainless steel substrates, etc.), glass substrates or resin substrates (for example, glass epoxy substrates, epoxy substrates, polycarbonate substrates, BT resins (bismaleimides) A substrate including a triazine resin base material) and a flexible base material having flexibility (for example, a polyimide base material, a polyethylene naphthalate (PEN) base material, a polyethylene terephthalate (PET) base material, etc.) or a package base material ( A combination of substrates including a device-embedded substrate, a device mounting substrate and the like can also be preferably used.
Furthermore, at least one of the first substrate and the second substrate may have at least one of a concave portion and a convex portion on the surface of the various base materials. For example, a device wafer having metal bumps, metal pillars, metal circuits, dicing grooves, MEMS structures, mounting chips, etc. on the surface of a substrate such as a silicon substrate is exemplified.
In addition, the first substrate and the second substrate may have a layer on the surface of the base material. Specifically, a mode in which a SiN film or a silicon oxide film is provided on the surface of the silicon base material, a mode in which a silicon oxide film is provided on the glass base material surface, and the like are exemplified. These films serve as a reinforcing film for the substrate. In addition, an embodiment in which an insulating film (inorganic insulating film or organic insulating film), a conductive film, a release layer, or the like is provided on the surface of a base material such as a silicon base material is also exemplified.

Temporary Adhesion Composition The temporary adhesion composition of the present invention contains a release agent and is powdery or granular at 25 ° C. and 101,300 Pa. The powdery or granular temporary bonding composition means that a fine solid substance is a main component. The main component means a component having the highest content in the temporary bonding composition, preferably 80% by mass or more, more preferably 90% by mass or more, further preferably 95% by mass or more, and still more preferably 98% by mass. The component which occupies more than%. The fine solid substance in the present invention preferably has an average maximum length of 1 mm or less, and more preferably 0.5 mm or less. For example, commercially available powdered resins and polymerizable monomers are included in the fine solid material of the present invention.

In the temporary bonding composition of the present invention, the content of the solvent is preferably 10% by mass or less of the temporary bonding composition. The content of the solvent is more preferably 5% by mass or less, more preferably 1% by mass or less, still more preferably 0.5% by mass or less, and more preferably 0% by mass or less. More preferably, it is 1% by mass or less, and further more preferably 0.05% by mass or less.
In addition, the composition for temporary bonding according to the present invention preferably has a content of components other than solids of 3% by mass or less, more preferably 1% by mass or less at 25 ° C. and 101,300 Pa. More preferably, it is 0.8 mass% or less, More preferably, it is 0.5 mass% or less, More preferably, it is 0.1 mass% or less, Furthermore, it is 0.05 mass% or less Even more preferred.

  The temporary bonding composition of the present invention preferably contains a resin and / or a thermopolymerizable monomer or oligomer and a release agent, and more preferably contains a resin and a release agent. Moreover, the composition for temporary adhesion of this invention may contain antioxidant and another component in addition to the said component.

The resin may be a thermoplastic resin or a thermosetting resin.
1st Embodiment of the composition for temporary bonding of this invention is a mode which contains a thermoplastic resin and a mold release agent, and content of a solvent is 1 mass% or less of the composition for temporary bonding. The first embodiment is particularly suitable when the temporary adhesive film is formed and the first substrate and the second substrate are temporarily bonded in the same process using a bonder apparatus.
2nd Embodiment of the composition for temporary adhesion of this invention contains a thermosetting resin and / or a thermopolymerizable monomer, and a mold release agent, and content of a solvent is 1 mass% or less of the composition for temporary adhesion. This is an embodiment. The second embodiment is particularly suitable when a temporary adhesive film is used using a compression mold apparatus. Moreover, in 2nd Embodiment, it is preferable that the composition for temporary adhesion contains a thermosetting resin.

<Resin>
The temporary bonding composition used in the present invention preferably contains at least one resin. The resin may be a thermoplastic resin or a thermosetting resin.

<< Elastomer >>
In the temporary bonding composition used in the present invention, the resin is preferably an elastomer. By using an elastomer as the resin, it is possible to follow a fine unevenness of a substrate (a substrate to be processed such as a carrier substrate or a device wafer), and to form a temporary adhesive composition having excellent adhesion by an appropriate anchor effect. . One or more elastomers can be used in combination.
In the present specification, an elastomer represents a polymer compound that exhibits elastic deformation. That is, when an external force is applied, it is defined as a polymer compound having a property of instantly deforming according to the external force and recovering the original shape in a short time when the external force is removed.

  In the present invention, the weight average molecular weight of the elastomer is preferably from 2,000 to 200,000, more preferably from 10,000 to 200,000, and even more preferably from 50,000 to 100,000. An elastomer having a weight average molecular weight in this range is excellent in solubility in a solvent. Therefore, after peeling the carrier substrate from the substrate to be processed, the solvent is used to derive from the elastomer remaining on the substrate to be processed or the carrier substrate. When removing the residue, the residue is easily dissolved in the solvent and removed. For this reason, there exists an advantage that a residue does not remain in a to-be-processed substrate, a carrier substrate, etc.

  In the present invention, the elastomer is not particularly limited, and an elastomer (polystyrene elastomer) containing a repeating unit derived from styrene, a polyester elastomer, a polyolefin elastomer, a polyurethane elastomer, a polyamide elastomer, a polyacryl elastomer, a silicone elastomer Elastomers, polyimide elastomers, etc. can be used. In particular, a polystyrene-based elastomer, a polyester-based elastomer, and a polyamide-based elastomer are preferable, and a polystyrene-based elastomer is more preferable from the viewpoint of heat resistance and peelability.

  In the present invention, the elastomer is preferably a hydrogenated product. In particular, a hydrogenated product of a polystyrene-based elastomer is preferable. When the elastomer is a hydrogenated product, thermal stability and storage stability are improved. Furthermore, the releasability and the removability of the temporary bonding composition after peeling are improved. When a hydrogenated product of polystyrene elastomer is used, the above effect is remarkable. The hydrogenated product means a polymer having a structure in which an elastomer is hydrogenated.

In the present invention, the elastomer preferably has a 5% thermal mass reduction temperature of 250 ° C. or higher when the temperature is increased from 25 ° C. at a temperature increase rate of 20 ° C./min, more preferably 300 ° C. or higher. Preferably, it is 350 degreeC or more, More preferably, it is 400 degreeC or more. Moreover, although an upper limit is not specifically limited, For example, 1000 degrees C or less is preferable and 800 degrees C or less is more preferable. According to this aspect, it can be set as the composition for temporary adhesion excellent in heat resistance.
The elastomer in the present invention can be deformed to 200% with a small external force at room temperature (20 ° C.) when the original size is 100%, and 130% or less in a short time when the external force is removed. It is preferable to have the property of returning to

<<<< Polystyrene Elastomer >>>>
There is no restriction | limiting in particular as a polystyrene-type elastomer, According to the objective, it can select suitably. For example, styrene-butadiene-styrene block copolymer (SBS), styrene-isoprene-styrene block copolymer (SIS), polystyrene-poly (ethylene-propylene) diblock copolymer (SEP), polystyrene-poly (ethylene -Propylene) -polystyrene triblock copolymer (SEPS), polystyrene-poly (ethylene-butylene) -polystyrene triblock copolymer (SEBS), polystyrene-poly (ethylene / ethylene-propylene) -polystyrene triblock copolymer. It is preferably at least one selected from the group consisting of (SEEPS).

  The proportion of the repeating unit derived from styrene in the polystyrene elastomer is preferably 90% by mass or less, more preferably 55% by mass or less, further preferably 48% by mass or less, still more preferably 35% by mass or less, and more preferably 33% by mass or less. Even more preferred. The lower limit of the ratio of the repeating unit derived from styrene may be 0% by mass, but may be 10% by mass or more. By setting it as such a range, the curvature of the laminated body which bonds substrates together with the composition for temporary adhesion can be suppressed more effectively.

As an embodiment of the polystyrene-based elastomer in the present invention, an elastomer A containing a repeating unit derived from styrene in a proportion of 10% by mass or more and 55% by mass or less in all repeating units, and a repeating unit derived from styrene in all repeating units. And an elastomer B contained in a proportion of more than 55% by mass and 95% by mass or less. By using the elastomer A and the elastomer B in combination, the occurrence of warpage can be effectively suppressed. It can be presumed that the mechanism for obtaining such an effect is as follows. That is, since the elastomer A is a relatively soft material, it is easy to form a layered temporary bonding composition (temporary bonding film) having elasticity. For this reason, when a laminate of a substrate and a carrier substrate is manufactured using the temporary bonding composition, and the substrate is polished to form a thin film, the temporary bonding composition is applied even if the polishing pressure is locally applied. An object (temporary adhesive film) is elastically deformed and easily returns to its original shape. As a result, excellent flat polishing properties can be obtained. Moreover, even if it heat-processes the laminated body of a carrier substrate, a to-be-processed substrate, and the composition for temporary bonding after grinding | polishing and it cools after that, the internal stress which generate | occur | produces at the time of cooling is a composition for temporary adhesion (temporary adhesive film) Can alleviate and effectively suppress the occurrence of warping.
Moreover, since the said elastomer B is a comparatively hard material, it can be set as the composition for temporary adhesion excellent in peelability by including the elastomer B.

  The mass ratio when blending the elastomer A and the elastomer B is preferably Elastomer A: Elastomer B = 1: 99 to 99: 1, more preferably 3:97 to 97: 3, and 5:95 to 95: 5. Is more preferable, and 10:90 to 90:10 is more preferable. If it is the said range, the effect mentioned above will be acquired more effectively.

The polystyrene-based elastomer is preferably a block copolymer of styrene and another monomer, more preferably a block copolymer in which one end or both ends are styrene blocks, and both ends are styrene blocks. It is particularly preferred. If both ends of the polystyrene elastomer are styrene blocks (repeating units derived from styrene), the heat resistance tends to be further improved. This is because a repeating unit derived from styrene having high heat resistance is present at the terminal. In particular, the block site of the repeating unit derived from styrene is preferably a reactive polystyrene hard block, which tends to be more excellent in heat resistance and chemical resistance. In addition, such an elastomer is more preferable from the viewpoint of solubility in a solvent and resistance to a resist solvent.
In addition, when the polystyrene elastomer is a hydrogenated product, the stability to heat is improved, and degradation such as decomposition and polymerization hardly occurs. Furthermore, it is more preferable from the viewpoint of solubility in a solvent and resistance to a resist solvent.
The amount of unsaturated double bonds of the polystyrene-based elastomer is preferably less than 15 mmol, more preferably less than 5 mmol, and more preferably less than 0.5 mmol per 1 g of the polystyrene-based elastomer from the viewpoint of peelability. Further preferred. In addition, the amount of unsaturated double bonds here does not include the amount of unsaturated double bonds in the benzene ring derived from styrene. The amount of unsaturated double bonds can be calculated by NMR (nuclear magnetic resonance) measurement.

  In the present specification, “a repeating unit derived from styrene” is a structural unit derived from styrene contained in a polymer when styrene or a styrene derivative is polymerized, and may have a substituent. Examples of the styrene derivative include α-methyl styrene, 3-methyl styrene, 4-propyl styrene, 4-cyclohexyl styrene, and the like. Examples of the substituent include an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an alkoxyalkyl group having 2 to 5 carbon atoms, an acetoxy group, and a carboxyl group.

  Examples of commercially available polystyrene elastomers include TUFPRENE A, TUFPRENE 125, TUFPRENE 126S, SORPREN T, ASAPRENE T-411, ASAPRENE T-432, ASAPRENE T-437, ASAPRENE T-438, ASAPRENE T-439, and Tuftec H1272. , Tuftec P1500, Tuftec H1052, Tuftec H1062, Tuftech M1943, Tuftec M1911, Tuftec H1041, Tuftec MP10, Tuftec M1913, Tuftec H1051, Tuftec H1053, Tuftec P2000, Tuftec H1043 (above, Asahi Kasei Chemicals AR) 850C, Elastomer AR-815C, Elastomer AR-840C, Elastomer AR-830C, Elasto -AR-860C, Elastomer AR-875C, Elastomer AR-885C, Elastomer AR-SC-15, Elastomer AR-SC-0, Elastomer AR-SC-5, Elastomer AR-710, Elastomer AR-SC-65, Elastomer AR SC-30, Elastomer AR-SC-75, Elastomer AR-SC-45, Elastomer AR-720, Elastomer AR-741, Elastomer AR-731, Elastomer AR-750, Elastomer AR-760, Elastomer AR-770, Elastomer AR-781, Elastomer AR-791, Elastomer AR-FL-75N, Elastomer AR-FL-85N, Elastomer AR-FL-60N, Elastomer AR-1050, Elastomer AR-1060 Elastomer AR-1040 (manufactured by Aron Kasei Co., Ltd.), Clayton D1111, Clayton D1113, Clayton D1114, Clayton D1117, Clayton D1119, Clayton D1124, Clayton D1126, Clayton D1161, Clayton D1162, Clayton D1163, Clayton D1164, Clayton D1165 Clayton D1183, Clayton D1193, Clayton DX406, Clayton D4141, Clayton D4150, Clayton D4153, Clayton D4158, Clayton D4270, Clayton D4433, Clayton D1170, Clayton D1171, Clayton D1173, Califlex IR0307, Califlex IR0310 Flex IR0401, Clayton D0242, Clayton D1101, Clayton D1102, Clayton D1116, Clayton D1118, Clayton D1133, Clayton D1152, Clayton D1153, Clayton D1155, Clayton D1184, Clayton D1186, Clayton D1189, Clayton D1192, Clayton DX405, Clayton DX405 Clayton DX410, Clayton DX414, Clayton DX415, Clayton A1535, Clayton A1536, Clayton FG1901, Clayton FG1924, Clayton G1640, Clayton G1641, Clayton G1642, Clayton G1643, Clayton G1645, Clayton G1633, Layton G1650, Clayton G1651, Clayton G1652 (G1652MU-1000), Clayton G1654, Clayton G1657, Clayton G1660, Clayton G1726, Clayton G1701, Clayton G1702, Clayton G1730, Clayton G1750, Clayton G1765, Clayton G4609 (Clayton G4610) Polymer Japan Co., Ltd.), TR2000, TR2001, TR2003, TR2250, TR2500, TR2601, TR2630, TR2787, TR2827, TR1086, TR1600, SIS5002, SIS5200, SIS5250, SIS5405, SIS5505, Dynalon6100P, Dynalon4600P, Dynaro 6200P, Dynalon 4630P, Dynalon 8601P, Dynalon 8630P, Dynalon 8600P, Dynalon 8903P, Dynalon 6201B, Dynalon 1321P, Dynalon 1320P, Dynalon 2324P (above, manufactured by JSR Corporation), Denka STR Series (Electrochemical Industry Co., Ltd.) )), Quintac 3520, Quintac 3433N, Quintac 3421, Quintac 3620, Quintac 3450, Quintac 3460 (manufactured by Nippon Zeon), TPE-SB series (manufactured by Sumitomo Chemical Co., Ltd.), Lavalon series (Mitsubishi Chemical Corporation), Septon 1001, Septon 1020, Septon 2002, Septon 2004, Septon 2005, Septon 2006, Septon 2007, Septon 2063, Septon 2104, Septon 4033, Septon 4044, Septon 4055, Septon 4077, Septon 4099, Septon HG252, Septon 8004, Septon 8006, Septon 8007, Septon 8076, Septon 8104, Septon V9461, Septon V9475, Septon V9827, Hibler 7311 , Hibler 7125, Hibler 5127, Hibler 5125 (above, manufactured by Kuraray Co., Ltd.), Sumiflex (manufactured by Sumitomo Bakelite Co., Ltd.), Rheostomer, Actimer (above, manufactured by Riken Technos Co., Ltd.), and the like.

<<< Polyester elastomer >>>
There is no restriction | limiting in particular as a polyester-type elastomer, According to the objective, it can select suitably. Examples thereof include those obtained by polycondensation of a dicarboxylic acid or a derivative thereof and a diol compound or a derivative thereof.
Examples of the dicarboxylic acid include aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, and naphthalenedicarboxylic acid, and aromatic dicarboxylic acids in which hydrogen atoms of these aromatic rings are substituted with a methyl group, an ethyl group, a phenyl group, or the like. Examples thereof include aliphatic dicarboxylic acids having 2 to 20 carbon atoms such as acid, sebacic acid and dodecanedicarboxylic acid, and alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid. These may be used alone or in combination of two or more.
Examples of the diol compound include aliphatic diols such as ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,10-decanediol, and 1,4-cyclohexanediol. Examples thereof include alicyclic diols and divalent phenols represented by the following structural formulas.

In the above formula, Y ^DO represents any one of an alkylene group having 2 to 10 carbon atoms, a cycloalkylene group having 4 to 8 carbon atoms, —O—, —S—, and —SO ₂ —, or a single bond. Represent. R ^DO1 and R ^DO2 each independently represent a halogen atom or an alkyl group having 1 to 12 carbon atoms. p ^do1 and p ^do2 each independently represent an integer of 0 to 4, and n ^do1 represents 0 or 1.

Specific examples of the divalent phenol include bisphenol A, bis- (4-hydroxyphenyl) methane, bis- (4-hydroxy-3-methylphenyl) propane, resorcin and the like. These may be used alone or in combination of two or more.
Also, as the polyester elastomer, a multi-block copolymer having an aromatic polyester (for example, polybutylene terephthalate) portion as a hard segment component and an aliphatic polyester (for example, polytetramethylene glycol) portion as a soft segment component should be used. You can also. The multi-block copolymer includes various grades depending on the kind, ratio, and molecular weight of the hard segment and the soft segment. Specific examples include Hytrel (manufactured by Toray DuPont Co., Ltd.), Perprene (manufactured by Toyobo Co., Ltd.), Primalloy (manufactured by Mitsubishi Chemical Corporation), Nouvelan (manufactured by Teijin Limited), Espel 1612 and 1620 (and above). , Hitachi Chemical Co., Ltd.).

<<< Polyolefin Elastomer >>>
There is no restriction | limiting in particular as a polyolefin-type elastomer, According to the objective, it can select suitably. Examples thereof include copolymers of α-olefins having 2 to 20 carbon atoms such as ethylene, propylene, 1-butene, 1-hexene and 4-methyl-1-pentene. Examples thereof include an ethylene-propylene copolymer (EPR) and an ethylene-propylene-diene copolymer (EPDM). Moreover, the copolymer of a C2-C20 nonconjugated diene, such as dicyclopentadiene, 1,4-hexadiene, cyclooctadiene, methylene norbornene, ethylidene norbornene, butadiene and isoprene, and an α-olefin are exemplified. Moreover, the carboxy modified nitrile rubber which copolymerized methacrylic acid to the butadiene-acrylonitrile copolymer is mentioned. Specifically, ethylene / α-olefin copolymer rubber, ethylene / α-olefin / non-conjugated diene copolymer rubber, propylene / α-olefin copolymer rubber, butene / α-olefin copolymer For example, rubber.
Commercially available products include Miralastomer (Mitsui Chemicals), Thermoran (Mitsubishi Chemical) EXACT (ExxonMobil), ENGAGE (Dow Chemical Japan), Espolex (Sumitomo Chemical) ), Sarlink (manufactured by Toyobo Co., Ltd.), Newcon (manufactured by Nippon Polypro Co., Ltd.), EXCELLINK (manufactured by JSR Corporation), and the like.

<<< Polyurethane Elastomer >>>
There is no restriction | limiting in particular as a polyurethane-type elastomer, According to the objective, it can select suitably. For example, an elastomer containing structural units of a hard segment composed of low-molecular glycol and diisocyanate and a soft segment composed of a high-molecular (long-chain) diol and diisocyanate can be used.
Examples of the polymer (long chain) diol include polypropylene glycol, polytetramethylene oxide, poly (1,4-butylene adipate), poly (ethylene / 1,4-butylene adipate), polycaprolactone, and poly (1,6-hexene). Xylene carbonate), poly (1,6-hexylene neopentylene adipate) and the like. The number average molecular weight of the polymer (long chain) diol is preferably 500 to 10,000.
As the low molecular weight glycol, short chain diols such as ethylene glycol, propylene glycol, 1,4-butanediol, and bisphenol A can be used. The number average molecular weight of the short chain diol is preferably 48 to 500.
Examples of commercially available polyurethane elastomers include PANDEX T-2185, T-2983N (manufactured by DIC Corporation), milactolan (manufactured by Nippon Miractoran Corporation), elastollan (manufactured by BASF Japan Ltd.), resamine ( Dainichi Seika Kogyo Co., Ltd.), Peresen (Dow Chemical Japan Co., Ltd.), Iron Rubber (NOK Co., Ltd.), Mobilon (Nisshinbo Chemical Co., Ltd.), and the like.

<<< Polyamide elastomer >>>
There is no restriction | limiting in particular as a polyamide-type elastomer, According to the objective, it can select suitably. For example, an elastomer using a polyamide such as polyamide 6, 11, or 12 as a hard segment and a polyether or polyester such as polyoxyethylene, polyoxypropylene, or polytetramethylene glycol as a soft segment. It is done. This elastomer is roughly classified into two types, a polyether block amide type and a polyether ester block amide type.
Commercially available products include UBE polyamide elastomer, UBESTA XPA (manufactured by Ube Industries), Daiamide (manufactured by Daicel Evonik), PEBAX (manufactured by ARKEMA), Grilon ELX (manufactured by Emschemy Japan Co., Ltd.), and GREAT (Toyobo Co., Ltd.), polyether ester amide PA-200, PA-201, TPAE-12, TPAE-32, polyester amide TPAE-617, TPAE-617C (above, manufactured by T & K TOKA). It is done.

<<< Polyacrylic elastomer >>>
There is no restriction | limiting in particular as a polyacrylic-type elastomer, According to the objective, it can select suitably. For example, copolymers containing acrylic acid esters such as ethyl acrylate, butyl acrylate, methoxyethyl acrylate, ethoxyethyl acrylate, etc. as the main component of the monomer material, or copolymers of acrylic acid esters with glycidyl methacrylate, allyl glycidyl ether, etc. Is mentioned. Furthermore, the thing etc. which copolymerize acrylic acid ester and crosslinking point monomers, such as acrylonitrile and ethylene, etc. are mentioned. Specific examples include acrylonitrile-butyl acrylate copolymer, acrylonitrile-butyl acrylate-ethyl acrylate copolymer, acrylonitrile-butyl acrylate-glycidyl methacrylate copolymer, and the like.

<<<< Other Elastomers >>>>
In the present invention, a rubber-modified epoxy resin (epoxy elastomer) can be used as the elastomer. Epoxy elastomers include, for example, bisphenol F-type epoxy resin, bisphenol A-type epoxy resin, salicylaldehyde-type epoxy resin, phenol novolac-type epoxy resin or cresol novolac-type epoxy resin with some or all of the epoxy groups at both terminal carboxylic acids. It can be obtained by modification with modified butadiene-acrylonitrile rubber, terminal amino-modified silicone rubber or the like.

<< Thermoplastic resin other than elastomer >>
In the present invention, a thermoplastic resin other than the above-described elastomer (hereinafter, also simply referred to as “other thermoplastic resin”) can be used. Other thermoplastic resins can be used alone or in combination of two or more.
Specific examples of other thermoplastic resins include, for example, thermoplastic hydrocarbon resins, acrylic resins, cycloolefin resins, thermoplastic siloxane resins, unsaturated polyester resins, thermoplastic polyimide resins, polyvinyl chloride resins, and polyvinyl acetate resins. Polycarbonate resin, polyphenylene ether resin, polybutylene terephthalate resin, polyethylene terephthalate resin, polyphenylene sulfide resin, polysulfone resin, polyethersulfone resin, polyarylate resin, cellulose resin and the like.

In the present invention, any hydrocarbon resin can be used.
The hydrocarbon resin basically means a resin consisting of only carbon atoms and hydrogen atoms, but if the basic skeleton is a hydrocarbon resin, it may contain other atoms as a side chain. That is, when a functional group other than a hydrocarbon group is directly bonded to a main chain, such as an acrylic resin, a polyvinyl alcohol resin, a polyvinyl acetal resin, or a polyvinyl pyrrolidone resin, to a hydrocarbon resin composed of only carbon atoms and hydrogen atoms. It is included in the hydrocarbon resin in the invention. In this case, the content of the repeating unit in which the hydrocarbon group is directly bonded to the main chain is 30 mol% or more based on the total repeating unit of the resin. Is preferred.
Examples of the hydrocarbon resin meeting the above conditions include terpene resin, terpene phenol resin, modified terpene resin, hydrogenated terpene resin, hydrogenated terpene phenol resin, rosin, rosin ester, hydrogenated rosin, hydrogenated rosin ester, and polymerized rosin. , Polymerized rosin ester, modified rosin, rosin modified phenolic resin, alkylphenol resin, aliphatic petroleum resin, aromatic petroleum resin, hydrogenated petroleum resin, modified petroleum resin, alicyclic petroleum resin, coumarone petroleum resin, indene petroleum resin, polystyrene -Polyolefin copolymers, olefin polymers (for example, methylpentene copolymers), and cycloolefin polymers (for example, norbornene copolymers, dicyclopentadiene copolymers, tetracyclododecene copolymers) and the like. .

The acrylic resin in the present invention is a resin obtained by polymerizing a (meth) acrylate monomer. (Meth) acrylate monomers include 2-ethylhexyl (meth) acrylate, ethyl (meth) acrylate, methyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, pentyl (meth) acrylate, n- Octyl (meth) acrylate, isooctyl (meth) acrylate, isononyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, hexyl (meth) acrylate, n-nonyl (meth) acrylate, isoamyl (meth) Acrylate, n-decyl (meth) acrylate, isodecyl (meth) acrylate, dodecyl (meth) acrylate, isobornyl (meth) acrylate, cyclohexyl (meth) acrylate, phenylmeta Acrylate), Benjirumeta (acrylate), and 2-methylbutyl (meth) acrylate.
The acrylic resin may be copolymerized with a (meth) acrylate monomer and another monomer without departing from the gist of the present invention. When copolymerizing a (meth) acrylate monomer and another monomer, the amount of the other monomer is preferably 10 mol% or less of the total monomers.
In addition to the above, Mitsubishi Rayon Co., Ltd., Acripet MF 001, 3M Japan Co., Ltd., LC-5320 F1035 and the like are exemplified.

In the present invention, an acrylic resin having an organopolysiloxane in the side chain is also preferable. Examples of the acrylic resin having an organopolysiloxane in the side chain include acrylic resins represented by the following formula (3).
Formula (3)
In the above formula (3), when there are a plurality of R ^{1 s} , they may be the same or different, and —CH ₃ , —C ₂ H ₅ , —CH ₃ (CH ₂ ) ₂ or —CH ₃ (CH ₂ ) ₃ is substituted. Show. When there are a plurality of R ^{2 s} , they may be the same or different and each represents —H, —CH ₃ , —C ₂ H ₅ , —CH ₃ (CH ₂ ) ₂ or —CH ₃ (CH ₂ ) ₃ . When there are a plurality of R ^{3 s} , they may be the same or different and represent —H or —CH ₃ . When there are a plurality of R ^{4 s} , they may be the same or different, and —H, —CH ₃ , —C ₂ H ₅ , —CH ₃ (CH ₂ ) ₂ , —CH ₃ (CH ₂ ) ₃ , or an epoxy group, An alkyl group having 1 to 6 carbon atoms substituted with at least one functional group selected from the group consisting of a hydroxyl group, a carboxyl group, an amino group, an alkoxy group, a vinyl group, a silanol group and an isocyanate group is shown. a is 50 to 150, b is 50 to 150, and c is 80 to 600. Moreover, m is 1-10.
Specific examples of the acrylic resin having an organopolysiloxane in the side chain include silicone graft acrylic resins manufactured by Shin-Etsu Chemical Co., Ltd., trade names: X-24-798A, X-22-8004 (R ⁴ : C ₂ H ₄ OH, the functional group equivalent: 3250 (g / mol)) , X-22-8009 (R 4: Si (OCH 3) 3 containing an alkyl group, the functional group equivalent: 6200 (g / mol)) , X-22- 8053 (R ⁴ : H, functional group equivalent: 900 (g / mol)), X-22-8084, X-22-8084EM, X-22-8195 (R ⁴ : H, functional group equivalent: 2700 (g / mol)), Toagosei Co., Ltd. Cymac series (US-270, US-350, US-352, US-380, US-413, US-450, etc.), Reseta GS-1000 series ( S-1015, GS-1302, etc.) and the like.

  Examples of cycloolefin polymers include norbornene polymers, monocyclic olefin polymers, cyclic conjugated diene polymers, vinyl alicyclic hydrocarbon polymers, and hydrides of these polymers. Preferred examples of the cycloolefin polymer include addition (co) polymers containing at least one repeating unit represented by the following formula (II), and at least one repeating unit represented by the formula (I) And addition (co) polymers further comprising Another preferred example of the cycloolefin polymer is a ring-opening (co) polymer containing at least one cyclic repeating unit represented by the formula (III).

In formula, m represents the integer of 0-4. R ^{1 to} R ⁶ each represent a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and X ^{1 to} X ³ and Y ^{1 to} Y ³ are respectively a hydrogen atom and 1 to 10 carbon atoms. hydrocarbon group, a halogen atom, a hydrocarbon group having 1 to 10 carbon atoms substituted with a halogen ^{_{atom, - (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 (—CO) ₂ O, (—CO) ₂ NR ¹⁷ composed of X ¹ and Y ¹ , X ² and Y ² , or X ³ and Y ³ . R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ and R ¹⁷ are each a hydrogen atom or a hydrocarbon group (preferably a hydrocarbon group having 1 to 20 carbon atoms), Z is a carbon Represents a hydrogen group or a hydrocarbon group substituted with halogen, W represents SiR ¹⁸ _p D _3-p (R ¹⁸ represents a hydrocarbon group having 1 to 10 carbon atoms, D represents a halogen atom, Represents OCOR ¹⁸ or —OR ¹⁸ , and p represents an integer of 0 to 3. n represents an integer of 0 to 10.
In formula (III), R ⁵ and R ⁶ are preferably hydrogen atoms or methyl groups, X ³ and Y ³ are more preferably hydrogen atoms, and other groups are appropriately selected.

  The norbornene-based polymer is disclosed in JP-A-10-7732, JP-T 2002-504184, US2004 / 229157A1, WO2004 / 070463A1, and the like. The norbornene-based polymer can be obtained by addition polymerization of norbornene-based polycyclic unsaturated compounds. If necessary, a norbornene-based polycyclic unsaturated compound and ethylene, propylene, butene; conjugated dienes such as butadiene and isoprene; non-conjugated dienes such as ethylidene norbornene can also be subjected to addition polymerization. The norbornene-based polymer is sold under the name of Apel by Mitsui Chemicals, Inc., and has different glass transition temperatures (Tg) such as APL8008T (Tg 70 ° C.), APL 6013T (Tg 125 ° C.) or APL 6015T (Tg 145 ° C.). There is a grade. Pellets such as TOPAS 8007, 5013, 6013, 6015 are sold by Polyplastics. Further, Appear 3000 is sold by Ferrania.

The hydrides of norbornene polymers are disclosed in JP-A-1-240517, JP-A-7-196736, JP-A-60-26024, JP-A-62-19801, and JP-A-2003-1159767. Alternatively, as disclosed in JP-A-2004-309979, etc., it can be produced by subjecting a polycyclic unsaturated compound to addition polymerization or metathesis ring-opening polymerization, followed by hydrogenation.
The norbornene-based polymer is sold under the trade name of Arton G or Arton F by JSR Co., Ltd., and ZEONOR ZF14, ZF16, ZEONEX 250, and the like from Zeon Corporation. These are commercially available under the trade names 280 and 480R, and these can be used.

  As the thermoplastic siloxane polymer, a siloxane polymer having a repeating unit represented by the following formula (1) is preferable.

In formula (1), R < ¹ > -R < ⁴ > shows monovalent hydrocarbon groups, such as a C1-C8 alkyl group which may be the same or different. m is an integer of 1 to 100, B is a positive integer, and A is 0 or a positive integer. X is a divalent organic group represented by the following formula (2).
In formula (2), Z is a divalent organic group selected from any of the following structural units, and n is 0 or 1. R ⁵ and R ⁶ are each independently an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 2 to 4 carbon atoms, and may be the same or different from each other. k is independently 0, 1, or 2, respectively.

In the formula (1), specific examples of R ^{1 to} R ⁴ include a methyl group, an ethyl group, a phenyl group, and the like, and m is preferably an integer of 3 to 60, more preferably 8 to 40. Moreover, B / A is 0-20, especially 0.5-5.

  Details of the siloxane polymer can be referred to the descriptions in paragraph numbers 0038 to 0044 of JP2013-243350A, the contents of which are incorporated herein.

A thermoplastic siloxane polymer can be used as the siloxane polymer.
The thermoplastic siloxane polymer is composed of R ²¹ R ²² R ²³ SiO _1/2 units (R ²¹ , R ²² , R ²³ are each an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms or a hydroxyl group. there.) an organopolysiloxane and containing _{SiO 4/2} units, the molar ratio of the ^R 21 ^R 22 ^R 23 _{SiO 1/2} units _{/ SiO 4/2} units is 0.6 to 1.7, the following The organopolysiloxane represented by formula (4) is partially dehydrated and condensed, and the ratio of the organopolysiloxane to be dehydrated and condensed to the organopolysiloxane is 99: 1 to 50:50. The weight average molecular weight is preferably 200,000 to 1,500,000.
Formula (4)
(In Formula (4), R ¹¹ and R ¹² each independently represent a monovalent hydrocarbon group having 1 to 10 carbon atoms that may have a substituent, and n is 5000 to 10,000.)

In the above formula (4), R ¹¹ and R ¹² are specifically methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, t-butyl group, n-pentyl group, and cyclopentyl group. , Hydrocarbon groups such as alkyl groups such as n-hexyl groups, cycloalkyl groups such as cyclohexyl groups, aryl groups such as phenyl groups and tolyl groups, and some or all of the hydrogen atoms of these hydrocarbon groups are substituted with halogen atoms Group, preferably a methyl group and a phenyl group.

The weight average molecular weight of the thermoplastic organopolysiloxane is preferably 200,000 or more, more preferably 350,000 or more, and preferably 1,500,000 or less, more preferably 1,000,000 or less. The content of low molecular weight components 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 commercial item, SILRES 604 (made by Asahi Kasei Wacker Silicone) is illustrated.

As the thermoplastic polyimide resin, one obtained by subjecting tetracarboxylic dianhydride and diamine to a condensation reaction by a known method can be used.
As a known method, for example, a method in which a tetracarboxylic acid dianhydride and a diamine are mixed in an approximately equimolar amount in a solvent, and a polyamic acid obtained by reacting at a reaction temperature of 80 ° C. or lower is dehydrated and cyclized. . Here, “substantially equimolar” means that the molar ratio of tetracarboxylic dianhydride to diamine is close to 1: 1. If necessary, the composition ratio of tetracarboxylic dianhydride and diamine is 0.5 to 2.0 mol of diamine with respect to 1.0 mol of tetracarboxylic dianhydride. You may adjust as follows. By adjusting the composition ratio of tetracarboxylic dianhydride and diamine within the above range, the weight average molecular weight of the thermoplastic polyimide resin can be adjusted.

  The tetracarboxylic dianhydride is not particularly limited, and examples thereof include pyromellitic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,2 ′, 3,3′-biphenyltetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propane dianhydride 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride, 1,1-bis (3,4-dicarboxyphenyl) ethane dianhydride, bis (2,3-dicarboxyphenyl) methane Dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, Screw 3,4-dicarboxyphenyl) ether dianhydride, benzene-1,2,3,4-tetracarboxylic dianhydride, 3,4,3 ′, 4′-benzophenone tetracarboxylic dianhydride, 2, 3,2 ′, 3′-benzophenone tetracarboxylic dianhydride, 2,3,3 ′, 4′-benzophenone tetracarboxylic dianhydride, 1,2,5,6-naphthalene tetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,2,4,5-naphthalenetetracarboxylic dianhydride, 2, 6-dichloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 2,7-dichloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 2,3,6,7- Tetrachloronaphthalene -1,4,5,8-tetracarboxylic dianhydride, phenanthrene-1,8,9,10-tetracarboxylic dianhydride, pyrazine-2,3,5,6-tetracarboxylic dianhydride, Thiophene-2,3,5,6-tetracarboxylic dianhydride, 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride, 3,4,3 ′, 4′-biphenyltetracarboxylic dianhydride Anhydride, 2,3,2 ′, 3′-biphenyltetracarboxylic dianhydride, bis (3,4-dicarboxyphenyl) dimethylsilane dianhydride, bis (3,4-dicarboxyphenyl) methylphenylsilane Dianhydride, bis (3,4-dicarboxyphenyl) diphenylsilane dianhydride, 1,4-bis (3,4-dicarboxyphenyldimethylsilyl) benzene dianhydride, 1,3-bis (3,4 - Carboxyphenyl) -1,1,3,3-tetramethyldicyclohexane dianhydride, p-phenylenebis (trimellitic anhydride), ethylenetetracarboxylic dianhydride, 1,2,3,4-butanetetracarboxylic acid Dianhydride, decahydronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 4,8-dimethyl-1,2,3,5,6,7-hexahydronaphthalene-1,2,5 , 6-tetracarboxylic dianhydride, cyclopentane-1,2,3,4-tetracarboxylic dianhydride, pyrrolidine-2,3,4,5-tetracarboxylic dianhydride, 1,2,3 , 4-cyclobutanetetracarboxylic dianhydride, bisoxabicyclo [2,2,1] heptane-2,3-dicarboxylic dianhydride, bicyclo- [2,2,2] -oct-7-ene-2 , 3, 5 6-tetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2′-bis [4- (3,4-dicarboxyphenyl) phenyl] propane Anhydride, 2,2'-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride, 2,2'-bis [4- (3,4-dicarboxyphenyl) phenyl] hexafluoropropane dianhydride 4,4′-bis (3,4-dicarboxyphenoxy) diphenyl sulfide dianhydride, 1,4-bis (2-hydroxyhexafluoroisopropyl) benzenebis (trimellitic anhydride), 1,3- Bis (2-hydroxyhexafluoroisopropyl) benzenebis (trimellitic anhydride), 5- (2,5-dioxotetrahydrofuryl) -3-methyl 3-cyclohexene-1,2-dicarboxylic dianhydride, tetrahydrofuran-2,3,4,5-tetracarboxylic dianhydride, 4,4′-oxydiphthalic dianhydride, 1,2- (ethylene) bis (Trimellitic anhydride), 1,3- (trimethylene) bis (trimellitic anhydride), 1,4- (tetramethylene) bis (trimellitic anhydride), 1,5- (pentamethylene) bis (trimellitic anhydride), 1,6- (hexamethylene) bis (trimellitic anhydride), 1,7- (heptamethylene) bis (trimellitic anhydride), 1,8- (octamethylene) bis (trimellitic anhydride), 1,9- ( Nonamethylene) bis (trimellitic anhydride), 1,10- (decamethylene) bis (trimellitic anhydride), 1,12- (dodecamethyle) ) Bis (trimellitate anhydride), 1,16- (hexadecamethylene) bis (trimellitate anhydride), 1,18- (octadecamethylene) bis (trimellitate anhydride) and the like. One species can be used alone, or two or more species can be used in combination. Among these, 3,4,3 ′, 4′-benzophenone tetracarboxylic dianhydride, 2,3,2 ′, 3′-benzophenone tetracarboxylic dianhydride, 2,3,3 ′, 4′- Benzophenone tetracarboxylic dianhydride is preferred, and 3,4,3 ′, 4′-benzophenone tetracarboxylic dianhydride is more preferred.

There is no restriction | limiting in particular as diamine, For example, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3 , 3′-diaminodiphenylmethane, 3,4′-diaminodiphenylmethane, bis (4-amino-3,5-dimethylphenyl) methane, bis (4-amino-3,5-diisopropylphenyl) methane, 3,3′- Diaminodiphenyldifluoromethane, 3,4'-diaminodiphenyldifluoromethane, 4,4'-diaminodiphenyldifluoromethane, 3,3'-diaminodiphenylsulfone, 3,4'-diaminodiphenylsulfone, 4,4'-diaminodiphenyl Sulfone, 3,3'-diaminodiph Nyl sulfide, 3,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl ketone, 3,4'-diaminodiphenyl ketone, 4,4'-diaminodiphenyl ketone, 3- (4-aminophenyl) -1,1,3-trimethyl-5-aminoindane, 2,2-bis (3-aminophenyl) propane, 2,2 ′-(3,4′-diaminodiphenyl) propane, 2 , 2-bis (4-aminophenyl) propane, 2,2-bis (3-aminophenyl) hexafluoropropane, 2,2- (3,4'-diaminodiphenyl) hexafluoropropane, 2,2-bis ( 4-aminophenyl) hexafluoropropane, 1,3-bis (3-aminophenoxy) benzene, 1,4-bis (3-aminophenoxy) ) Benzene, 1,4-bis (4-aminophenoxy) benzene, 3,3 ′-(1,4-phenylenebis (1-methylethylidene)) bisaniline, 3,4 ′-(1,4-phenylenebis ( 1-methylethylidene)) bisaniline, 4,4 ′-(1,4-phenylenebis (1-methylethylidene)) bisaniline, 2,2-bis (4- (3-aminophenoxy) phenyl) propane, 2,2 -Bis (4- (3-aminophenoxy) phenyl) hexafluoropropane, 2,2-bis (4- (4-aminophenoxy) phenyl) hexafluoropropane, bis (4- (3-aminoethoxy) phenyl) sulfide Bis (4- (4-aminoethoxy) phenyl) sulfide, bis (4- (3-aminoethoxy) phenyl) sulfone, bis (4- (4- Minoethoxy) phenyl) sulfone, 3,3′-dihydroxy-4,4′-diaminobiphenyl, aromatic diamines such as 3,5-diaminobenzoic acid, 1,3-bis (aminomethyl) cyclohexane, 2,2-bis (4-aminophenoxyphenyl) propane, polyoxypropylenediamine, 4,9-dioxadodecane-1,12-diamine, 4,9,14-trioxaheptadecane-1,17-diamine, 1,2-diaminoethane 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, , 10-diaminodecane, 1,11-diaminoundecane, 1,12-diaminododecane, 1,2-diaminosi Examples include chlorohexane and 1,3-bis (3-aminopropyl) tetramethyldisiloxane.
Among these diamines, 3- (4-aminophenyl) -1,1,3-trimethyl-5-aminoindane, 1,3-bis (3-aminopropyl) tetramethyldisiloxane, polyoxypropylene diamine, 2 , 2-bis (4-aminophenoxyphenyl) propane, 4,9-dioxadodecane-1,12-diamine, 1,6-diaminohexane, and 4,9,14-trioxaheptadecane-1,17- One or more selected from the group consisting of diamines are preferred, and 3- (4-aminophenyl) -1,1,3-trimethyl-5-aminoindane is more preferred.

Examples of the solvent used in the reaction of the tetracarboxylic dianhydride and diamine include N, N-dimethylacetamide, N-methyl-2-pyrrolidone, and N, N-dimethylformamide. In order to adjust the solubility of raw materials and the like, a nonpolar solvent (for example, toluene or xylene) may be used in combination.
The reaction temperature between the tetracarboxylic dianhydride and the diamine is preferably less than 100 ° C, more preferably less than 90 ° C. The imidation of polyamic acid is typically performed by heat treatment under an inert atmosphere (typically vacuum or nitrogen atmosphere). The heat treatment temperature is preferably 150 ° C. or higher, more preferably 180 to 450 ° C.

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

In the present invention, the thermoplastic polyimide resin is at least one solvent selected from γ-butyrolactone, cyclopentanone, N-methylpyrrolidone, N-ethyl-2-pyrrolidone, cyclohexanone, glycol ether, dimethyl sulfoxide and tetramethylurea. A thermoplastic polyimide resin having a solubility at 25 ° C. of 10% by mass or more is preferable.
Examples of the thermoplastic polyimide resin having such solubility include 3,4,3 ′, 4′-benzophenonetetracarboxylic dianhydride and 3- (4-aminophenyl) -1,1,3-trimethyl. Examples thereof include thermoplastic polyimide resins obtained by reacting with -5-aminoindane. This thermoplastic polyimide resin is particularly excellent in heat resistance.

A commercially available product may be used as the thermoplastic polyimide resin. For example, Durimide (registered trademark) 200, 208A, 284 (manufactured by FUJIFILM Corporation), GPT-LT (manufactured by Gunei Chemical Industry Co., Ltd.), SOXR-S, SOXR-M, SOXR-U, SOXR -C (Nippon Advanced Paper Industries Co., Ltd.), EXTEM VH1003, VH1003F, VH1003M, XH1015 (above, SABIC Japan GK) are included.
In addition, the thermoplastic resins described in paragraphs 0065 to 0083 of WO2016 / 076261 can also be preferably used.

<< Thermosetting resin >>
In the present invention, a thermosetting resin can also be used as the resin. Examples of the thermosetting resin include an epoxy resin and a phenol resin, and it is preferable that at least an epoxy resin is included.

As an epoxy resin, the epoxy resin represented by Formula (11) is illustrated.
Formula (11)
In the above formula (11), R 1 and R 2 are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. a is an integer of 0 to 3, b is an integer of 0 to 4, n is an average value, and is an integer of 1 to 5.
Formula (12)
In the above formula (12), X is a group selected from a single bond, —O—, —S—, — (R 2) C (R 2) —, and R 1 is an alkyl group having 1 to 6 carbon atoms. It may be the same or different. m is an integer of 0-4. R2 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms and may be the same as or different from each other.

  The epoxy resin (A) represented by the formula (11) and the epoxy resin (B) represented by the formula (12) are preferably used in combination. The mass ratio [(A) / (B)] when blending the epoxy resin (A) and the epoxy resin (B) is preferably 10/90 to 90/10, more preferably 20/80 to 70 /. 30, particularly preferably 30/70 to 50/50.

As a phenol resin, resin represented by Formula (13) is preferable.
Formula (13)
In the above formula (13), R1 and R2 are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. a is an integer of 0 to 3, b is an integer of 0 to 4, n is an average value, and is an integer of 1 to 5.

Although it does not specifically limit as a butadiene acrylonitrile copolymer, The compound represented by Formula (14) which has a carboxyl group at the both ends of the structure is preferable.
Formula (14)
In the above formula (14), Bu represents butadiene and ACN represents acrylonitrile. x is a positive number less than 1, y is a positive number less than 1, and x + y = 1. z is an integer of 50-80.

  In addition, you may use the thermosetting resin as described in Paragraphs 0024-0034 of Unexamined-Japanese-Patent No. 2006-274184, Furthermore, it is preferable to blend according to the blend form of the thermosetting resin as described in the said paragraph. The contents of paragraphs 0024 to 0034 of JP-A-2006-274184 are incorporated in this specification.

  Further, when a thermosetting resin is added to the temporary bonding composition, the curing accelerator (triphenylphosphine or the like) described in paragraph 0035 of JP-A-2006-274184, the wax (carbana) described in paragraph 0037 is used. Wax) or the like may be blended.

<< Tension modulus E of resin >>
The resin preferably has a tensile elastic modulus E of 1 MPa or more and 4000 MPa or less, more preferably 1 MPa or more and 100 MPa or less, more preferably 1 MPa or more, at 25 ° C., in accordance with JIS (Japanese Industrial Standard) K 7161: 1994. More preferably, it is 60 MPa or less, more preferably 1 MPa or more and 35 MPa or less, still more preferably 1 MPa or more and 20 MPa or less, still more preferably 1 MPa or more and 15 MPa or less, and 3 MPa or more and 10 MPa or less. It is even more preferable. By setting it as such a range, it becomes possible to suppress curvature more effectively.

<< Resin compounding amount >>
The composition for temporary bonding used in the present invention preferably contains the resin in a proportion of 50.00 to 99.99% by mass in the total solid content of the temporary bonding composition (all components excluding the solvent), More preferably, it is contained at a rate of 70.00 to 99.99% by mass, and particularly preferably at a rate of 88.00 to 99.99% by mass. When the resin content is within the above range, the adhesiveness and the peelability are excellent.
When using an elastomer as the resin, the elastomer is preferably included in the total solid content of the temporary bonding composition in a proportion of 50.00 to 99.99% by mass, and in a proportion of 70.00 to 99.99% by mass. It is more preferable to include it, and it is especially preferable to include it in the ratio of 88.0 to 99.99 mass%. If the content of the elastomer is in the above range, the adhesiveness and peelability are excellent. When two or more elastomers are used, the total is preferably in the above range.
Moreover, when using an elastomer as resin, it is preferable to contain the content of the elastomer in the resin total mass in the ratio of 50-100 mass%, It is more preferable to include in the ratio of 70-100 mass%, 80-100 mass It is more preferable to include it in the ratio of%, and it is still more preferable to include in the ratio of 90-100 mass%. The resin may be substantially only an elastomer. In addition, when the resin is substantially only an elastomer, the content of the elastomer in the total mass of the resin is preferably 99% by mass or more, more preferably 99.9% by mass or more, and only the elastomer is included. Even more preferred.

<Thermal polymerizable monomer>
The temporary bonding composition of the present invention may contain a powdery or granular thermopolymerizable monomer instead of or together with the resin. By applying thermal energy to the thermopolymerizable monomer, it is cured to obtain a temporary adhesive film. The thermopolymerizable monomer is not particularly defined as long as it is a powdery or granular thermopolymerizable monomer at 25 ° C. and 101,300 Pa. For example, a thermosetting (meth) acrylate monomer is exemplified. The details of the thermosetting (meth) acrylate monomer are exemplified by the (meth) acrylate monomer that is a raw material for the above-mentioned acrylic resin.

  When the composition for temporary adhesion contains a thermopolymerizable monomer, it is preferable that the thermopolymerizable monomer is contained in the total solid content of the composition for temporary adhesion in a proportion of 50.00 to 99.99% by mass. More preferably, it is contained at a rate of 00 to 99.99% by mass, and more preferably at a rate of 88.00 to 99.99% by mass. If content of a thermopolymerizable monomer is the said range, it will be excellent in adhesiveness and peelability. When two or more thermopolymerizable monomers are used, the total is preferably within the above range.

<Release agent>
The composition for temporary bonding used by this invention contains a mold release agent. As the release agent, a compound containing at least one of a fluorine atom and a silicon atom is preferable, a compound containing a silicon atom is more preferable, and a silicone compound is more preferable.
The release agent is preferably oily at 25 ° C. and 101,300 Pa.
The silicone compound is a compound containing a Si—O bond, and examples thereof include low molecular weight silicones such as polyether-modified silicone, silane coupling agent, silicone resin, silicone rubber, and cyclic siloxane, and are preferably polyether-modified silicone. .
The refractive index of light of the silicone compound is preferably 1.350 to 1.480, more preferably 1.390 to 1.440, and still more preferably 1.400 to 1.430.
The silicone compound 280 ° C., _{N 2} mass reduction rate when heated for 30 minutes under a stream of air is preferably 0 to 70 wt%, more preferably from 5 to 50 mass%, more preferably 10 to 30 mass%.

The polyether-modified silicone used in the present invention preferably has a ratio represented by the formula (A) of 80% or more.
Formula (A) {(MO + EO) / AO} × 100
In the above formula (A), MO is the mol% of methylene oxide contained in the polyether structure in the polyether-modified silicone, and EO is the mol% of ethylene oxide contained in the polyether structure in the polyether-modified silicone. Yes, AO refers to the mole percent of alkylene oxide contained in the polyether structure in the polyether-modified silicone.
The ratio represented by the above formula (A) is preferably 90% or more, more preferably 95% or more, further preferably 98% or more, and further preferably 99% or more. 100% is even more preferable.

  500-100000 are preferable, as for the weight average molecular weight of polyether modified silicone, 1000-50000 are more preferable, and 2000-40000 are further more preferable.

  In the present invention, the polyether-modified silicone is heated at a temperature increase rate of 20 ° C./min from 20 ° C. to 280 ° C. under a nitrogen stream of 60 mL / min for 30 minutes at a temperature of 280 ° C. It is preferable that the mass reduction rate when held is 50% by mass or less. By using such a compound, the surface shape of the substrate after heating tends to be further improved. The mass reduction rate of the polyether-modified silicone is preferably 45% by mass or less, more preferably 40% by mass or less, further preferably 35% by mass or less, and further preferably 30% by mass or less. The lower limit of the mass reduction rate of the polyether-modified silicone may be 0% by mass, but 15% by mass or more, and even 20% by mass or more is sufficiently practical.

  In the present invention, the refractive index of light of the polyether-modified silicone is preferably 1.440 or less. The lower limit is not particularly defined, but even if it is 1.400 or more, it is sufficiently practical.

The polyether-modified silicone used in the present invention is preferably a polyether-modified silicone represented by any of the following formulas (101) to (104).
Formula (101)
In the above formula (101), R ¹¹ and R ¹⁶ are each independently a substituent, R ¹² and R ¹⁴ are each independently a divalent linking group, and R ¹³ and R ¹⁵ are hydrogen It is an atom or an alkyl group having 1 to 5 carbon atoms, m11, m12, n1 and p1 are each independently a number from 0 to 20, and x1 and y1 are each independently a number from 2 to 100.
Formula (102)
In the above formula (102), R ²¹ , R ²⁵ and R ²⁶ are each independently a substituent, R ²² is a divalent linking group, and R ²³ is a hydrogen atom or a carbon number of 1 to 5 M2 and n2 are each independently a number of 0 to 20, and x2 is a number of 2 to 100.
Formula (103)
In the above formula (103), R ³¹ and R ³⁶ are each independently a substituent, R ³² and R ³⁴ are each independently a divalent linking group, and R ³³ and R ³⁵ are hydrogen. It is an atom or an alkyl group having 1 to 5 carbon atoms, m31, m32, n3 and p3 are each independently a number from 0 to 20, and x3 is a number from 2 to 100.
Formula (104)
In the above formula (104), R ⁴¹ , R ⁴² , R ⁴³ , R ⁴⁴ , R ⁴⁵ and R ⁴⁶ are each independently a substituent, R ⁴⁷ is a divalent linking group, and R ⁴⁸ is , A hydrogen atom or an alkyl group having 1 to 5 carbon atoms, m4 and n4 are each independently a number from 0 to 20, and x4 and y4 are each independently a number from 2 to 100.

In the formula ^{(101), R 11} and ^{R 16} are each independently a substituent, preferably an alkyl group or a phenyl group having 1 to 5 carbon atoms, more preferably a methyl group.
In the above formula (101), R ¹² and R ¹⁴ are each independently a divalent linking group, and are a carbonyl group, an oxygen atom, an alkylene group having 1 to 6 carbon atoms, or a cycloalkylene group having 6 to 16 carbon atoms. , An alkenylene group having 2 to 8 carbon atoms, an alkynylene group having 2 to 5 carbon atoms, and an arylene group having 6 to 10 carbon atoms are preferable, and an oxygen atom is more preferable.
In formula (101), R ¹³ and R ¹⁵ are a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. An alkyl group is more preferred.

In the above formula (102), R ²¹ , R ²⁵ and R ²⁶ are each independently a substituent, which has the same meaning as R ¹¹ and R ¹⁶ in formula (101), and the preferred range is also the same.
In the above formula (102), R ²² is a divalent linking group, has the same meaning as R ¹² in formula (101), and the preferred range is also the same.
In the above formula (102), R ²³ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and is synonymous with R ¹³ and R ¹⁵ in the formula (101), and the preferred range is also the same.

In the above formula (103), R ³¹ and R ³⁶ are each independently a substituent, which has the same meaning as R ¹¹ and R ¹⁶ in formula (101), and the preferred range is also the same.
In the formula (103), R ³² and R ³⁴ are each independently a divalent linking group, and have the same meaning as R ¹² in the formula (101), and the preferred range is also the same.
In the above formula (103), R ³³ and R ³⁵ are a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and are synonymous with R ¹³ and R ¹⁵ in the formula (101), and their preferred ranges are also the same.

In the formula (104), R ⁴¹ , R ⁴² , R ⁴³ , R ⁴⁴ , R ⁴⁵ and R ⁴⁶ are each independently a substituent, and have the same meaning as R ¹¹ and R ¹⁶ in the formula (101), The preferable range is also the same.
In the above formula (104), R ⁴⁷ is a divalent linking group and has the same meaning as R ¹² in the formula (101), and the preferred range is also the same.
In the above formula (104), R ⁴⁸ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and has the same meaning as R ¹³ and R ¹⁵ in formula (101), and the preferred range is also the same.

  Of the polyether-modified silicones of formula (101) to formula (104), those of formula (103) or formula (104) are preferred, and those of formula (104) are more preferred.

In the polyether-modified silicone used in the present invention, the content of the polyoxyalkylene group in the molecule is not particularly limited, but it is desirable that the content of the polyoxyalkylene group exceeds 1% by mass in the total molecular weight.
The content of the polyoxyalkylene group is defined by “{(formula weight of polyoxyalkylene group in one molecule) / molecular weight of one molecule} × 100”.

Examples of silane coupling agents include fluorine atom-containing silane coupling agents, such as chlorodimethyl [3- (2,3,4,5,6-pentafluorophenyl) propyl] silane, pentafluorophenyldimethylchlorosilane, Pentafluorophenylethoxydimethylsilane, pentafluorophenylethoxydimethylsilane, trichloro (1H, 1H, 2H, 2H-tridecafluoro-n-octyl) silane, trichloro (1H, 1H, 2H, 2H-heptadecafluorodecyl) silane , Trimethoxy (3,3,3-trifluoropropyl) silane, triethoxy (1H, 1H, 2H, 2H-nonafluorohexyl) silane, triethoxy-1H, 1H, 2H, 2H-heptadecafluorodecylsilane, trimethoxy (1H , 1H, H, 2H-heptadecafluorodecyl) silane, trimethoxy (1H, 1H, 2H, 2H-nonafluorohexyl) silane, trichloro [3- (pentafluorophenyl) propyl] silane, trimethoxy (11-pentafluorophenoxyundecyl) Silane, triethoxy [5,5,6,6,7,7,7-heptafluoro-4,4-bis (trifluoromethyl) heptyl] silane, trimethoxy (pentafluorophenyl) silane, triethoxy (1H, 1H, 2H , 2H-nonafluorohexyl) silane, γ-glycidylpropyltrimethoxysilane.
Furthermore, JP-A-62-36663, JP-A-61-226746, JP-A-61-226745, JP-A-62-170950, JP-A-63-34540, JP-A-7-230165, The surfactants described in Kaihei 8-62834, JP-A-9-54432, JP-A-9-5988, and JP-A-2001-330953 are also exemplified as those usable in the present invention.

A commercial item can also be used for the silicone compound used by this invention.
For example, ADVALON FA33, FLUID L03, FLUID L033, FLUID L051, FLUID L053, FLUID L060, FLUID L066, IM22, WACKER-Belsil DMC 6038 (above, manufactured by Asahi Kasei Silicone Co., Ltd.), KF-352A, KF-352A, KF-352A KF-615A, KP-112, KP-341, X-22-4515, KF-354L, KF-355A, KF-6004, KF-6011, KF-6011P, KF-6012, KF-6013, KF-6015, KF-6016, KF-6017, KF-6017P, KF-6020, KF-6028, KF-6028P, KF-6038, KF-6043, KF-6048, KF-6123, KF-6204, KF-640 KF-642, KF-643, KF-644, KF-945, KP-110, KP-355, KP-369, KS-604, Polon SR-Conc, X-22-4272, X-22-4492 (above , Manufactured by Shin-Etsu Chemical Co., Ltd.), 8526 ADDITIVE, FZ-2203, FZ-5609, L-7001, SF 8410, 2501 COSMETIC WAX, 5200 FORMULATION AID, 57 ADDITIVE, 8019 ADDITIVE, 8029 ADDITIVE, 8029 036, BY16-201, ES-5612 FORMULATION AID, FZ-2104, FZ-2108, FZ-2123, FZ-2162, FZ-2164, FZ-2191, FZ-2207, Z-2208, FZ-2222, FZ-7001, FZ-77, L-7002, L-7604, SF8427, SF8428, SH 28 PAINR ADDITION, SH3749, SH3773M, SH8400, SH8700 (above, Toray Dow Corning Co., Ltd.) Manufactured by), BYK-378, BYK-302, BYK-307, BYK-331, BYK-345, BYK-B, BYK-347, BYK-348, BYK-349, BYK-377 (above, BYK Chemie Japan, Inc. )), Silwet L-7001, Silwet L-7002, Silwet L-720, Silwet L-7200, Silwet L-7210, Silwet L-7220, Silwet L-7230, Silwet L-7605, TSF44 45, TSF4446, TSF4452, Silwet Hydrostable 68, Silwet L-722, Silwet L-7280, Silwet L-7500, Silwet L-7550, Silwet L-7600, Silwet L-7602, Silwet L-7604, Silwet L-7604, 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 The product is manufactured by
Commercially available products are also trade names “BYK-300”, “BYK-306”, “BYK-310”, “BYK-315”, “BYK-313”, “BYK-320”, “BYK-322”. , “BYK-323”, “BYK-325”, “BYK-330”, “BYK-333”, “BYK-337”, “BYK-341”, “BYK-344”, “BYK-370”, “ “BYK-375”, “BYK-UV3500”, “BYK-UV3510”, “BYK-UV3570”, “BYK-3550”, “BYK-SILCLEAN3700”, “BYK-SILCLEAN3720” (above, manufactured by Big Chemie Japan Co., Ltd.) ), Trade names “AC FS 180”, “AC FS 360”, “AC S 20” (above, made by Algin Chemie), quotient Product names “Polyflow KL-400X”, “Polyflow KL-400HF”, “Polyflow KL-401”, “Polyflow KL-402”, “Polyflow KL-403”, “Polyflow KL-404”, “Polyflow KL-700” ( Kyoeisha Chemical Co., Ltd.), trade names “KP-301”, “KP-306”, “KP-109”, “KP-310”, “KP-310B”, “KP-323”, “KP” -326 "," KP-341 "," KP-104 "," KP-110 "," KP-112 "," KP-360A "," KP-361 "," KP-354 "," KP-357 ”,“ KP-358 ”,“ KP-359 ”,“ KP-362 ”,“ KP-365 ”,“ KP-366 ”,“ KP-368 ”,“ KP-330 ”,“ KP-650 ”, "KP- 51 "," KP-390 "," KP-391 "," KP-392 "(manufactured by Shin-Etsu Chemical Co., Ltd.), trade names" LP-7001 "," LP-7002 "," 8032 ADDIIVE ""FZ-2110","FZ-2105","67ADDITIVE","8618ADDITIVE","3ADDITIVE","56ADDITIVE" (manufactured by Toray Dow Corning Co., Ltd.), "TEGO WET 270" (Evonik Degussa Japan Co., Ltd.), “NBX-15” (Neos Co., Ltd.) and the like can also be used.

Examples of the compound containing a fluorine atom include a fluorine-based liquid compound.
As the fluorinated liquid compound, paragraph numbers 0025 to 0035 of International Publication No. WO2015 / 190477 can be referred to, the contents of which are incorporated herein. In a commercial item, what corresponds to a fluorine-type liquid compound among the DIC Corporation make and mega-fac series, for example, mega-fac F-557 etc. are illustrated.

The content of the release agent in the temporary bonding composition is preferably 0.001 to 1.0 mass% of the solid content of the temporary bonding composition. The lower limit of the content of the release agent is more preferably 0.004% by mass or more, further preferably 0.006% by mass or more, still more preferably 0.008% by mass or more, and even more preferably 0.009% by mass or more. preferable. The upper limit of the content of the release agent is preferably 0.8% by mass or less, more preferably 0.6% by mass or less, further preferably 0.3% by mass or less, and further preferably 0.15% by mass or less. 0.09% by mass or less is even more preferable.
The temporary bonding composition used in the present invention may contain only one type of release agent, or may contain two or more types. When 2 or more types are included, the total amount is preferably within the above range.

<Plasticizer>
The composition for temporary adhesion used by this invention may contain the plasticizer as needed. By blending a plasticizer, a temporary adhesive film satisfying the above-mentioned various performances can be obtained.
As the plasticizer, phthalic acid esters, fatty acid esters, aromatic polycarboxylic acid esters, polyesters, and the like can be used.

Examples of the phthalate ester include DMP, DEP, DBP, # 10, BBP, DOP, DINP, DIDP (above, manufactured by Daihachi Chemical Industry Co., Ltd.), PL-200, DOIP (above, manufactured by CG Esther Co., Ltd.) ), Sansosizer DUP (manufactured by Shin Nippon Rika).
Examples of fatty acid esters include butyl stearate, Unistar M-9676, Unistar M-2222SL, Unistar H-476, Unistar H-476D, Panaceto 800B, Panaceto 875, Panaceto 810 (above, NOF Corporation), DBA , DIBA, DBS, DOA, DINA, DIDA, DOS, BXA, DOZ, DESU (above, manufactured by Daihachi Chemical) and the like.
Examples of the aromatic polycarboxylic acid ester include TOTM, Monosizer W-705 (above, manufactured by Daihachi Chemical Industry Co., Ltd.), UL-80, UL-100 (above, made by ADEKA Corporation), and the like. .
Examples of the polyester include Polycizer TD-1720, Polycizer S-2002, Polycizer S-2010 (manufactured by DIC Corporation), BAA-15 (Daihachi Chemical Industry Co., Ltd.), and the like.
Among the plasticizers, DIDP, DIDA, TOTM, Unistar M-2222SL, and Polycizer TD-1720 are preferable, DIDA and TOTM are more preferable, and TOTM is particularly preferable.
Only one type of plasticizer may be used, or two or more types may be combined.

  From the viewpoint of preventing sublimation during heating, the plasticizer has a temperature at which the mass is reduced by 1% by mass when a mass change is measured under a nitrogen gas stream under a temperature rising condition of 20 ° C./min. It is preferably 250 ° C or higher, more preferably 270 ° C or higher, and particularly preferably 300 ° C or higher. The upper limit is not particularly defined, but can be, for example, 500 ° C. or less.

  The addition amount of the plasticizer is preferably 0.01% by mass to 5.0% by mass and more preferably 0.1% by mass to 2.0% by mass with respect to the total solid content of the temporary bonding composition. .

<Antioxidant>
The temporary bonding composition used in the present invention may contain an antioxidant. As the antioxidant, a phenol-based antioxidant, a sulfur-based antioxidant, a phosphorus-based antioxidant, a quinone-based antioxidant, an amine-based antioxidant, and the like can be used.
Examples of the phenol-based antioxidant include p-methoxyphenol, 2,6-di-tert-butyl-4-methylphenol, Irganox 1010, Irganox 1330, Irganox 3114, Irganox 1035 (above, manufactured by BASF Japan Ltd.), Sumilizer MDP- S, Sumilizer GA-80 (above, manufactured by Sumitomo Chemical Co., Ltd.).
Examples of the sulfur-based antioxidants include 3,3′-thiodipropionate distearyl, Sumilizer TPM, Sumilizer TPS, and Sumilizer TP-D (manufactured by Sumitomo Chemical Co., Ltd.).
Examples of phosphorus antioxidants include tris (2,4-di-tert-butylphenyl) phosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, and poly (dipropylene glycol) phenyl. Examples include phosphite, diphenylisodecyl phosphite, 2-ethylhexyl diphenyl phosphite, triphenyl phosphite, Irgafos 168, Irgafos 38 (above, manufactured by BASF Japan Ltd.).
Examples of the quinone antioxidant include p-benzoquinone and 2-tert-butyl-1,4-benzoquinone.
Examples of amine-based antioxidants include dimethylaniline and phenothiazine.
As the antioxidant, Irganox 1010, Irganox 1330, 3,3′-thiodipropionate distearyl and Sumilizer TP-D are preferable, Irganox 1010 and Irganox 1330 are more preferable, and Irganox 1010 is particularly preferable.
Of the above antioxidants, it is preferable to use a phenol-based antioxidant and a sulfur-based antioxidant or a phosphorus-based antioxidant in combination, and a phenol-based antioxidant and a sulfur-based antioxidant are used in combination. Most preferred. In particular, when a polystyrene-based elastomer is used as the elastomer, it is preferable to use a phenol-based antioxidant and a sulfur-based antioxidant in combination. By using such a combination, it can be expected that the deterioration of the temporary bonding composition due to the oxidation reaction can be efficiently suppressed. When a phenolic antioxidant and a sulfurous antioxidant are used in combination, the mass ratio of the two is preferably phenolic antioxidant: sulfuric antioxidant = 95: 5 to 5:95, and 25:75 to 75. : 25 is more preferable.
As the combination of antioxidants, Irganox 1010 and Sumilizer TP-D, Irganox 1330 and Sumilizer TP-D, and Sumilizer GA-80 and Sumilizer TP-D are preferable, Irganox 1010 and Sumilizer TP-o, Ir30x TP-D, 13g More preferred are Irganox 1010 and Sumilizer TP-D.

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

When the temporary bonding composition contains an antioxidant, the content of the antioxidant is preferably 0.001 to 20.0% by mass with respect to the total solid content of the temporary bonding composition, 0.005 -10.0 mass% is more preferable.
Only one type of antioxidant may be used, or two or more types may be used. When there are two or more antioxidants, the total is preferably in the above range.

<Other additives>
In the range which does not impair the effect of this invention, the composition for temporary adhesion | attachment used by this invention is various additives, for example, a hardening | curing agent, a curing catalyst, a filler, adhesion promotion as needed in addition to the additive mentioned above. An agent, an ultraviolet absorber, an aggregation inhibitor and the like can be blended. When these additives are blended, the total blending amount is preferably 3% by mass or less based on the total solid content of the temporary bonding composition.

  The composition for temporary adhesion of this invention can be prepared by mixing each component. In particular, stirring with a mixer or the like is preferable.

Temporary adhesive film The temporary adhesive film according to the present invention is a temporary adhesive film containing a release agent and a resin, and the temporary adhesive film has at least one of a concave portion and a convex portion on the surface, and has an average thickness. Discloses 5 to 500 μm. Such a temporary adhesive film is formed by curing the aforementioned temporary adhesive composition. Since the conventional temporary adhesive film was manufactured by applying a liquid temporary adhesive composition on a substrate and curing it, it was difficult to manufacture a temporary adhesive film having concave and convex portions on the surface. . On the other hand, if it manufactures using a compression mold apparatus, the temporary adhesive film which has a recessed part and a convex part on the surface can be manufactured easily. Furthermore, the temporary adhesive film according to the present invention can be configured without an edge bead.

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples unless it exceeds the gist thereof. Unless otherwise specified, “part” and “%” are based on mass.
Moreover, this Example was performed at 25 ° C. and 101,300 Pa unless otherwise specified.

<Production of Example 1-1 to Example 1-17 Temporary Adhesion Composition>
The composition for temporary bonding which shows a composition below was stirred with a mixer for 60 seconds at a frequency of 60 Hz, an acceleration of 100 G, and an amplitude of 15 mm.
<< Composition of composition for temporary bonding >>
-Resins listed in Table 1: 97.9 parts by mass (when two types of resins are blended, blended so that resin 1 accounts for 80% by mass of resin and resin 2 accounts for 20% by mass of resin)
Additives (release agents) listed in Tables 1 and 3: 0.1 parts by mass <<<< Components (oxidation) blended in all temporary bonding compositions of Examples 1-1 to 1-17 Inhibitor) >>
・ Irganox 1010 (manufactured by BASF Japan Ltd.): 1 part by mass ・ Sumilizer TP-D (manufactured by Sumitomo Chemical Co., Ltd., powder): 1 part by mass

The compounds (resins) listed in Table 1 are as follows.

The resins listed in Table 2 are all powders.
In Table 2 above, the styrene ratio (ratio of styrene-derived repeating units, mass%) is obtained by forming a temporary bonding composition on a wafer and peeling it, and then trichlorobenzene / heavy benzene = 80/20 (volume%). ), And using H-NMR (JEOL-JSX400, manufactured by JEOL Ltd.), the integral intensity of signals attributed to styrene and other copolymer components in the resin is measured, and each copolymer is measured. Calculated by multiplying the specific gravity of the components.
In the said Table 2, E has shown the tensile elasticity modulus based on JISK7161: 1994 in 25 degreeC of resin.
In Table 2 above, COP refers to a cycloolefin polymer, and TPI refers to a thermoplastic polyimide resin.

  The compounds A-1 to A-12 (release agents) are oily.

<< Method for Measuring Mass Decrease Rate of Polyether Modified Silicone after Heating at 280 ° C for 30 Minutes >>
The “280 ° C. 30 minute mass reduction rate” shown in Table 3 above is from 20 ° C. to 280 ° C. using a thermogravimetry apparatus (TGA-50, manufactured by Shimadzu Corporation) under a nitrogen stream of 60 mL / min. The temperature is increased at a rate of temperature increase of 20 ° C./min until the temperature is maintained at 280 ° C. for 30 minutes, and the mass reduction rate is calculated based on the following equation.
Mass reduction rate (mass%) =
{(Mass at 20 ° C.−mass after holding at 280 ° C. for 30 minutes) / mass at 20 ° C.} × 100

<< Measurement Method of Refractive Index >>
Using a precision refractometer (KPR-3000, manufactured by Shimadzu Corporation), the refractive index of light having a wavelength of 589 nm was measured at 25 ° C.

<< Method for Measuring Ratio Represented by Formula (A) >>
Using NMR (nuclear magnetic resonance), the peak of hydrogen atom specific to methylene oxide, ethylene oxide, and propylene oxide was measured, and the area ratio of each was calculated.

<Example 2-1 to Example 2-17>
In Examples 2-1 to 2-17, laminates were manufactured using the temporary bonding compositions manufactured in Examples 1-1 to 1-17, respectively.

<< Bonding >>
A disc-shaped silicon substrate having a diameter of 300 mm and a metal frame having an inner diameter of 299 mm were installed in this order as a carrier substrate on a bond chuck of an EVG540 bonder (bonder device) manufactured by EV Group. The temporary bonding composition was put into the metal frame so as to have an average thickness of 0.2 mm. After the introduction, the metal frame was gently removed, and spacers mounted on the bond chuck were inserted at three locations on the edge portion.
Next, the device wafer was set on the spacer with the device surface facing down (on the bonder side).
Here, the carrier substrate and the device wafer were set so as to be concentric. Further, the device wafer is obtained by providing copper pillars at equal intervals of 100 μm on the surface of a silicon substrate having a diameter of 300 mm. The copper pillar has a cylindrical shape with a height of 30 μm and a diameter of 50 μm.
Next, the temperature of the pressure plate provided on the upper side and the lower side of the bonder device (the device surface side of the device wafer and the substrate surface side of the carrier substrate) was previously heated to 200 ° C. After the carrier substrate, temporary bonding composition, and device wafer set on the bond chuck are set on the lower pressure plate, the inside of the bonder is sucked with a vacuum pump, and the degree of vacuum is 1 × 10 ⁻³ Pa or less. After that, the spacer is removed, and at the same time as the device wafer is brought into contact with the temporary bonding composition, the upper pressure plate is brought into contact with the upper surface of the device wafer while being heated, and the pressure is applied as it is for 5 minutes at a pressure of 20 kN. After heating, the pressure was released, and then the bond chuck was pulled out of the bonder apparatus with the material on it and cooled to room temperature. As a result, a laminate of carrier substrate / temporary adhesive film / device wafer was obtained. The average thickness of the temporary adhesive film was 100 μm, and it was a uniform film without edge beads.

<< Processing >>
Next, the back surface of the device wafer was processed. Specifically, the back surface of the device wafer was back grinded with a grinder, and the thickness of the substrate portion of the device was reduced to 20 μm.

<< Debonding >>
While rotating the laminated body processed at 1000 rpm with a spin coater with the carrier substrate side facing down, the mesitylene solvent is allowed to flow from the device wafer side, so that the end of the laminated body (circumferential direction of the substrate surface) The foreign matter adhering to (2), for example, the temporary adhesive film protruding from the substrate was removed.
Next, the laminate was attached to the dicing tape 9 attached to the dicing frame with the device wafer facing down.
A device on the dicing tape 9 is manufactured by setting a laminate adhered to the dicing tape 9 using a debonder device, Synapse Z, manufactured by Tokyo Electron Co., Ltd., and peeling at the interface between the carrier substrate and the temporary adhesive film. A laminated body having a temporary adhesive film on the surface of the wafer with a thickness of about 100 μm was obtained.

<< Cleaning >>
By using a debonder device Synapse Z manufactured by Tokyo Electron Co., Ltd. and spin cleaning with a mesitylene solvent, the temporary adhesive film on the device wafer was dissolved and removed to obtain a thinned device wafer.

<Example 3>
The components shown below were mixed with a mixer, then kneaded using two rolls having surface temperatures of 90 ° C. and 45 ° C., cooled and pulverized to obtain a temporary bonding composition.
Epoxy resin 1: phenol biphenyl aralkyl type epoxy resin (manufactured by Nippon Kayaku Co., Ltd., NC3000, epoxy equivalent 274, softening point 58 ° C.)
23.8 parts by mass Epoxy resin 2: bisphenol A type crystalline epoxy resin (manufactured by Mitsubishi Chemical Corporation, YL6810, epoxy equivalent 171, melting point 45 ° C.)
23.9 parts by mass Phenol resin 1: Phenol biphenyl aralkyl resin (Maywa Kasei Co., Ltd., MEH-7851SS, hydroxyl group equivalent 203, softening point 65 ° C.)
45.7 parts by mass

Butadiene / acrylonitrile copolymer 1 (Ube Industries, Ltd., HYCAR CTBN 1008-SP, in the following formula, x = 0.82, y = 0.18, and the average value of z is 62) 1.4 Parts by mass
Release agent (Momentive Performance Materials Japan GK, TSF4445) 0.05 parts by weight Triphenylphosphine 1.4 parts by weight γ-glycidylpropyltrimethoxysilane 1.9 parts by weight Carnauba wax 1.9 parts by weight

<Example 4>
In Example 4, a laminate was manufactured using the temporary bonding composition manufactured in Example 3 above.

<< Compression mold >>
On the lower pressure plate of the compression molding apparatus, a carrier substrate which is a disc-shaped silicon substrate having a diameter of 300 mm and a metal frame having an inner diameter of 299 mm were installed in this order.
The temporary bonding composition was introduced into the metal frame so that the average thickness was 0.4 mm. After the addition, the metal frame was gently removed.
Next, on the surface of the aluminum plate having a thickness of 6 mm, a release plate in which a release surface is formed by coating a heat-resistant fluororesin after forming unevenness that becomes reverse unevenness at a position corresponding to the unevenness of the device described later by machining. Was placed so that the release surface was on the lower side (the temporary bonding composition side).
The temperature of the pressure plate of the compression mold apparatus was preliminarily heated to 200 ° C. on both the upper side (peeling plate side) and the lower side (carrier substrate side), and pressurized for 5 minutes at a pressure of 20 kN.
Then, the cooling water was poured into the water cooling pipe in the pressure plate, and when it was cooled to 60 ° C., the pressure plate was opened.
By removing the release plate placed on the upper side, a laminate having a temporary adhesive film on the device wafer was obtained.

<< Bonding >>
Using the EVG540 bonder (bonder device) manufactured by EV Group, the laminate obtained above was placed on the bond chuck so that the device wafer side was on the lower side. Next, the edge spacer was set.
The device wafer is obtained by providing devices at equal intervals of a pitch of 1000 μm on a device surface of a silicon substrate having a diameter of 300 mm. The device is a rectangular parallelepiped having a height of 100 μm, a width and a length of 500 μm.
Next, the temperature of the pressure plate provided on the upper side and the lower side of the bonder device (the device surface side of the device wafer and the substrate surface side of the carrier substrate) is preheated to 200 ° C. After heating for 5 minutes, the pressure was released. A laminate of carrier substrate / temporary adhesive film / device wafer was obtained. The average thickness of the part without the device of the temporary adhesive film was 200 μm, the average thickness of the device part (convex part) was 100 μm, and it was a uniform film without edge beads.

<< Processing >>
Next, the back surface of the device wafer was processed. Specifically, the back surface of the device wafer was back-ground with a grinder, and the thickness of the substrate portion of the device was reduced to 20 μm.

<< Debonding >>
While rotating the laminated body after processing with a spin coater at 1000 rpm with the carrier substrate side down, the mesitylene solvent is flowed from the device wafer side to the edge of the laminated body (circumferential direction of the substrate surface). The adhering foreign matter, for example, the temporary adhesive film protruding from the substrate was removed.
Next, the laminated body was affixed to the dicing tape affixed to the dicing frame with the device wafer facing down.
The surface of the device wafer on the dicing tape is set by using a debonder device Synapse Z made by Tokyo Electron Co., Ltd. To obtain a laminate on which the temporary adhesive film is placed with a thickness of about 100 μm.

<< Cleaning >>
By using a debonder device Synapse Z manufactured by Tokyo Electron Co., Ltd. and spin cleaning with a mesitylene solvent, the temporary adhesive film on the device wafer was dissolved and removed to obtain a thinned device wafer.

DESCRIPTION OF SYMBOLS 1 Bonder apparatus 2 1st board | substrate 3 Composition for temporary bonding 4 Frame 6 2nd board | substrate 7 Compression molding apparatus 8 Mold type | mold 9 Dicing tape 33 Temporary adhesive film 66 Processed 2nd board | substrate

Claims (8)

A method of manufacturing a laminate having a structure in which a first substrate, a temporary adhesive film, and a second substrate are adjacent to each other in the order,
Applying the temporary bonding composition to one surface of the first substrate or mold, and applying the mold or second substrate to the surface of the temporary bonding composition;
Applying energy to the temporary bonding composition to form a temporary bonding film in the order described above,
The temporary bonding composition comprises a release agent, and, 25 ° C., Ri powdery or granular der in 101,300Pa,
Applying a temporary bonding composition to the surface of the first substrate and applying a mold to the surface of the temporary bonding composition; or
Applying a temporary bonding composition to the surface of the mold, and applying the second substrate to the surface of the temporary bonding composition;
Furthermore, after forming the temporary adhesive film, the mold die is peeled off, and the second substrate or the first substrate is applied to the surface of the temporary adhesive film on the side where the mold die is peeled off. Manufacturing method.   The manufacturing method of the laminated body of Claim 1 with which the provision of the said energy includes a heating.   The manufacturing method of the laminated body of Claim 1 or 2 with which application of the said energy includes application of a pressure.   The manufacturing method of the laminated body of any one of Claims 1-3 with which the said composition for temporary adhesion contains resin.   The manufacturing method of the laminated body of any one of Claims 1-4 in which the said mold release agent contains at least one of a fluorine atom and a silicon atom.   The manufacturing method of the laminated body of any one of Claims 1-5 in which the said composition for temporary adhesion contains antioxidant. The manufacturing method of the laminated body of any one of Claims 1-6 in which the said mold has at least one of a recessed part and a convex part in the surface at the side which contacts the said composition for temporary adhesion. The manufacturing method of a semiconductor device containing the manufacturing method of the laminated body of any one of Claims 1-7 .