JP6646726B2 - Temporary bonding composition and laminate - Google Patents

Description

  The present invention relates to a temporary bonding composition and a laminate formed using the temporary bonding composition.

In a process of manufacturing 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 singulated by dicing.
With the need for further miniaturization and higher performance of electronic devices, further miniaturization and higher integration are also required for IC chips mounted on the electronic devices. Integration is approaching its limits.

  As a method for electrically connecting 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 order to reduce the size of the IC chip, a device wafer has recently been used. A method is known in which a through hole is provided in a substrate, and a metal plug as an external terminal is connected to an integrated circuit so as to penetrate the through hole (a method of forming a through silicon via (TSV)). However, the method of forming the through silicon vias alone cannot sufficiently meet the needs for higher integration of recent IC chips described above.

  In view of the above, there has been known a technology for improving the degree of integration per unit area of a device wafer by increasing the number of integrated circuits in an IC chip. However, increasing the number of layers in an integrated circuit increases the thickness of the IC chip, so that the members constituting the IC chip need to be thinner. As a reduction in the thickness of such members, for example, a reduction in the thickness of a device wafer is being studied. The reduction in the thickness of the device wafer not only leads to a reduction in the size of the IC chip, but also a reduction in the size of the device wafer in the manufacture of through silicon vias. This is promising because it can save labor in the through-hole manufacturing process. Also, in semiconductor devices such as power devices and image sensors, thinning of device wafers has been attempted from the viewpoint of improving the degree of integration and the degree of freedom in device structure.

As device wafers, those having a thickness of about 700 to 900 μm are widely known. Have been tried.
However, a device wafer having a thickness of 200 μm or less is very thin, and a member for manufacturing a semiconductor device based on the device wafer is also very thin. It is difficult to stably support the member without damaging it when, for example, the user simply moves.

In order to solve the above problems, the device wafer before thinning and the carrier substrate are temporarily fixed (temporarily bonded) with a temporary bonding composition, 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.

Specifically, Patent Document 1 discloses an adhesive composition for temporarily attaching a substrate and a support for supporting the substrate, and includes a thermoplastic resin and a release agent. An adhesive composition is disclosed. Patent Document 2 also discloses that a heat-stable polymer layer comprises a base material, a semiconductor substrate, and a heat-stable polymer layer, and the heat-stable polymer layer contains a surface energy adjuster in an amount of 2.5% or more based on the heat-stable polymer. A wafer stack is described.

JP-A-2005-214675 U.S. Patent Publication No. 2014/0178701

Patent Literature 1 and Patent Literature 2 describe that a release agent or a surface energy adjuster is mixed with a resin such as a polystyrene-based elastomer and used as a composition for temporary bonding. However, the present inventor has studied and found that the type and the amount of the release agent and the surface energy regulator greatly affect the releasability of the temporary bonding composition. That is, depending on the type and the amount of the release agent in the temporary bonding composition, when the base materials (the device wafer and the carrier base material) are temporarily fixed using the temporary bonding composition, the base material is It was found that there was a case where it could not be peeled off properly. Furthermore, it was also found that the surface condition of the processed substrate may be deteriorated.
The present invention has been made to solve the above-described problem, and after temporarily fixing the base materials, the base material can be appropriately peeled off, and the surface shape of the processed base material is good. It is an object of the present invention to provide a temporary bonding composition capable of providing a body and a laminate.

Under such circumstances, the present inventors have conducted studies and found that the resin is a polyether-modified silicone, which has a high content of methylene oxide and ethylene oxide among the alkylene oxides contained in the polyether structure. It has been found that the above problems can be solved by blending a small amount of silicone. Specifically, the above-mentioned subject was solved by the following means <1>, and preferably by <2> to <11>.
<1> A temporary bonding composition comprising a resin and a polyether-modified silicone A having a ratio represented by the following formula (A) of 80% or more,
A composition for temporary bonding, wherein the content of the polyether-modified silicone A is 0.001 to 1.0% by mass of the solid content of the composition for temporary bonding;
Formula (A) {(MO + EO) / AO} × 100
In the above formula (A), MO is mol% of methylene oxide contained in the polyether structure in the polyether-modified silicone, and EO is mol% of ethylene oxide contained in the polyether structure in the polyether-modified silicone. AO refers to the mole% of alkylene oxide contained in the polyether structure in the polyether-modified silicone.
<2> The composition for temporary bonding according to <1>, wherein the resin is a polystyrene-based elastomer.
<3> The resin is a polystyrene-poly (ethylene-propylene) diblock copolymer, a polystyrene-poly (ethylene-propylene) -polystyrene triblock copolymer, or a polystyrene-poly (ethylene-butylene) -polystyrene triblock copolymer. <1> The composition for temporary bonding according to <1>, which is a polystyrene-based elastomer selected from at least one of a polymer and a polystyrene-poly (ethylene / ethylene-propylene) -polystyrene triblock copolymer.
<4> The composition for temporary bonding according to <2> or <3>, wherein the proportion of the repeating unit derived from styrene in the polystyrene-based elastomer is 55% by mass or less.
<5> The temporary bonding composition according to any one of <1> to <4>, wherein the resin has a tensile modulus E of 1 to 60 MPa at 25 ° C. in accordance with JIS K 7161: 1994.
<6> The composition for temporary bonding according to any one of <1> to <5>, wherein the ratio of the polyether-modified silicone A represented by the formula (A) is 90% or more.
<7> When the temperature of the above polyether-modified silicone A is increased from 20 ° C. to 280 ° C. at a rate of 20 ° C./min under a nitrogen flow of 60 mL / min, and held at a temperature of 280 ° C. for 30 minutes. The composition for temporary adhesion according to any one of <1> to <6>, wherein the mass reduction rate is 50% by mass or less.
<8> the composition for temporary bonding according to any one of <1> to <7>, wherein the polyether-modified silicone A is represented by any of the following formulas (101) to (104);
Equation (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. An atom or an alkyl group having 1 to 5 carbon atoms, m11, m12, n1 and p1 are each independently a number of 0 to 20, and x1 and y1 are each independently a number of 2 to 100;
Equation (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 atom having 1 to 5 carbon atoms. M2 and n2 are each independently a number from 0 to 20, and x2 is a number from 2 to 100;
Equation (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. An atom or an alkyl group having 1 to 5 carbon atoms, m31, m32, n3 and p3 are each independently a number of 0 to 20, and x3 is a number of 2 to 100;
Equation (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 of 0 to 20, and x4 and y4 are each independently a number of 2 to 100.
<9> The composition for temporary bonding according to any one of <1> to <8>, wherein the polyether-modified silicone A has a refractive index of 1.440 or less.
<10> The temporary bonding composition according to any one of <1> to <9>, wherein the temporary bonding composition has a release force of 1 to 20 N / m: the temporary bonding composition is a temporary bonding composition. A temporary adhesive film having a thickness of 15 μm is formed on the surface of the silicon wafer by using an object, and at a temperature of 25 ° C. and a speed of 300 mm / min. It refers to the force that can be peeled off by pulling up the end of the temporary adhesive film and that the force applied when pulling up is measured using a force gauge.
<11> A laminate having a first substrate, a temporary adhesive film, and a second substrate adjacent to each other in the above order, wherein the temporary adhesive film is any one of <1> to <10>. A laminate formed from the temporary bonding composition according to any one of the above.

  According to the present invention, after the base materials are temporarily fixed to each other, the base material can be appropriately peeled off, and the composition for temporary bonding can provide a laminate having a good surface condition of the processed base material, and the lamination. It became possible to provide a body.

FIG. 3 is a schematic view of a first embodiment illustrating a method for manufacturing a semiconductor device. FIG. 7 is a schematic view of a second embodiment illustrating a method for manufacturing a semiconductor device. It is a schematic sectional drawing explaining release of the temporary adhesion state of the conventional adhesive carrier base material and a device wafer.

Hereinafter, the contents of the present invention will be described in detail. In this specification, a numerical range represented by using “to” means a range including numerical values described before and after “to” as a lower limit and an upper limit.
In the notation of a group (atomic group) in the present specification, the notation of not indicating substituted or unsubstituted includes a group having a substituent as well as a group having no 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).
As used herein, the term “active light” or “radiation” includes, for example, visible light, ultraviolet light, far ultraviolet light, electron beams, X-rays, and the like.
In this specification, “exposure” includes not only exposure using light, but also drawing using a particle beam such as an electron beam or an ion beam, unless otherwise specified. The light used for exposure generally includes an active ray or radiation such as a bright line spectrum of a mercury lamp, far ultraviolet represented by excimer laser, extreme ultraviolet (EUV light), X-ray, and electron beam.
In the present specification, the term “total solids” refers to the total mass of components excluding the solvent from all components of the composition.
In the present specification, “(meth) acrylate” represents acrylate and methacrylate, “(meth) acryl” represents acryl and methacryl, “(meth) acryloyl” represents “acryloyl” and “methacryloyl” .
In the present specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are defined as values in terms of polystyrene measured by gel permeation chromatography (GPC). In the present specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are, for example, HLC-8220 (manufactured by Tosoh Corporation) and TSKgel Super AWM-H (manufactured by Tosoh Corporation; (ID) 6.0 mm × 15.0 cm), and can be determined by using 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 reference numerals or corresponding reference numerals in the drawings to simplify or omit the description.

The temporary bonding composition of the present invention is a temporary bonding composition containing a resin and a polyether-modified silicone A having a ratio represented by the formula (A) of 80% or more, wherein the polyether-modified silicone is The content of A is 0.001 to 1.0% by mass of the solid content of the composition for temporary bonding.
Formula (A) {(MO + EO) / AO} × 100
In the above formula (A), MO is mol% of methylene oxide contained in the polyether structure in the polyether-modified silicone, and EO is mol% of ethylene oxide contained in the polyether structure in the polyether-modified silicone. AO is the mole% of the alkylene oxide contained in the polyether structure in the polyether-modified silicone.
With such a configuration, the base material can be appropriately temporarily fixed to each other to form a laminate, and further, the base material can be appropriately peeled after processing. In addition, a temporary bonding composition that can provide a laminate having an excellent surface condition of the processed substrate is obtained.
This mechanism is presumed to be as follows. That is, the polyether-modified silicone A having the ratio represented by the formula (A) of 80% or more is selectively localized at the interface in the temporary adhesive film. This also makes it possible to appropriately temporarily fix the base material and appropriately peel it. Furthermore, even if processing involving heating is performed, the generation of outgas due to decomposition is small, so that the surface shape of the base material after processing is improved.
Furthermore, by using the polyether-modified silicone A, a resin having a low tensile modulus, for example, a styrene-based elastomer having a repeating unit derived from styrene having a proportion of 55% by mass or less can be used as a resin component, and the warping effect can be obtained. It is possible to suppress it.

<Resin>
The composition for temporary bonding of the present invention contains at least one resin. In the present invention, the type of the resin is not particularly limited as long as the various properties of the temporary adhesive film can be achieved.
Examples of the resin include a block copolymer, a random copolymer, and a graft copolymer, and a block copolymer is preferable. With a block copolymer, the flow of the temporary bonding composition during the heating process can be suppressed, so that adhesion can be maintained even during the heating process, and the effect that the releasability does not change even after the heating process is expected. it can.
The type of the resin is not particularly limited, and may be a polystyrene-based copolymer, a polyester-based copolymer, a polyolefin-based copolymer, a polyurethane-based copolymer, a polyamide-based copolymer, a polyacryl-based copolymer, or a silicone-based copolymer. Copolymers, polyimide copolymers, cycloolefin polymers and the like can be used.
In the present invention, the resin is a styrene-butadiene-styrene block copolymer, a styrene-isoprene-styrene block copolymer, a polystyrene-poly (ethylene-propylene) diblock copolymer, and a polystyrene-poly (ethylene-propylene). A polystyrene triblock copolymer, a polystyrene-poly (ethylene-butylene) -polystyrene triblock copolymer, a polystyrene-poly (ethylene / ethylene-propylene) -polystyrene triblock copolymer, a cycloolefin-based polymer, and The thermoplastic resin is preferably selected from at least one of thermoplastic polyimide resins, and is preferably a polystyrene-poly (ethylene-propylene) diblock copolymer, a polystyrene-poly (ethylene-propylene) -polystyrene trib. Polystyrene-based elastomer selected from at least one of a rubber copolymer, a polystyrene-poly (ethylene-butylene) -polystyrene triblock copolymer, and a polystyrene-poly (ethylene / ethylene-propylene) -polystyrene triblock copolymer. Is more preferable.
Among them, the resin is preferably a block copolymer of styrene and another monomer, and particularly preferably a styrene block copolymer in which one or both terminals are styrene blocks.
Further, the resin is preferably a hydrogenated product of a block copolymer. When the resin is a hydrogenated product, heat stability and storage stability are improved. Furthermore, the releasability and the removability of the temporary adhesive film after the removal are improved. The hydrogenated product means a polymer having a structure in which a block copolymer is hydrogenated.

In the present invention, the resin is preferably an elastomer. By using an elastomer as a resin, it follows fine irregularities on the carrier substrate and device wafer (first substrate and second substrate), and has a temporary anchor with excellent adhesion due to a suitable anchor effect. A film can be formed. Elastomers can be used alone or in combination of two or more.
In this specification, the term “elastomer” refers to a polymer compound that exhibits elastic deformation. That is, it is defined as a polymer compound having a property of being instantaneously deformed in response to an external force when applied with the external force and recovering the original shape in a short time when the external force is removed.
In this specification, the term “adhesiveness” means not only the performance of “providing a high adhesive strength simply by bonding at high pressure” but also the performance of “adhesion at low pressure (for example, low-pressure bonding at 0.4 MPa)”. To provide sufficiently high adhesion ".

<< Elastomer >>
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 still more preferably from 50,000 to 100,000. Elastomers with a weight average molecular weight in this range have excellent solubility in solvents, so after peeling the carrier substrate from the device wafer, the solvent is used to remove elastomer-derived residues remaining on the device wafer and carrier substrate. Upon removal, the residue is easily dissolved in a solvent and removed. For this reason, there is an advantage that no residue remains on the device wafer, the carrier base material, and the like.

  In the present invention, the elastomer is not particularly limited, and includes an elastomer containing a repeating unit derived from styrene (polystyrene-based elastomer), a polyester-based elastomer, a polyolefin-based elastomer, a polyurethane-based elastomer, a polyamide-based elastomer, a polyacryl-based elastomer, and a silicone-based elastomer. And polyimide-based elastomers. Among them, polystyrene-based elastomers, polyester-based elastomers, and polyamide-based elastomers are preferred, and polystyrene-based elastomers are particularly preferred from the viewpoint of heat resistance and releasability.

  In the present invention, the elastomer is preferably a hydrogenated product. In particular, a hydrogenated product of a polystyrene elastomer is preferable. When the elastomer is a hydrogenated product, heat stability and storage stability are improved. Furthermore, the releasability and the removability of the temporary adhesive film after the removal are improved. When a hydrogenated product of a polystyrene-based 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 5% thermal mass loss temperature when the elastomer is heated at a heating rate of 20 ° C./min from 25 ° C. is preferably 250 ° C. or more, more preferably 300 ° C. or more. Preferably, it is 350 ° C. or higher, more preferably 400 ° C. or higher. The upper limit is not particularly limited, but is preferably, for example, 1000 ° C. or lower, more preferably 800 ° C. or lower. According to this aspect, it is easy to form a temporary adhesive film having excellent 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 is 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 >>>>
The polystyrene-based elastomer is not particularly limited and can be appropriately selected depending on the purpose. 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 a polystyrene elastomer selected from at least one of (SEEPS).

The proportion of the repeating unit derived from styrene in the polystyrene-based elastomer is preferably 90% by mass or less, more preferably 55% by mass or less, still more preferably 48% by mass or less, further preferably 35% by mass or less, and more preferably 33% by mass or less. More preferred. The lower limit of the proportion of the repeating unit derived from styrene may be a value exceeding 0% by mass, and may be, for example, 10% by mass or more. By setting such a range, the warpage of the laminate can be more effectively suppressed.
The method of calculating the ratio of the repeating unit derived from styrene follows the method described in Examples described later.

As one embodiment of the polystyrene-based elastomer in the present invention, an elastomer A containing 10% by mass or more and 55% by mass or less of a repeating unit derived from styrene in all repeating units, and a repeating unit derived from styrene in all repeating units. In combination with an elastomer B containing more than 55% by mass and not more than 95% by mass. By using the elastomer A and the elastomer B together, the occurrence of warpage can be effectively suppressed. The mechanism by which such effects are obtained can be assumed to be as follows.
That is, since the elastomer A is a relatively soft material, it is easy to form a temporary adhesive film having elasticity. For this reason, a laminate of a substrate and a support is manufactured using the temporary bonding composition of the present invention, and when the substrate is polished into a thin film, pressure during polishing is locally applied. In addition, the temporary adhesive film can be easily elastically deformed to return to the original shape. As a result, excellent flat polishing properties can be obtained. Further, even if the laminated body after polishing is subjected to a heat treatment and then cooled, the temporary adhesive film can reduce internal stress generated at the time of cooling, and can effectively suppress the occurrence of warpage.
Further, since the elastomer B is a relatively hard material, by including the elastomer B, a temporary adhesive film having excellent releasability can be manufactured.

  When the elastomer A and the elastomer B are mixed, the mass ratio of the elastomer A: the elastomer B is preferably 1:99 to 99: 1, more preferably 3:97 to 97: 3, and more preferably 5:95 to 95: 5. Is more preferable, and 10:90 to 90:10 is more preferable. Within the above range, the above-described effects can be obtained more effectively.

The polystyrene-based elastomer is preferably a block copolymer of styrene and another monomer, more preferably a block copolymer having one end or both ends being a styrene block, and both ends being a styrene block. Block copolymers are particularly preferred. When both ends of the polystyrene-based elastomer are styrene blocks (a repeating unit derived from styrene), the heat resistance tends to be further improved. This is because a repeating unit derived from styrene having high heat resistance exists at the terminal. In particular, when the block portion of the repeating unit derived from styrene is a reactive polystyrene hard block, heat resistance and chemical resistance tend to be more excellent, which is preferable. 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-based elastomer is a hydrogenated product, the stability to heat is improved, and deterioration 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.
From the viewpoint of releasability, the unsaturated double bond amount 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. Most preferred. Here, the amount of unsaturated double bond does not include the amount of unsaturated double bond 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, the “styrene-derived repeating unit” is a styrene-derived structural unit contained in a polymer when styrene or a styrene derivative is polymerized, and may have a substituent. Examples of the styrene derivative include α-methylstyrene, 3-methylstyrene, 4-propylstyrene, 4-cyclohexylstyrene, 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.

  Commercially available polystyrene elastomers include, for example, Tufprene A, Tufprene 125, Tufprene 126S, Solprene T, Asaprene T-411, Asaprene T-432, Asaprene T-437, Asaprene T-438, Asaprene T-439, Tuftec H1272. Tuftec P1500, Tuftec H1052, Tuftec H1062, Tuftec M1943, Tuftec M1911, Tuftec H1041, Tuftech MP10, Tuftec M1913, Tuftec H1051, Tuftec H1053, Tuftec P2000, Tuftec H1043 (all manufactured by Asahi Kasei Chemicals AR-) 850C, Elastomer AR-815C, Elastomer AR-840C, Elastomer AR-830C, Elast -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 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 D4271, Clayton D4433, Clayton D1170, Clayton D1171, Clayton D1173, Califlex IR0307, Califflex 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 D1191, 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, Clayton 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 (and above) Polymer Japan Co., Ltd.), TR2000, TR2001, TR2003, TR2250, TR2500, TR2601, TR2630, TR2787, TR2827, TR1086, TR1600, SIS5002, SIS5200, SIS5250, SIS5405, SIS5505, Dinalon 6100P, Dinalon 4600P, Dynaro 6200P, Dynalon 4630P, Dynaron 8601P, Dynaron 8630P, Dynaron 8600P, Dynaron 8903P, Dynaron 6201B, Dynaron 1321P, Dynaron 1320P, Dynalon 2324P, Dynaron 9901P (all manufactured by JSR Corporation), Denka STR Series (Denka Chemical Industries, Ltd.) ), Quintac 3520, Quintac 3433N, Quintac 3421, Quintac 3620, Quintac 3450, Quintac 3460 (all manufactured by Zeon Corporation), TPE-SB series (Sumitomo Chemical Co., Ltd.), Lavalon series (Manufactured by Mitsubishi Chemical Corporation), Septon 1001, Septon 1020, Septon 2002, Septon 2004, Septon 2005, Septon 2006, Septon 2007, Septon 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 V9875, Septon V987, Septon V9827. , Hibler 7125, Hibler 5127, Hibler 5125 (manufactured by Kuraray Co., Ltd.), Sumiflex (manufactured by Sumitomo Bakelite Co., Ltd.), Leostomer, Actimer (manufactured by RIKEN TECHNOS)

<<< Polyester-based elastomer >>>
The polyester-based elastomer is not particularly limited and can be appropriately selected depending on the purpose. For example, those obtained by polycondensation of a dicarboxylic acid or a derivative thereof and a diol compound or a derivative thereof may be mentioned.
Examples of the dicarboxylic acid include aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, and naphthalenedicarboxylic acid (including aromatic dicarboxylic acids in which hydrogen atoms of these aromatic rings are substituted with a methyl group, an ethyl group, a phenyl group, etc. ); Aliphatic dicarboxylic acids having 2 to 20 carbon atoms such as adipic 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 include alicyclic diols and divalent phenol compounds represented by the following formulas.

In the above formula, Y ^DO represents any 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 ( (Direct bond between benzene rings). R ^DO1 and R ^DO2 each independently represent a halogen atom or an alkyl group having 1 to 12 carbon atoms. p ^do1 and p ^do2 each independently represent an integer of 0 to 4, and n ^do1 represents 0 or 1.

Specific examples of the divalent phenol compound include bisphenol A, bis- (4-hydroxyphenyl) methane, bis- (4-hydroxy-3-methylphenyl) propane, and resorcinol. These may be used alone or in combination of two or more.
As a polyester elastomer, a multi-block copolymer containing a hard segment component composed of an aromatic polyester (eg, polybutylene terephthalate) portion and a soft segment component composed of an aliphatic polyester (eg, polytetramethylene glycol) portion is used. Coalescence can also be used. Examples of the multi-block copolymer include various grades depending on the type, ratio, and molecular weight of the hard segment and the soft segment. As specific examples, Hytrel (manufactured by Toray Dupont), perprene (manufactured by Toyobo Co., Ltd.), Primalloy (manufactured by Mitsubishi Chemical Corporation), Nuberan (manufactured by Teijin Limited), Espel 1612, 1620 (or more) And Hitachi Chemical Co., Ltd.).

<<<< Polyolefin elastomer >>
The polyolefin-based elastomer is not particularly limited and can be appropriately selected depending on the purpose. For example, copolymers of α-olefins having 2 to 20 carbon atoms, such as ethylene, propylene, 1-butene, 1-hexene, and 4-methyl-1-pentene, may be mentioned. For example, ethylene-propylene copolymer (EPR), ethylene-propylene-diene copolymer (EPDM) and the like can be mentioned. Further, a copolymer of a non-conjugated diene having 4 to 20 carbon atoms, such as dicyclopentadiene, 1,4-hexadiene, cyclooctadiene, methylenenorbornene, ethylidene norbornene, butadiene, isoprene, and an α-olefin may be used. Further, a carboxy-modified nitrile rubber obtained by copolymerizing methacrylic acid with a butadiene-acrylonitrile copolymer may be used. Specifically, ethylene / α-olefin copolymer rubber, ethylene / α-olefin / non-conjugated diene copolymer rubber, propylene / α-olefin copolymer rubber, butene / α-olefin copolymer rubber, etc. No.
Commercially available products include Mirastomer (manufactured by Mitsui Chemicals, Inc.), Thermolan (manufactured by Mitsubishi Chemical Corporation), EXACT (manufactured by ExxonMobil), ENGAGE (manufactured by Dow Chemical Japan), and Esporex (manufactured by Sumitomo Chemical Co., Ltd.) ), Sarlink (manufactured by Toyobo Co., Ltd.), Newcon (manufactured by Nippon Polypropylene Co., Ltd.), EXCELLINK (manufactured by JSR Corporation), and the like.

<<< Polyurethane elastomer >>>
The polyurethane-based elastomer is not particularly limited and can be appropriately selected depending on the purpose. For example, an elastomer containing a structural unit of a hard segment composed of low molecular weight glycol and diisocyanate and a soft segment composed of high molecular weight (long chain) diol and diisocyanate is exemplified.
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-hexadiene). Xylene carbonate), poly (1,6-hexylene / neopenthylene adipate) and the like. The number average molecular weight of the high molecular (long chain) diol is preferably from 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 from 48 to 500.
Commercially available polyurethane elastomers include PANDEX T-2185, T-2983N (above, manufactured by DIC Corporation), milactran (manufactured by Nippon Milactran Co., Ltd.), Elastran (manufactured by BASF Japan Co., Ltd.), and rezamin ( Dainichi Seika Kogyo Co., Ltd.), Pelesen (Dow Chemical Japan Co., Ltd.), Iron Rubber (NOK Co., Ltd.), Mobilon (Nisshinbo Chemical Co., Ltd.) and the like.

<<< Polyamide-based elastomer >>>
The polyamide-based elastomer is not particularly limited and can be appropriately selected depending on the purpose. For example, an elastomer including a hard segment composed of polyamide such as polyamide-6, 11, 12 and a soft segment composed of at least one of polyether and polyester such as polyoxyethylene, polyoxypropylene and polytetramethylene glycol, etc. Is mentioned. This elastomer is roughly classified into two types, a polyether block amide type and a polyether ester block amide type.
Commercially available UBE polyamide elastomers, UBESTA XPA (manufactured by Ube Industries, Ltd.), Daiamide (manufactured by Daicel Evonik), PEBAX (manufactured by ARKEMA), GRILLON ELX (manufactured by Ms. Chemie Japan), Nopamid (Manufactured by Mitsubishi Chemical Corporation), Gleex (manufactured by Toyobo), polyetheresteramide PA-200, PA-201, TPAE-12, TPAE-32, polyesteramide TPAE-617, TPAE-617C And T & K TOKA).

<<<< Polyacrylic elastomer >>
The polyacrylic elastomer is not particularly limited and can be appropriately selected depending on the purpose. For example, an acrylic ester such as ethyl acrylate, butyl acrylate, methoxyethyl acrylate, or ethoxyethyl acrylate as a main component of the monomer material, or a copolymer obtained by copolymerizing an acrylic ester with glycidyl methacrylate, allyl glycidyl ether, or the like. Coalescence. Further, those obtained by copolymerizing an acrylate ester and a crosslinking point monomer such as acrylonitrile or ethylene may be used. Specific examples include an acrylonitrile-butyl acrylate copolymer, an acrylonitrile-butyl acrylate-ethyl acrylate copolymer, and an acrylonitrile-butyl acrylate-glycidyl methacrylate copolymer.

<<< Silicone elastomer >>>
The silicone-based elastomer is not particularly limited and can be appropriately selected depending on the purpose. For example, a polydimethylsiloxane-based, polymethylphenylsiloxane-based, polydiphenylsiloxane-based, or the like containing an organopolysiloxane as a main component can be used. Specific examples of commercially available products include KE series (manufactured by Shin-Etsu Chemical Co., Ltd.), SE series, CY series, and SH series (all manufactured by Toray Dow Corning Co., Ltd.).

<<<< Other elastomers >>>>
In the present invention, a rubber-modified epoxy resin (epoxy-based 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 novolak-type epoxy resin or cresol novolak-type epoxy resin, in which a part or all of epoxy groups are converted to carboxylic acid at both ends. It can be obtained by modification with a modified butadiene-acrylonitrile rubber, a terminal amino-modified silicone rubber, or the like.

<< other polymer compounds >>
In the present invention, as the resin, a polymer compound other than the above-described resin (also referred to as another polymer compound) can be used. One or more of the other high molecular compounds can be used in combination.
Specific examples of other polymer compounds include, for example, hydrocarbon resins, novolak resins, phenolic resins, epoxy resins, melamine resins, urea resins, unsaturated polyester resins, alkyd resins, polyamide resins, thermoplastic polyimide resins, polyamideimides Resin, polybenzimidazole resin, polybenzoxazole resin, polyvinyl chloride resin, polyvinyl acetate resin, polyacetal resin, polycarbonate resin, polyphenylene ether resin, polybutylene terephthalate resin, polyethylene terephthalate resin, polyphenylene sulfide resin, polysulfone resin, polyether Examples include a sulfone resin, a polyarylate resin, and a polyetheretherketone resin. Among them, hydrocarbon resins, thermoplastic polyimide resins, and polycarbonate resins are preferable, and hydrocarbon resins are more preferable.
In the present invention, a resin containing a fluorine atom described later can be used as the resin, but it is preferable that the resin containing a fluorine atom (hereinafter, also referred to as a fluorine-based resin) is not substantially contained. To be substantially free of a fluorine-based resin means that the content of the fluorine-based resin is, for example, preferably 0.1% by mass or less, more preferably 0.05% by mass or less, based on the total mass of the resin, and is not contained. Is more preferable.

<<<< Hydrocarbon resin >>>>
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 may have other atoms as side chains as long as the basic skeleton is a hydrocarbon resin. That is, even when a functional group other than a hydrocarbon group is directly bonded to the main chain, such as an acrylic resin, a polyvinyl alcohol resin, a polyvinyl acetal resin, and a polyvinyl pyrrolidone resin, to a hydrocarbon resin consisting of only carbon atoms and hydrogen atoms. It is included in the hydrocarbon resin in the invention, and 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 all the repeating units 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, cumarone petroleum resin, indene petroleum resin, polystyrene -Polyolefin copolymers, olefin polymers (for example, methylpentene copolymer), and cycloolefin polymers (for example, norbornene copolymer, dicyclopentadiene copolymer, tetracyclododecene copolymer) and the like.
Preferably, the hydrocarbon resin is a terpene resin, a rosin, a petroleum resin, a hydrogenated rosin, a polymerized rosin, an olefin polymer, or a cycloolefin polymer. More preferably, it is more preferably a cycloolefin polymer.

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

In the formula, m represents an integer of 0 to 4. R ^{1 to} R ⁶ each independently 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 each independently represent a hydrogen atom or a carbon number. 1-10 hydrocarbon group, a halogen atom, a hydrocarbon group having 1 to 10 carbon atoms substituted with a halogen _{^{atom, - (CH 2) nCOOR 11}} , - (CH 2) nOCOR 12, - (CH 2) nNCO, _{- (CH 2) nNO 2,} - (CH 2) nCN, - (CH 2) nCONR 13 R 14, - (CH 2) nNR 15 R 16 _{or, - (CH 2) nOZ,} - a _(CH 2) nW or represents, or, ^{X 1} and ^Y 1, ^{X 2} and ^{Y 2,} and ^{X 3} and ^{Y 3} are each independently - constituting _(CO) 2 O or _(-CO) 2 ^{NR 17,.} R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ and R ¹⁷ each independently represent a hydrogen atom or a hydrocarbon group (preferably a hydrocarbon group having 1 to 20 carbon atoms); Z represents a hydrocarbon group or a hydrocarbon group substituted with a halogen, W represents SiR ¹⁸ _p D _3-p (R ¹⁸ represents a hydrocarbon group having 1 to 10 carbon atoms, and D represents a halogen atom. , -OCOR ¹⁸ or -OR ¹⁸ , p represents an integer of 0 to 3), and n represents an integer of 0 to 10.

  The norbornene-based polymer is disclosed in JP-A-10-7732, JP-T-2002-504184, U.S. Patent Publication No. 2004 / 229157A1, International Publication WO2004-070463A1, and the like. The norbornene-based polymer can be obtained by addition polymerization of norbornene-based polycyclic unsaturated compounds. Further, if necessary, addition polymerization of a norbornene-based polycyclic unsaturated compound and a conjugated diene such as ethylene, propylene or butene; butadiene or isoprene; or a non-conjugated diene such as ethylidene norbornene can also be carried out. This norbornene-based polymer is marketed by Mitsui Chemicals, Inc. under the trade name of Apel and has different glass transition temperatures (Tg), for example, APL8008T (Tg 70 ° C), APL6013T (Tg 125 ° C) and APL6015T (Tg145 ° C). There are grades. Pellets such as TOPAS8007, 5013, 6013, and 6015 are sold by Polyplastics. In addition, Appear 3000 has been released by Ferrania.

Hydrates of norbornene-based 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. As disclosed in JP-A-2004-309979 and the like, a polycyclic unsaturated compound can be produced by addition polymerization or metathesis ring-opening polymerization followed by hydrogenation.
In the formula (III), R ⁵ and R ⁶ are preferably a hydrogen atom or a methyl group, X ³ and Y ³ are preferably a hydrogen atom, and the other groups are appropriately selected. This norbornene-based polymer is marketed by JSR Corporation under the trade name of Arton G or Arton F, and is also manufactured by Zeon Corporation of Japan under the name of Zeonor ZF14, ZF16, ZONEX 250, It is commercially available under the trade names 280 and 480R, and these can be used.

<<<< Thermoplastic polyimide resin >>>>
As the thermoplastic polyimide resin, a resin obtained by subjecting a tetracarboxylic dianhydride and a diamine to a condensation reaction by a known method can be used.
As a known method, for example, in an organic solvent, tetracarboxylic dianhydride and a diamine are mixed substantially equimolarly, and reacted at a reaction temperature of 80 ° C. or lower to synthesize a polyamic acid, and the obtained polyamic acid is obtained. Dehydration ring closure (imidization) and the like can be mentioned. Here, “substantially equimolar” means that the molar ratio of tetracarboxylic dianhydride to diamine is about 1: 1. In addition, if necessary, the composition ratio of tetracarboxylic dianhydride and diamine is 0.5 to 2.0 mol with respect to the total of 1.0 mol of tetracarboxylic dianhydride and the total of diamine. It may be adjusted so that 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, but for example, 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′-benzophenonetetracarboxylic dianhydride, 2, 3,2 ′, 3′-benzophenonetetracarboxylic dianhydride, 2,3,3 ′, 4′-benzophenonetetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic 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- Tetrachloronaphthale -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 (trimellitate 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, bis (oxabicyclo [2.2.1] heptane-2,3-dicarboxylic acid) 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 dianhydride Product, 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride, 2,2′bis [4- (3,4-dicarboxyphenyl) phenyl] hexafluoropropane dianhydride, 1,4'-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- Clohexene-1,2-dicarboxylic dianhydride, tetrahydrofuran-2,3,4,5-tetracarboxylic dianhydride, 4,4′-oxydiphthalic dianhydride, 1,2- (ethylene) bis (trimellitate Anhydride), 1,3- (trimethylene) bis (trimellitate anhydride), 1,4- (tetramethylene) bis (trimellitate anhydride), 1,5- (pentamethylene) bis (trimellitate anhydride), 1, 6- (hexamethylene) bis (trimellitate anhydride), 1,7- (heptamethylene) bis (trimellitate anhydride), 1,8- (octamethylene) bis (trimellitate anhydride), 1,9- (nonamethylene) Bis (trimellitate anhydride), 1,10- (decamethylene) bis (trimellitate anhydride), 1,12- (dodecamethylene) bi (Trimellitate anhydride), 1,16- (hexadecamethylene) bis (trimellitate anhydride), 1,18- (octadecamethylene) bis (trimellitate anhydride), and the like. Or a combination of two or more. Among these, 3,4,3 ′, 4′-benzophenonetetracarboxylic dianhydride, 2,3,2 ′, 3′-benzophenonetetracarboxylic dianhydride, 2,3,3 ′, 4′- Benzophenone tetracarboxylic dianhydride is preferred, and 3,4,3 ', 4'-benzophenone tetracarboxylic dianhydride is more preferred.

The diamine is not particularly limited, and examples thereof include o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 3,3′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, 4,4′-diaminodiphenyl ether, , 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'-diami Diphenyl sulfide, 3,4'-diamino diphenyl sulfide, 4,4'-diamino diphenyl sulfide, 3,3'-diamino diphenyl ketone, 3,4'-diamino diphenyl ketone, 4,4'-diamino diphenyl ketone, 3- (4-aminophenyl) -1,1,3-trimethyl-5-aminoindan, 2,2-bis (3-aminophenyl) propane, 2,2 ′-(3,4′-diaminodiphenyl) propane, , 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-aminophen Noxy) 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-aminophenoxy) phenyl) Sulfide, bis (4- (4-aminophenoxy) phenyl) sulfide, bis (4- (3-aminophenoxy) phenyl) sulfone, Aromatic diamines such as (4- (4-aminophenoxy) phenyl) sulfone, 3,3′-dihydroxy-4,4′-diaminobiphenyl, 3,5-diaminobenzoic acid, and 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, 1,10-diaminodecane, 1,11-diaminoundecane, 1,12-diaminododecane, Examples thereof include 1,2-diaminocyclohexane and 1,3-bis (3-aminopropyl) tetramethyldisiloxane.
Among these diamines, 3- (4-aminophenyl) -1,1,3-trimethyl-5-aminoindan, 1,3-bis (3-aminopropyl) tetramethyldisiloxane, polyoxypropylenediamine, , 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 is preferred, and 3- (4-aminophenyl) -1,1,3-trimethyl-5-aminoindane is more preferred.

Examples of the solvent used for the reaction between the tetracarboxylic dianhydride and the diamine include N, N-dimethylacetamide, N-methyl-2-pyrrolidone, and N, N-dimethylformamide. In order to adjust the solubility of the raw materials and the like, a non-polar solvent (for example, toluene or xylene) may be used in combination.
The reaction temperature of the tetracarboxylic dianhydride with the diamine is preferably lower than 100 ° C, more preferably lower than 90 ° C. The imidization of the polyamic acid is typically performed by heat treatment under an inert atmosphere (for example, a vacuum or a 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 from 10,000 to 1,000,000, and more preferably from 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. It is preferable that the solubility at 25 ° C. in the solvent is 10 g / 100 g Solvent or more.
Examples of the thermoplastic polyimide resin having such a solubility include 3,4,3 ′, 4′-benzophenonetetracarboxylic dianhydride and 3- (4-aminophenyl) -1,1,3-trimethyl A thermoplastic polyimide resin obtained by reacting -5-aminoindan; This thermoplastic polyimide resin has particularly excellent heat resistance.

  A commercially available product may be used as the thermoplastic polyimide resin. For example, Durimide (registered trademark) 200, 208A, 284 (all manufactured by Fuji Film Co., Ltd.), GPT-LT (Gunei Chemical Industry Co., Ltd.), SOXR-S, SOXR-M, SOXR-U, SOXR -C (all manufactured by Nippon Advanced Paper Industry Co., Ltd.), EXTEM VH1003, VH1003F, VH1003M, and XH1015 (all manufactured by SABIC Japan GK).

<<<< Polycarbonate resin >>>>
In the present invention, the polycarbonate resin preferably has a repeating unit represented by the following formula (1).

In the formula (1), Ar ¹ and Ar ² each independently represent an aromatic group, and L represents a single bond or a divalent linking group.

Ar ¹ and Ar ² in the formula (1) each independently represent an aromatic group. Examples of the aromatic group include a benzene ring, a naphthalene ring, a pentalene ring, an indene ring, an azulene ring, a heptalene ring, an indacene ring, a perylene ring, a pentacene ring, an acenaphthene ring, a phenanthrene ring, an anthracene ring, a naphthacene ring, a chrysene ring, and a triphenylene ring. , Fluorene ring, biphenyl ring, pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, indolizine ring, indole ring, benzofuran ring, benzothiophene ring , Isobenzofuran ring, quinolidine ring, quinoline ring, phthalazine ring, naphthyridine ring, quinoxaline ring, quinoxazoline ring, isoquinoline ring, carbazole ring, phenanthridine ring, acridine ring, phenanthroline ring, thianthrene , Chromene ring, xanthene ring, phenoxathiin ring, a phenothiazine ring, and a phenazine ring. Of these, a benzene ring is preferred.
These aromatic groups may have a substituent, but preferably do not have a substituent.
Examples of the substituent which the aromatic group may have include a halogen atom, an alkyl group, an alkoxy group and an aryl group.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
Examples of the alkyl group include an alkyl group having 1 to 30 carbon atoms. 1-20 are preferable and, as for carbon number of an alkyl group, 1-10 are more preferable. The alkyl group may be linear or branched. In addition, some or all of the hydrogen atoms of the alkyl group may be substituted with halogen atoms. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a fluorine atom is preferred.
As the alkoxy group, an alkoxy group having 1 to 30 carbon atoms is preferable. The carbon number of the alkoxy group is preferably 1 to 20, more preferably 1 to 10. The alkoxy group may be linear, branched, or cyclic.
As the aryl group, an aryl group having 6 to 30 carbon atoms is preferable, and an aryl group having 6 to 20 carbon atoms is more preferable.

  The weight average molecular weight (Mw) of the polycarbonate resin is preferably from 1,000 to 1,000,000, and more preferably from 10,000 to 80,000. Within the above range, the solubility in a solvent and the heat resistance are good.

  Commercially available polycarbonate resins include, for example, PCZ-200, PCZ-300, PCZ-500, PCZ-800 (manufactured by Mitsubishi Gas Chemical Co., Ltd.), APEC 9379 (manufactured by Bayer), Panlite L-1225LM ( Manufactured by Teijin Limited).

<< Resin Tensile Modulus E >>
The resin used for the temporary bonding composition of the present invention preferably has a tensile modulus E at 25 ° C in accordance with JIS (Japanese Industrial Standards) K7161: 1994 of 1 MPa or more and 4000 MPa or less, and preferably 1 MPa or more and 100 MPa or less. Is more preferably 1 MPa or more and 60 MPa or less, still more preferably 1 MPa or more and 35 MPa or less, still more preferably 1 MPa or more and 20 MPa or less, further preferably 1 MPa or more and 15 MPa or less. More preferably, it is more preferably 3 MPa or more and 10 MPa or less. With such a range, the warpage can be more effectively suppressed.
The tensile modulus E of the resin is measured by a method described in Examples described later.

<< Resin blending amount >>
The composition for temporary bonding of the present invention preferably contains a resin at a ratio of 50.00 to 99.99% by mass in the total solid content of the composition for temporary bonding, and 70.00 to 99.99% by mass. Is more preferable, and 88.0 to 99.99 mass% is particularly preferable. When the content of the resin is in the above range, the adhesiveness and the peelability are excellent.
When an elastomer is used as the resin, the elastomer is preferably contained at a ratio of 50.00 to 99.99% by mass in the total solid content of the temporary bonding composition, and more preferably 70.00 to 99.99% by mass. It is particularly preferably from 88.0 to 99.99% by mass. When the content of the elastomer is in the above range, the adhesiveness and the peelability are excellent. When two or more elastomers are used, the total is preferably within the above range.
When an elastomer is used as the resin, the content of the elastomer in the total mass of the resin is preferably 50 to 100% by mass, more preferably 70 to 100% by mass, still more preferably 80 to 100% by mass, and 90 to 100% by mass. Is more preferred. Further, the resin may be substantially only an elastomer. In addition, that the resin is substantially only an elastomer means that 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 further preferably only the elastomer. .

<Polyether-modified silicone A>
The polyether-modified silicone A used in the temporary bonding composition of the present invention has a ratio represented by the following formula (A) of 80% or more.
Formula (A) {(MO + EO) / AO} × 100
In the above formula (A), MO is mol% of methylene oxide contained in the polyether structure in the polyether-modified silicone, and EO is mol% of ethylene oxide contained in the polyether structure in the polyether-modified silicone. AO is the mole% of the alkylene oxide contained in the polyether structure in the polyether-modified silicone.
The ratio represented by the formula (A) is preferably 90% or more, more preferably 95% or more, further preferably 98% or more, and still more preferably 99% or more. , 100%.

  The weight average molecular weight of the polyether-modified silicone A is preferably from 500 to 100,000, more preferably from 1,000 to 50,000, and still more preferably from 2,000 to 40,000.

The polyether-modified silicone A used in the temporary bonding composition of the present invention is obtained by heating the polyether-modified silicone A from 20 ° C. to 280 ° C. at a rate of 20 ° C./min under a nitrogen stream of 60 mL / min. It is preferable that the mass reduction rate when held at a temperature of 280 ° C. for 30 minutes is 50% by mass or less. By using such a compound, the surface state of the substrate after processing involving heating tends to be further improved. The mass reduction rate of the polyether-modified silicone A is more preferably 45% by mass or less, further preferably 40% by mass or less, further preferably 35% by mass or less, and still more preferably 30% by mass or less. The lower limit of the mass reduction rate of the polyether-modified silicone A may be 0% by mass, but 15% by mass or more, and even 20% by mass or more is a sufficiently practical level.
The mass reduction rate in the present invention is measured by the method described in Examples.

  The polyether-modified silicone A used for the temporary bonding composition of the present invention preferably has a refractive index of 1.440 or less. The lower limit is not particularly specified, but even if it is 1.400 or more, it is a sufficiently practical level.

The polyether-modified silicone A used for the temporary bonding composition of the present invention preferably has a molecular weight of 500 or more. In particular, in the present invention, a polyether-modified silicone represented by any of the following formulas (101) to (104) is preferable.
Equation (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. An atom or an alkyl group having 1 to 5 carbon atoms, m11, m12, n1, and p1 are each independently a number of 0 to 20, and x1 and y1 are each independently a number of 2 to 100. .
Equation (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 atom having 1 to 5 carbon atoms. M2 and n2 are each independently a number from 0 to 20, and x2 is a number from 2 to 100.
Equation (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. An atom or an alkyl group having 1 to 5 carbon atoms, m31, m32, n3 and p3 are each independently a number of 0 to 20, and x3 is a number of 2 to 100.
Equation (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 of 0 to 20, and x4 and y4 are each independently a number of 2 to 100.

In the above formula (101), R ¹¹ and R ¹⁶ are each independently a substituent, preferably an alkyl group having 1 to 5 carbon atoms or a phenyl group, more preferably a methyl group.
In the formula (101), R ¹² and R ¹⁴ are each independently a divalent linking group, and include a carbonyl group, an oxygen atom, an alkylene group having 1 to 6 carbon atoms, and 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 the 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 more preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. Alkyl groups are more preferred.

In the above formula (102), R ²¹ , R ²⁵ and R ²⁶ are each independently a substituent, have the same meanings as R ¹¹ and R ¹⁶ in formula (101), and the preferred range is also the same.
In the formula (102), R ²² is a divalent linking group, has the same meaning as R ¹² and R ¹⁴ in the formula (101), and the preferable 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 has the same meaning as R ¹³ and R ¹⁵ in the formula (101), and the preferred range is also the same.

In the formula (103), R ³¹ and R ³⁶ are each independently a substituent, have the same meaning as R ¹¹ and R ¹⁶ in the formula (101), and the preferable range is also the same.
In the formula (103), R ³² and R ³⁴ are each independently a divalent linking group, have the same meaning as R ¹² and R ¹⁴ in the formula (101), and the preferable 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 have the same meaning as R ¹³ and R ¹⁵ in the formula (101), and the preferable range is also the same.

In the above formula (104), R ⁴¹ , R ⁴² , R ⁴³ , R ⁴⁴ , R ⁴⁵ and R ⁴⁶ are each independently a substituent, and have the same meanings as R ¹¹ and R ¹⁶ in formula (101). The same applies to the preferred range.
In the above formula (104), R ⁴⁷ is a divalent linking group, has the same meaning as R ¹² and R ¹⁴ in the formula (101), and the preferable range is also the same.
In the 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 the formula (101), and the preferable range is also the same.

  In Formulas (101) to (104), Formula (103) or Formula (104) is preferable, and Formula (104) is more preferable.

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

  Commercial products can also be used as the polyether-modified silicone A used in the temporary bonding composition of the present invention. For example, among the following commercially available products, a release agent having a ratio represented by the formula (A) of 80% or more can be used. ADVALON FA33, FLUID L03, FLUID L033, FLUID L051, FLUID L053, FLUID L060, FLUID L066, IM22, PACKER-Belsil DMC 6038 (all manufactured by Asahi Kasei Wacker Silicone, K-F-3, K-F-3, K-F-3) 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, F-642, KF-643, KF-644, KF-945, KP-110, KP-355, KP-369, KS-604, Polon SR-Conc, X-22-4272, X-22-4952 (or more 8526 ADDITIVE, FZ-2203, FZ-5609, L-7001, SF 8410, 2501 COSMETIC WAX, 5200 FORMULATION AID, 57 ADDITIVE, 8019 ADDITIVE, 8029 ADDITIVE, 8054, manufactured by Shin-Etsu Chemical Co., Ltd. 036, BY16-201, ES-5612 FORMULATION AID, FZ-2104, FZ-2108, FZ-2110, FZ-2123, FZ-2162, FZ-2164, FZ-21 91, FZ-2207, FZ-2208, FZ-2222, FZ-7001, FZ-77, L-7002, L-7604, SF8427, SF8428, SH28 PAIN ADDITIVE, SH3749, SH3773M, SH8400, SH8700 (Toray) -Dow Corning Co., Ltd.), BYK-378, BYK-302, BYK-307, BYK-331, BYK-345, BYK-3455, BYK-347, BYK-348, BYK-349, BYK-377 (or more) Silwet L-7001, Silwet L-7002, Silwet L-720, Silwet L-7200, Silwet L-7210, Silwet L-7220, Silwet L-7230, manufactured by Big Chemie Japan Co., Ltd. Ilwet L-7605, TSF4445, TSF4446, TSF4452, Silwet Hydrostable 68, Silwet L-722, Silwet L-7280, Silwet L-7500, Silwet L-7550, Silwet L-7600, Silwet L-026, Silwet L-026 Silwet L-7607, Silwet L-7608, Silwet L-7622, Silwet L-7650, Silwet L-7657, Silwet L-77, Silwet L-8500, Silwet L-8610, TSF4440, TSF4441, TSF4450, TSF4450 Momentive Performance Materials Japan GK).

The content of the polyether-modified silicone A in the temporary bonding composition of the present invention is 0.001 to 1.0% by mass of the solid content of the temporary bonding composition. The lower limit of the content of the polyether-modified silicone A is preferably 0.004% by mass or more, more preferably 0.006% by mass or more, further preferably 0.008% by mass or more, and more preferably 0.009% by mass or more. preferable. The upper limit of the content of the polyether-modified silicone A is preferably 0.8% by mass or less, more preferably 0.6% by mass or less, still more preferably 0.3% by mass or less, and more preferably 0.15% by mass or less. More preferably, the content is more preferably 0.09% by mass or less.
The composition for temporary adhesion of the present invention may contain only one kind of polyether-modified silicone A, or may contain two or more kinds. When two or more kinds are included, the total amount is preferably in the above range.

<Other release agents>
The composition for temporary adhesion of the present invention may contain a release agent other than the polyether-modified silicone A. Examples of other release agents include fluorine-based liquid compounds and silicone compounds other than those described above.
When another release agent is contained, its content is preferably in the range of 0.001 to 0.005% by mass of the solid content of the temporary bonding composition. The other release agent may include only one type, or may include two or more types. When two or more kinds are included, the total amount is preferably in the above range.
Further, in the present invention, a configuration that does not substantially contain another release agent can be adopted. The phrase "substantially free from other release agents" means that the content of the other release agents is 1% by mass or less of the content of the polyether-modified silicone A.

<Plasticizer>
The temporary bonding composition of the present invention may contain a plasticizer as needed. By blending a plasticizer, a temporary adhesive film satisfying the above various properties can be formed.
As the plasticizer, phthalic acid esters, fatty acid esters, aromatic polycarboxylic acid esters, polyesters and the like can be used.

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

  From the viewpoint of preventing sublimation during heating, the temperature at which the weight decreases by 1% by mass is measured from a viewpoint of preventing sublimation during heating, when the weight change is measured under a nitrogen gas flow at a constant rate of 20 ° C./min. 250 ° C. or higher is preferable, 270 ° C. or higher is more preferable, and 300 ° C. or higher is particularly preferable. The upper limit is not particularly defined, but may be, for example, 500 ° C. or lower.

  The amount of the plasticizer added is preferably from 0.01% by mass to 5.0% by mass, more preferably from 0.1% by mass to 2% by mass, based on the total solid content of the temporary bonding composition of the present invention. 0.0% by mass.

<Antioxidant>
The composition for temporary adhesion of the present invention may contain an antioxidant. As the antioxidant, a phenolic antioxidant, a sulfuric antioxidant, a phosphorus antioxidant, a quinone antioxidant, an amine antioxidant and the like can be used.
Examples of the phenolic antioxidant include p-methoxyphenol, 2,6-di-tert-butyl-4-methylphenol, Irganox1010, Irganox1330, Irganox3114, Irganox1035 (all manufactured by BASF Japan Ltd.), Sumilizer MDP -S, Sumilizer GA-80 (all manufactured by Sumitomo Chemical Co., Ltd.) and the like.
Examples of the sulfur-based antioxidant include 3,3′-thiodipropionate distearyl, Sumilizer TPM, Sumilizer TPS, and Sumilizer TP-D (all manufactured by Sumitomo Chemical Co., Ltd.).
Examples of the phosphorus-based antioxidant include tris (2,4-di-tert-butylphenyl) phosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, poly (dipropylene glycol) ) Phenyl phosphite, diphenyl isodecyl phosphite, 2-ethylhexyl diphenyl phosphite, triphenyl phosphite, Irgafos 168, Irgafos 38 (all manufactured by BASF Japan Ltd.) and the like.
Examples of the quinone-based antioxidant include p-benzoquinone and 2-tert-butyl-1,4-benzoquinone.
Examples of the amine-based antioxidant include dimethylaniline and phenothiazine.
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.
Further, among the above antioxidants, it is preferable to use a phenolic antioxidant in combination with a sulfur-based antioxidant or a phosphorus-based antioxidant, and to use a phenol-based antioxidant and a sulfur-based antioxidant in combination. Is most preferred. In particular, when a polystyrene-based elastomer is used as the resin, it is preferable to use a phenol-based antioxidant and a sulfur-based antioxidant in combination. By adopting such a combination, an effect that the deterioration of the resin due to the oxidation reaction can be efficiently suppressed can be expected. When a phenolic antioxidant and a sulfuric antioxidant are used in combination, the mass ratio of the phenolic antioxidant to the sulfuric antioxidant is: phenolic antioxidant: sulfur antioxidant = 95: 5 5:95 is preferred, and 25:75 to 75:25 is more preferred.
As a 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, and Irganox 1010 and Sumilizer TP-D-Silger TP-D, Irganx TP-D, Irganx 1030 and Sumilizer TP-Dzir More preferred are Irganox 1010 and Sumilizer TP-D.

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

When the composition for temporary bonding has an antioxidant, the content of the antioxidant is preferably from 0.001 to 20.0% by mass, and more preferably from 0.005 to 20.0% by mass based on the total solid content of the composition for temporary bonding. 10.0 mass% is more preferable.
The antioxidant may be used alone or in combination of two or more. When two or more antioxidants are used, the total is preferably within the above range.

<Solvent>
The composition for temporary bonding of the present invention preferably contains a solvent. Known solvents can be used without limitation, and organic solvents are preferable.
Examples of the organic solvent include ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, and alkyl alkoxyacetate (for example, alkoxyacetic acid). Methyl, ethyl alkoxyacetate, butylalkoxyacetate (for example, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate), alkyl esters of 3-alkoxypropionic acids (for example, 3-alkoxypropion) Methyl acrylate, ethyl 3-alkoxypropionate (eg, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate), 2-alcohol Alkyl cypropionates (eg, methyl 2-alkoxypropionate, ethyl 2-alkoxypropionate, propyl 2-alkoxypropionate, etc. (eg, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, 2-methoxy Propyl propionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), methyl 2-alkoxy-2-methylpropionate and ethyl 2-alkoxy-2-methylpropionate (e.g., 2-methoxy-2- Methyl methyl propionate, ethyl 2-ethoxy-2-methylpropionate), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, 1 Methoxy-2-propyl acetate, ethyl carbitol acetate, esters such as butyl carbitol acetate;
Diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol Ethers such as monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol methyl ether, and propylene glycol methyl ether acetate;
Ketones such as methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, N-methyl-2-pyrrolidone, γ-butyrolactone;
Pyrrolidones such as N-methyl-2-pyrrolidone and N-ethyl-2-pyrrolidone;
Toluene, xylene, anisole, mesitylene, pseudocumene, ethylbenzene, propylbenzene, cumene, n-butylbenzene, sec-butylbenzene, isobutylbenzene, tert-butylbenzene, amylbenzene, isoamylbenzene, (2,2-dimethylpropyl) benzene , 1-phenylhexane, 1-phenylheptane, 1-phenyloctane, 1-phenylnonane, 1-phenyldecane, cyclopropylbenzene, cyclohexylbenzene, 2-ethyltoluene, 1,2-diethylbenzene, o-cymene, indane , 1,2,3,4-tetrahydronaphthalene, 3-ethyltoluene, m-cymene, 1,3-diisopropylbenzene, 4-ethyltoluene, 1,4-diethylbenzene, p-cymene, 1,4-diisoprop Pyrbenzene, 4-tert-butyltoluene, 1,4-di-tert-butylbenzene, 1,3-diethylbenzene, 1,2,3-trimethylbenzene, 1,2,4-trimethylbenzene, 4-tert-butyl- o-xylene, 1,2,4-triethylbenzene, 1,3,5-triethylbenzene, 1,3,5-triisopropylbenzene, 5-tert-butyl-m-xylene, 3,5-di-tert- Aromatic hydrocarbons such as butyltoluene, 1,2,3,5-tetramethylbenzene, 1,2,4,5-tetramethylbenzene, pentamethylbenzene and decahydronaphthalene;
Preferable examples include aliphatic hydrocarbons such as ethylcyclohexane, limonene, p-menthane, nonane, decane, dodecane and decalin.

  A form in which two or more of these solvents are mixed is also preferable from the viewpoint of improving the coated surface condition. In this case, mesitylene, tert-butylbenzene, pseudocumene, p-menthane, γ-butyrolactone, N-ethyl-2-pyrrolidone, anisole, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve are particularly preferred. From acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, cyclopentanone, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether, and propylene glycol methyl ether acetate It is a mixed solution composed of two or more selected types.

When the composition for temporary bonding of the present invention has a solvent, the content of the solvent in the composition for temporary bonding is such that the total solid content of the composition for temporary bonding is 5 to 80% by mass from the viewpoint of applicability. The amount is preferably from 5 to 70% by mass, more preferably from 10 to 60% by mass.
The solvent may be only one kind or two or more kinds. When two or more solvents are used, the total is preferably within the above range.

<Surfactant>
The composition for temporary adhesion of the present invention preferably contains a surfactant.
As the surfactant, any of anionic, cationic, nonionic, and amphoteric surfactants can be used. Preferred surfactants are nonionic surfactants.
Preferred examples of the nonionic surfactant include polyoxyethylene higher alkyl ethers, polyoxyethylene higher alkyl phenyl ethers, and higher fatty acid diesters of polyoxyethylene glycol.

  When the composition for temporary bonding of the present invention has a surfactant, the content of the surfactant in the composition for temporary bonding is 0.1% based on the total solid content of the composition for temporary bonding from the viewpoint of applicability. It is preferably from 001 to 5% by mass, more preferably from 0.005 to 1% by mass, even more preferably from 0.01 to 0.5% by mass. The surfactant may be only one kind or two or more kinds. When two or more surfactants are used, the total is preferably within the above range.

<Other additives>
The temporary bonding composition of the present invention is, if necessary, various additives such as a curing agent, a curing catalyst, a filler, an adhesion promoter, an ultraviolet absorber, and an agglomeration prevention within a range not to impair the effects of the present invention. Agents and the like can be added. When these additives are blended, the total blending amount is preferably 3% by mass or less of the total solids of the composition for temporary bonding.

The temporary bonding composition of the present invention preferably does not contain impurities such as metals. The content of impurities contained in these materials is preferably 1 mass ppm (parts per million) or less, more preferably 100 mass ppt (parts per trillion) or less, still more preferably 10 mass ppt or less, and substantially no content. (Below the detection limit of the measuring device) is particularly preferable.
Examples of the method for removing impurities such as metals from the temporary bonding composition include filtration using a filter. The filter pore size is preferably 10 nm or less, more preferably 5 nm or less, and even more preferably 3 nm or less. As the material of the filter, polytetrafluoroethylene, polyethylene, and nylon are preferable. The filter may be one that has been washed in advance with an organic solvent. In the filter filtration step, a plurality of types of filters may be connected in series or in parallel. When a plurality of types of filters are used, filters having different hole diameters and / or materials may be used in combination. Further, various materials may be filtered a plurality of times, and the step of filtering a plurality of times may be a circulation filtration step.
Further, as a method for reducing impurities such as metals contained in the temporary bonding composition, a raw material having a low metal content is selected as a raw material forming the temporary bonding composition, and a raw material forming the temporary bonding composition is selected. For example, filtration under a condition where contamination is suppressed as much as possible by lining the inside of the apparatus with Teflon (registered trademark) or the like. Preferred conditions for the filter filtration performed on the raw materials constituting the temporary bonding composition are the same as those described above.
In addition to filter filtration, removal of impurities by an adsorbent may be performed, or filter filtration and removal of impurities by an adsorbent may be performed in combination. As the adsorbent, a known adsorbent can be used. For example, an inorganic adsorbent such as silica gel and zeolite, and an organic adsorbent such as activated carbon can be used.

<Formation of temporary adhesive film>
The temporary adhesive film can be formed on at least one surface of the first base material and the second base material using the temporary bonding composition of the present invention. A temporary adhesive film may be formed on only one of the first base material and the second base material and bonded to the other base material. Alternatively, a temporary adhesive film may be provided on both base materials and both bonded together. Is also good.
For the formation of the temporary adhesive film, the composition for temporary adhesion can be used by a conventionally known spin coating method, spray method, slit coating method, roller coating method, flow coating method, doctor coating method, immersion method and the like.
Next, since the temporary bonding composition usually contains a solvent, heating is performed to evaporate the solvent. The heating temperature is preferably higher than the boiling point of the solvent, more preferably 110 ° C or higher, further preferably 130 ° C to 200 ° C, and particularly preferably 160 ° C to 190 ° C.

<Preparation of composition for temporary bonding>
The composition for temporary adhesion of the present invention can be prepared by mixing the above-mentioned components. Mixing of each component is usually performed in the range of 0 ° C to 100 ° C. Further, it is preferable that the components are mixed and then filtered, for example, with a filter. Filtration may be performed in multiple stages or may be repeated many times. Further, the filtered liquid can be re-filtered.
The filter can be used without any particular limitation as long as it has been conventionally used for filtration or the like. For example, a fluororesin such as PTFE (polytetrafluoroethylene), a polyamide resin such as nylon-6, nylon-6,6, a polyolefin resin such as polyethylene and polypropylene (PP) (a high-density, ultrahigh-molecular-weight polyolefin resin) may be used. And the like. Among these materials, polypropylene (including high-density polypropylene) and nylon are preferred.
The filter preferably has a pore size of, for example, about 0.003 to 5.0 μm. By setting the content in this range, it is possible to reliably remove fine foreign substances such as impurities and aggregates contained in the composition while suppressing filter clogging.
When using filters, different filters may be combined. At that time, the filtering by the first filter may be performed only once or may be performed two or more times. In the case where filtering is performed two or more times by combining different filters, it is preferable that the hole diameters of the second and subsequent times are equal to or smaller than the hole diameters of the first filtering. Further, first filters having different hole diameters within the above-described range may be combined. The pore diameter here can refer to the nominal value of the filter manufacturer. Commercially available filters can be selected from various filters provided by, for example, Nippon Pall Co., Advantech Toyo Co., Ltd., Nippon Integris Co., Ltd., or Kitz Microfilter Co., Ltd.

<Peeling force of composition for temporary adhesion>
The temporary adhesive composition of the present invention preferably has a peeling force of 1 to 20 N / m, more preferably 1 to 25 N / m. More preferably, the lower limit of the peeling force is 3.0 N / m or more. The upper limit of the peeling force is more preferably 20 N / m or less, further preferably 15 N / m or less, further preferably 10 N / m or less, and even more preferably 9 N / m or less. preferable. By setting the content in such a range, the effect of enabling peeling without damaging the processed substrate is more effectively exhibited.
Here, the peeling force means that a temporary adhesive film having a thickness of 15 μm is formed on the surface of a silicon wafer using the temporary adhesive composition, and the silicon wafer is temporarily bonded at a speed of 300 mm / min at 25 ° C. This is a force that can be peeled off by pulling up the end of the temporary adhesive film in a direction perpendicular to the surface on which the film is formed, and that the force applied when pulling up is measured using a force gauge. Specifically, the method described in the embodiment described later is used.

Laminate The present invention also discloses a laminate having a first substrate, a temporary adhesive film, and a second substrate adjacent to each other in the above order. The temporary adhesive film is formed from the above-described temporary adhesive composition of the present invention. In the laminate of the present invention, the first base material and the second base material are temporarily bonded to each other using the temporary bonding composition.

Semiconductor Device Manufacturing Method <First Embodiment>
Hereinafter, an embodiment of a method of manufacturing a semiconductor device through a step of manufacturing a stacked body will be described with reference to FIG. Note that the present invention is not limited to the following embodiments.
1A to 1E are schematic cross-sectional views (FIGS. 1A and 1B) for explaining temporary bonding between a carrier substrate and a device wafer, respectively, showing a device temporarily bonded to a carrier substrate. The state where the wafer is thinned (FIG. 1 (C)), the state where the carrier base material and the device wafer are separated (FIG. 1 (D)), and the state after removing the temporary adhesive film from the device wafer (FIG. 1 (E)). FIG.

In this embodiment, as shown in FIG. 1A, first, an adhesive carrier substrate 100 in which a temporary adhesive film 11 is provided on a carrier substrate 12 is prepared.
The temporary adhesive film 11 can be formed using the temporary adhesive composition of the present invention. It is preferable that the temporary adhesive film 11 be in a mode that does not substantially contain a solvent.
The device wafer 60 has a plurality of device chips 62 provided on a surface 61 a of a silicon substrate 61.
The thickness of the silicon substrate 61 is preferably, for example, 200 to 1200 μm. The device chip 62 is preferably a metal structure, for example, and preferably has a height of 10 to 100 μm.
In the process of forming the temporary adhesive film, a step of cleaning the back surfaces of the carrier base material and the device wafer with a solvent may be provided. Specifically, by removing the residue of the temporary adhesive film adhered to the end surface or the back surface of the base material or the wafer using a solvent that dissolves the temporary adhesive film, it is possible to prevent the contamination of the apparatus and to reduce the thickness of the thin device. TTV (Total Thickness Variation) of the wafer can be reduced.
As the solvent used in the step of cleaning the back surface of the carrier substrate and the device wafer with the solvent, the solvent contained in the above-mentioned composition for temporary bonding can be used.

Next, as shown in FIG. 1B, the adhesive carrier base material and the device wafer 60 are pressed, and the carrier base material 12 and the device wafer 60 are temporarily bonded.
The temporary adhesive film 11 preferably completely covers the device chip 62, and when the height of the device chip is X μm and the thickness of the temporary adhesive film is Y μm, the relationship of “X + 100 ≧ Y> X” is satisfied. Is preferred.
The fact that the temporary adhesive film 11 completely covers the device chip 62 is effective when it is desired to further reduce the TTV of the thinned device wafer (ie, when it is desired to further improve the flatness of the thinned device wafer). .
That is, when the device wafer is thinned, the plurality of device chips 62 are protected by the temporary adhesive film 11, so that the uneven surface on the contact surface with the carrier substrate 12 can be almost eliminated. Therefore, even if the device is thinned while being supported in this manner, the possibility that the shape derived from the plurality of device chips 62 is transferred to the back surface 61b1 of the thinned device wafer is reduced, and as a result, the finally obtained thinner TTV of the device wafer can be further reduced.

  Next, as shown in FIG. 1C, the rear surface 61b of the silicon substrate 61 is subjected to mechanical or chemical processing (though not particularly limited, for example, thinning processing such as gliding or chemical mechanical polishing (CMP)). High-temperature and vacuum treatments such as chemical vapor deposition (CVD) and physical vapor deposition (PVD), treatments with chemicals such as organic solvents, acidic treatment solutions and basic treatment solutions, plating treatments, and actinic rays Irradiation, heat treatment, cooling treatment, etc.). In FIG. 1C, the thickness of the silicon substrate 61 is reduced (for example, the thickness is reduced to the above-described thickness) to obtain a thinned device wafer 60a.

After thinning the device wafer and before performing the process under high temperature and vacuum, a step of cleaning the temporary adhesive film that has protruded outside the substrate surface area of the device wafer with a solvent may be provided. . Specifically, after thinning the device wafer, the protruding temporary adhesive film is removed using a solvent that dissolves the temporary adhesive film, so that processing at a high temperature and in a vacuum is directly applied to the temporary adhesive film. This prevents deformation and deterioration of the temporary adhesive film. As the solvent used in the step of cleaning the temporary adhesive film protruding outside the area of the substrate surface of the carrier substrate or the substrate surface of the device wafer with a solvent, the solvent contained in the temporary bonding composition is used. Can be used.
That is, in the present invention, the area of the film surface of the temporary adhesive film is preferably smaller than the area of the substrate surface of the carrier substrate. In the present invention, when the diameter of the substrate surface of the carrier substrate is C μm, the diameter of the substrate surface of the device wafer is D μm, and the diameter of the temporary adhesion film is T μm, (C−200) ≧ T It is more preferable to satisfy ≧ D. Further, the diameter of the substrate surface of the carrier substrate is _C μm, the diameter of the substrate surface of the device wafer is _D μm, the diameter of the temporary adhesive film on the side in contact with the carrier substrate is _TC μm, When the diameter of the film surface in contact with the device wafer is T _D μm, it is preferable to satisfy (C-200) ≧ T _C > T _D ≧ D. With such a configuration, it is possible to further suppress deformation and deterioration of the temporary adhesive film due to the high temperature and vacuum treatment being directly applied to the temporary adhesive film.
In addition, the area of the film surface of the temporary adhesive film refers to an area when viewed from a direction perpendicular to the carrier substrate, and does not consider irregularities on the film surface. The same applies to the substrate surface of the device wafer. That is, the substrate surface of the device wafer referred to here is, for example, a surface corresponding to the surface 61a in FIG. 1 and is a surface on which the device chips are provided. The same applies to the diameter of the temporary adhesive film such as the film surface.
Further, the diameter T of the film surface of the temporary adhesive film is defined as T _C μm, the diameter of the film surface of the temporary adhesive film in contact with the carrier substrate, and the film surface of the temporary adhesive film in contact with the device wafer. Is T _D μm, T = (T _C + T _D ) / 2. The diameter of the substrate surface of the carrier substrate and the diameter of the substrate surface of the device wafer refer to the diameter of the surface in contact with the temporary adhesive film.
Note that the carrier base material and the like are defined as “diameter”. However, it is not essential that the carrier base material and the like have a circular shape (a perfect circle) in a mathematical sense. Good. If the circle is not a perfect circle, the diameter when converted to a perfect circle of the same area is the above diameter.
Further, as a mechanical or chemical treatment, a through hole (not shown) penetrating the silicon substrate is formed from the back surface 61b1 of the thinned device wafer 60a after the thinning process, and a silicon through electrode is formed in the through hole. (Not shown) may be performed.
Further, after the carrier base material 12 and the device wafer 60 are temporarily bonded at the stage of FIG. As an example of the heat treatment, heating is performed when mechanical or chemical treatment is performed.
The maximum temperature in the heat treatment is preferably from 80 to 400C, more preferably from 130C to 400C, even more preferably from 180C to 350C. It is preferable that the highest temperature in the heat treatment is lower than the decomposition temperature of the temporary adhesive film. The heat treatment is preferably heating at the highest temperature for 30 seconds to 30 minutes, and more preferably heating at the highest temperature for 1 minute to 10 minutes.
However, irrespective of the decomposition temperature of the components contained in the temporary bonding composition, it can be used satisfactorily if there is no swelling or void generation in the temporary bonding film after the heat treatment. The occurrence of voids can be detected by observation with an ultrasonic microscope.

Next, as shown in FIG. 1D, the carrier base material 12 is peeled from the thinned device wafer 60a. The temperature at the time of peeling is preferably 40 ° C. or lower, and may be 30 ° C. or lower. The lower limit of the temperature at the time of peeling is, for example, 0 ° C. or higher, and preferably 10 ° C. or higher. The use of the composition for temporary bonding of the present invention is highly valuable in that it can be peeled at room temperature of about 15 to 35 ° C.
The method of peeling is not particularly limited, but it is preferable that the thinned device wafer 60a is fixed, and the thinned device wafer 60a is pulled up from the end of the carrier base material laminate in a direction perpendicular to the thinned device wafer 60a and peeled off. At this time, the separation interface is preferably separated at the interface between the carrier base material 12 and the temporary adhesive film 11. The lifting speed at the time of peeling is preferably 30 to 100 mm / min, more preferably 40 to 80 mm / min. In this case, the adhesive strength A at the interface between the carrier base material 12 and the temporary adhesive film 11 and the adhesive strength B between the device wafer surface 61a and the temporary adhesive film 11 preferably satisfy the following expressions.
A <B ... Formula (A1)
Further, the force at the time of lifting the end portion at the time of peeling is preferably 0.33 N / mm or less, and may be 0.2 N / mm or less. The lower limit is preferably 0.07 N / mm or more. The force at this time can be measured using a force gauge.

Then, as shown in FIG. 1E, by removing the temporary adhesive film 11 from the thinned device wafer 60a, a thinned device wafer can be obtained.
The method of removing the temporary adhesive film 11 includes, for example, a method of peeling and removing the temporary adhesive film as it is and a method of removing the temporary adhesive film using a peeling liquid (peeling after swelling the temporary adhesive film with a peeling liquid). Removal method, method of breaking and removing the temporary adhesive film by spraying a release liquid, method of dissolving and removing the temporary adhesive film in the release liquid, etc.), decomposing the temporary adhesive film by irradiation with actinic rays, radiation or heat And a method of vaporizing and removing. From the viewpoint of reducing the amount of the stripping solution used, it is preferable to strip and remove the film as it is (in the form of a film). From the viewpoint of reducing the damage on the surface of the device wafer, dissolution and removal are preferable. The method of peeling and removing the temporary adhesive film as it is means that the temporary adhesive film is peeled as it is (film-like) without performing a chemical treatment such as using a peeling liquid. When peeling the temporary adhesive film as it is, mechanical peeling is preferable. In order to remove the temporary adhesive film as it is (in the form of a film), it is preferable that the adhesion strength B between the device wafer surface 61a and the temporary adhesive film 11 satisfies the following expression (B1).
B ≦ 4N / cm ··· Formula (B1)
When the temporary protective film is removed using a stripper, the following strippers can be preferably used.

<< Release liquid >>
As the stripping solution, water and a solvent (organic solvent) can be used.
Further, as the stripping liquid, an organic solvent that dissolves the temporary adhesive film 11 is preferable. Examples of the organic solvent include aliphatic hydrocarbons (hexane, heptane, isoper E, H, G (manufactured by Esso Chemical Co., Ltd.), limonene, p-menthane, nonane, decane, dodecane, decalin, etc.), aromatics Hydrocarbons (toluene, xylene, anisole, mesitylene, pseudocumene, ethylbenzene, propylbenzene, cumene, n-butylbenzene, sec-butylbenzene, isobutylbenzene, tert-butylbenzene, amylbenzene, isoamylbenzene, (2,2- Dimethylpropyl) benzene, 1-phenylhexane, 1-phenylheptane, 1-phenyloctane, 1-phenylnonane, 1-phenyldecane, cyclopropylbenzene, cyclohexylbenzene, 2-ethyltoluene, 1,2-diethylbenzene, o -Shimen Indane, 1,2,3,4-tetrahydronaphthalene, 3-ethyltoluene, m-cymene, 1,3-diisopropylbenzene, 4-ethyltoluene, 1,4-diethylbenzene, p-cymene, 1,4-diisopropylbenzene , 4-tert-butyltoluene, 1,4-di-tert-butylbenzene, 1,3-diethylbenzene, 1,2,3-trimethylbenzene, 1,2,4-trimethylbenzene, 4-tert-butyl-o -Xylene, 1,2,4-triethylbenzene, 1,3,5-triethylbenzene, 1,3,5-triisopropylbenzene, 5-tert-butyl-m-xylene, 3,5-di-tert-butyl Toluene, 1,2,3,5-tetramethylbenzene, 1,2,4,5-tetramethylbenzene, pentamethylbenzene Zen, etc.), halogenated hydrocarbons (methylene dichloride, ethylene dichloride, trichlorethylene, monochlorobenzene, etc.), polar solvents. Examples of the polar solvent include alcohols (methanol, ethanol, propanol, isopropanol, 1-butanol, 1-pentanol, 1-hexanol, 1-heptanol, 1-octanol, 2-octanol, 2-ethyl-1-hexanol, -Nonanol, 1-decanol, benzyl alcohol, ethylene glycol monomethyl ether, 2-ethoxyethanol, diethylene glycol monoethyl ether, diethylene glycol monohexyl ether, triethylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether, polyethylene glycol monomethyl Ether, polypropylene glycol, tetraethylene glycol, ethylene glycol monobutyl ether Ter, ethylene glycol monobenzyl ether, ethylene glycol monophenyl ether, propylene glycol monophenyl ether, methylphenyl carbinol, n-amyl alcohol, methyl amyl alcohol, etc., ketones (acetone, methyl ethyl ketone, ethyl butyl ketone, methyl isobutyl ketone) , Cyclohexanone, cyclopentanone, etc.), esters (ethyl acetate, propyl acetate, butyl acetate, amyl acetate, benzyl acetate, methyl lactate, butyl lactate, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, diethylene glycol acetate, diethyl phthalate) , Butyl levulinate, etc.), others (triethyl phosphate, tricresyl phosphate, -Phenylethanolamine, N-phenyldiethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, 4- (2-hydroxyethyl) morpholine, N, N-dimethylacetamide, N-methylpyrrolidone, N-ethyl-2-pyrrolidone, etc. ).

Further, from the viewpoint of peelability, the peeling solution may contain an alkali, an acid, and a surfactant. When these components are blended, the blending amount is preferably 0.1 to 5.0% by mass of the stripping solution.
Further, from the viewpoint of peelability, a form in which two or more kinds of organic solvents and water, two or more kinds of alkalis, acids and surfactants are mixed is also preferable.

  As the alkali, for example, sodium phosphate tribasic, potassium phosphate tribasic, ammonium phosphate tribasic, sodium phosphate dibasic, potassium phosphate dibasic, ammonium phosphate dibasic, sodium carbonate, potassium carbonate, ammonium carbonate Sodium bicarbonate, potassium bicarbonate, ammonium bicarbonate, sodium borate, potassium borate, ammonium borate, sodium hydroxide, ammonium hydroxide, inorganic alkali agents such as potassium hydroxide and lithium hydroxide, and monomethylamine, Dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine, triisopropylamine, n-butylamine, monoethanolamine, diethanolamine, triethanolamine Emissions, monoisopropanolamine, diisopropanolamine, ethyleneimine, ethylenediamine, pyridine, may be used an organic alkali agent such as tetramethylammonium hydroxide. These alkaline agents can be used alone or in combination of two or more.

  Examples of the acid include inorganic acids such as hydrogen halide, sulfuric acid, nitric acid, phosphoric acid, and boric acid; alkylsulfonic acid, benzenesulfonic acid, alkylbenzenesulfonic acid, p-toluenesulfonic acid, trifluoromethanesulfonic acid, acetic acid, and citric acid. And organic acids such as formic acid, gluconic acid, lactic acid, oxalic acid and tartaric acid.

As the surfactant, anionic, cationic, nonionic and zwitterionic surfactants can be used. In this case, the content of the surfactant is preferably 1 to 20% by mass, more preferably 1 to 10% by mass, based on the total amount of the aqueous alkali solution.
By setting the content of the surfactant within the above-described range, there is a tendency that the releasability between the temporary adhesive film 11 and the thinned device wafer 60a can be further improved.

  Examples of the anionic surfactant include, but are not particularly limited to, fatty acid salts, abietic acid salts, hydroxyalkane sulfonates, alkane sulfonates, dialkyl sulfosuccinates, linear alkyl benzene sulfonates, branched alkyl benzene sulfonates, Alkyl naphthalene sulfonates, alkyl diphenyl ether (di) sulfonates, alkyl phenoxy polyoxyethylene alkyl sulfonates, polyoxyethylene alkyl sulfophenyl ether salts, N-alkyl-N-oleyltaurine sodium, N-alkyl sulfosuccinic acid Monoamide disodium salts, petroleum sulfonates, sulfated castor oil, sulfated tallow oil, sulfates of fatty acid alkyl esters, alkyl sulfates, polyoxy Ethylene alkyl ether sulfates, fatty acid monoglyceride sulfates, polyoxyethylene alkyl phenyl ether sulfates, polyoxyethylene styryl phenyl ether sulfates, alkyl phosphates, polyoxyethylene alkyl ether phosphates, poly Oxyethylene alkylphenyl ether phosphates, partially saponified styrene-maleic anhydride copolymers, partially saponified olefin-maleic anhydride copolymers, naphthalene sulfonate formalin condensates, and the like. . Of these, alkyl benzene sulfonates, alkyl naphthalene sulfonates, and alkyl diphenyl ether (di) sulfonates are particularly preferably used.

  The cationic surfactant is not particularly limited, but a conventionally known cationic surfactant can be used. Examples include alkylamine salts, quaternary ammonium salts, alkylimidazolinium salts, polyoxyethylene alkylamine salts, and polyethylenepolyamine derivatives.

  The nonionic surfactant is not particularly limited, but includes polyethylene glycol type higher alcohol ethylene oxide adduct, alkylphenol ethylene oxide adduct, alkyl naphthol ethylene oxide adduct, phenol ethylene oxide adduct, naphthol ethylene oxide adduct, fatty acid Ethylene oxide adduct, polyhydric alcohol fatty acid ester ethylene oxide adduct, higher alkylamine ethylene oxide adduct, fatty acid amide ethylene oxide adduct, ethylene oxide adduct of fats and oils, polypropylene glycol ethylene oxide adduct, dimethylsiloxane-ethylene oxide block Copolymer, dimethylsiloxane- (propylene oxide-ethylene oxide) block copolymer Fatty acid esters of polyhydric alcohol type glycerol, fatty acid esters of pentaerythritol, fatty acid esters of sorbitol and sorbitan, fatty acid esters of sucrose, alkyl ethers of polyhydric alcohols, fatty acid amides of alkanolamines. Among them, those having an aromatic ring and an ethylene oxide chain are preferable, and alkyl-substituted or unsubstituted phenol ethylene oxide adducts or alkyl-substituted or unsubstituted naphthol ethylene oxide adducts are more preferable.

  Examples of the amphoteric surfactant include, but are not particularly limited to, amine oxides such as alkyldimethylamine oxide, betaines such as alkyl betaines, and amino acids such as sodium alkylamino fatty acids. In particular, an alkyldimethylamine oxide which may have a substituent, an alkylcarboxybetaine which may have a substituent, and an alkylsulfobetaine which may have a substituent are preferably used. Specifically, the compound represented by the formula (2) in paragraph No. 0256 of JP-A-2008-203359, the formula (I), the formula (II), the formula (II) in paragraph 0028 of JP-A-2008-276166 Compounds represented by VI) and compounds represented by paragraphs 0022 to 0029 of JP-A-2009-47927 can be used.

  Furthermore, if necessary, additives such as an antifoaming agent and a water softener can be contained.

When peeling the carrier base material 12 from the thinned device wafer 60a, it is preferable that the carrier base material 12 be pulled up from an end of the thinned device wafer 60a in a direction perpendicular to the device wafer without any treatment, and the device wafer surface 61a As a method for removing the temporary adhesive film 11 above, it is preferable to remove the temporary adhesive film 11 in a film form.
Assuming that the adhesive strength at the interface between the carrier base material 12 and the temporary adhesive film 11 is A, and that the adhesive strength B between the device wafer surface 61a and the temporary adhesive film 11 is B, the carrier is satisfied by satisfying both the above-described equations (A1) and (B1). The substrate 12 and the temporary adhesive film 11 can be removed from the device wafer in the manner described above.
After the carrier base material 12 is peeled off from the thinned device wafer 60a, various known processes are performed on the thinned device wafer 60a as necessary to manufacture a semiconductor device having the thinned device wafer 60a.

When the temporary adhesive film is attached to the carrier substrate, the carrier substrate can be regenerated by removing the temporary adhesive film. As a method of removing the temporary adhesive film, as a film, brush, ultrasonic waves, ice particles, a method of physically removing by spraying aerosol, and a method of dissolving and removing by dissolving in an aqueous solution or an organic solvent, Chemical removal methods such as a method of decomposing and vaporizing by irradiation with actinic rays, radiation or heat may be mentioned, and conventionally known removal methods can be used depending on the carrier base material.
For example, when a silicon substrate is used as a carrier substrate, a conventionally known method for cleaning a silicon wafer can be used.For example, as an aqueous solution or an organic solvent that can be used for chemical removal, a strong acid, a strong base, Strong oxidants, or mixtures thereof, specifically, sulfuric acid, hydrochloric acid, hydrofluoric acid, nitric acid, acids such as organic acids, tetramethylammonium, ammonia, bases such as organic bases, hydrogen peroxide and the like Oxidant, or mixture of ammonia and hydrogen peroxide, mixture of hydrochloric acid and hydrogen peroxide, mixture of sulfuric acid and hydrogen peroxide, mixture of hydrofluoric acid and hydrogen peroxide, mixture of hydrofluoric acid and ammonium fluoride, etc. Is mentioned.

  When a regenerated carrier substrate is used, the method of removing the temporary adhesive film is preferably a method using a carrier substrate cleaning solution from the viewpoint of adhesiveness. The carrier substrate cleaning liquid preferably contains an acid (strong acid) having a pKa of less than 0 and hydrogen peroxide. The acid having a pKa of less than 0 is selected from inorganic acids such as hydrogen iodide, perchloric acid, hydrogen bromide, hydrogen chloride, nitric acid and sulfuric acid, and organic acids such as alkylsulfonic acid and arylsulfonic acid. From the viewpoint of the cleaning property of the temporary adhesive film on the carrier substrate, an inorganic acid is preferable, and sulfuric acid is most preferable.

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

<Second embodiment>
A second embodiment of a method for manufacturing a semiconductor through a step of manufacturing a laminate will be described with reference to FIG. The same parts as those in the first embodiment described above are denoted by the same reference numerals, and description thereof will be omitted.
2A to 2E are schematic cross-sectional views (FIGS. 2A and 2B) for explaining temporary bonding between a carrier substrate and a device wafer, respectively, showing a device temporarily bonded to a carrier substrate. The state where the wafer is thinned (FIG. 2 (C)), the state where the carrier base material and the device wafer are separated (FIG. 2 (D)), and the state after removing the temporary adhesive film from the device wafer (FIG. 2 (E)). FIG.
This embodiment is different from the first embodiment in that a temporary adhesive film is formed on a surface 61a of a device wafer as shown in FIG.
When the temporary adhesive film 11a is provided on the surface 61a of the device wafer 60, the temporary adhesive composition is applied (preferably applied) to the surface of the surface 61a of the device wafer 60, and then dried (baked). Can be formed. Drying can be performed, for example, at 60 to 150 ° C. for 10 seconds to 2 minutes.
Next, as shown in FIG. 2B, the carrier base material 12 and the device wafer 60 are press-bonded, and the carrier base material 12 and the device wafer 60 are temporarily bonded. Next, as shown in FIG. 2C, the back surface 61b of the silicon substrate 61 is subjected to a mechanical or chemical treatment to reduce the thickness of the silicon substrate 61 as shown in FIG. The thinned device wafer 60a is obtained. Next, as shown in FIG. 2D, the carrier substrate 12 is peeled off from the thinned device wafer 60a. Then, as shown in FIG. 2E, the temporary adhesive film 11a is removed from the thinned device wafer 60a.

<Conventional embodiment>
Next, a conventional embodiment will be described.
FIG. 3 is a schematic cross-sectional view for explaining the release of the temporary adhesion state between the conventional adhesive carrier substrate and the device wafer.
In the conventional embodiment, as shown in FIG. 3, an adhesive formed by providing a temporary adhesive film 11b formed of a conventional temporary adhesive composition on a carrier substrate 12 as an adhesive carrier substrate. Otherwise, the adhesive carrier substrate 100a and the device wafer are temporarily bonded to each other in the same manner as described with reference to FIG. 1 to reduce the thickness of the silicon substrate 61 in the device wafer. The processing is performed, and then, the thinned device wafer 60a is peeled off from the adhesive carrier base material 100a in the same manner as described above.

However, according to the conventional temporary bonding composition, it is difficult to temporarily support the device wafer with a high adhesive force and easily release the temporary support to the device wafer without damaging the device wafer. For example, if a conventional adhesive composition having a high adhesiveness is used in order to sufficiently provide temporary bonding between the device wafer and the carrier base material, the temporary bonding between the device wafer and the carrier base material is reduced. It tends to be too strong. Therefore, in order to release the temporary adhesion that is too strong, for example, as shown in FIG. When the device wafer 60a is peeled, a problem that the device 63 is damaged is likely to occur because the structure 63 is peeled from the device chip 62 on which the structure 63 is provided.
On the other hand, when a composition having low adhesiveness is employed among the conventional temporary bonding compositions, temporary support for the device wafer can be easily released, but the temporary adhesion between the device wafer and the carrier substrate is too weak in the first place. In addition, a problem that the device wafer cannot be reliably supported by the carrier base material is likely to occur.

  On the other hand, the laminate of the present invention exhibits sufficient adhesiveness and can easily release the temporary adhesion between the device wafer 60 and the carrier base material 12. That is, according to the laminate of the present invention, the device wafer 60 can be temporarily bonded with a high adhesive force, and the temporary bonding to the thinned device wafer 60a can be easily released without damaging the thinned device wafer 60a.

The method of manufacturing a semiconductor device according to the present invention is not limited to the above-described embodiment, and appropriate modifications and improvements can be made.
In the above-described embodiments, a silicon substrate is described as a device wafer. However, the present invention is not limited to this, and any device that can be subjected to mechanical or chemical processing in a method of manufacturing a semiconductor device. It may be a processing member.
Further, in the above-described embodiment, as the mechanical or chemical processing for the device wafer (silicon substrate), the processing for thinning the device wafer and the processing for forming the through silicon via have been described, but are not limited thereto. Instead, any process required in a method for manufacturing a semiconductor device may be used.
In addition, the shapes, dimensions, numbers, arrangement locations, and the like of the device chips on the device wafer illustrated in the above-described embodiment are arbitrary and are not limited.
Further, as another embodiment, the following configuration is also possible.
The temporary bonding composition is applied to a glass, silicon, or metal carrier to form a temporary adhesive film, and a diced chip is bonded thereon. The bonding temperature at this time is preferably in the range of 10 ° C to 250 ° C. Further, the bonded chip is sealed with a molding resin, and the molding resin in which the chip is embedded is peeled from the adhesive carrier base material in the same manner as described above, and the temporary adhesive film is removed.

  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 of the present invention. Unless otherwise specified, “parts” and “%” are based on mass.

<Preparation of composition for temporary bonding>
As shown below, the components of the temporary bonding composition were mixed to form a uniform solution, and then filtered using a polytetrafluoroethylene filter having a pore size of 5 μm to prepare a temporary bonding composition. .

<< Composition of Temporary Adhesive Composition >>
-Resin described in Table 1: Amount described in Table 1-Additive described in Table 1: Amount described in Table 1-Solvent described in Table 1: Amount described in Table 1 <<<< All temporary adhesion Ingredients in the composition for use >>
-Irganox 1010 (manufactured by BASF Japan Ltd.): 1 part by mass-Sumilizer TP-D (manufactured by Sumitomo Chemical Co., Ltd.): 1 part by mass

  In Table 1 above, E indicates the tensile modulus of the resin at 25 ° C. in accordance with JIS K 7161: 1994.

  The styrene ratio (proportion of styrene-derived repeating units, mass%) was determined by forming a temporary bonding composition on a wafer, peeling it off, dissolving it in trichlorobenzene / deuterated benzene = 80/20 (volume%), Using H-NMR (JEOL-JSX400, manufactured by JEOL Ltd.), the integrated intensity of the signal attributed to styrene and other copolymer components in the resin was measured, and the specific gravity of each copolymer component was multiplied. It calculated by doing.

The compounds described in Table 1 are as follows.
In the above table, COP refers to a cycloolefin-based polymer, and TPI refers to a thermoplastic polyimide resin.

<< Measuring method of mass loss rate of polyether-modified silicone after heating at 280 ° C. for 30 minutes >>
The “weight loss rate at 280 ° C. for 30 minutes” described in the above table was measured from 20 ° C. to 280 ° C. under a nitrogen flow of 60 mL / min using a thermogravimeter (TGA-50, manufactured by Shimadzu Corporation). The temperature was raised at a rate of 20 ° C./min, kept at a temperature of 280 ° C. for 30 minutes, and calculated based on the following equation.
Mass reduction rate (% by mass) =
{(Mass at 20 ° C.-mass after holding at 280 ° C. for 30 minutes) / mass at 20 ° C.} × 100

<< Measuring method of refractive index >>
The refractive index was measured using a precision refractometer (KPR-3000, manufactured by Shimadzu Corporation) at a temperature of 25 ° C. and a wavelength of 589 nm.

<< Method of measuring ratio represented by formula (A) >>
The ratio represented by the formula (A) was calculated from the area ratio of each of the peaks of hydrogen atoms specific to methylene oxide, ethylene oxide, and propylene oxide using NMR (nuclear magnetic resonance).

<Formation of laminate>
<< Formation of Laminate (Examples 1 to 16, 18 to 19, Comparative Examples 1 to 8) >>
A 12-inch diameter silicon wafer (1 inch is 2.54 cm) is used as a first base material, and a temporary bonding composition shown in Table 1 is coated on the surface of the silicon wafer with a wafer bonding apparatus (Tokyo Electron Limited) (Synapse V). Using a hot plate, the mixture was heated at 130 ° C. for 3 minutes, and further heated at 190 ° C. for 3 minutes to form a temporary adhesive film on the surface of the first base material. At this time, the thickness of the temporary adhesive film was 60 μm.

<< Formation of Laminated Body (Example 17) >>
A 12-inch diameter silicon wafer was used as the first base material, and the composition for temporary bonding was applied on the surface thereof by a wafer bonding apparatus (Synapse V, manufactured by Tokyo Electron Limited) to form a film. Using a hot plate, the mixture was heated at 130 ° C. for 3 minutes, and further heated at 190 ° C. for 3 minutes to form a temporary adhesive film on the surface of the first base material. At this time, the thickness of the temporary adhesive film was 30 μm.
A silicon wafer having a diameter of 12 inches was used as the second base material, and the composition for temporary bonding was applied on the surface thereof using a wafer bonding apparatus (Synapse V, manufactured by Tokyo Electron Limited) to form a film. Using a hot plate, heating was performed at 130 ° C. for 3 minutes, and further heating was performed at 190 ° C. for 3 minutes to form a temporary adhesive film on the surface of the second base material. At this time, the thickness of the temporary adhesive film was 30 μm.

<< Bonding Process (Examples 1 to 18, Comparative Examples 1 to 8) >>
The first base material and the second base material on which the temporary adhesive film is formed, or the first base material on which the temporary adhesive film is formed and the second base material on which the temporary adhesive film is formed are bonded to a wafer bonding apparatus ( The laminate was thermocompression-bonded under a pressure of 10 Pa, a temperature of 200 ° C., and a pressure of 0.5 MPa for 5 minutes under a pressure of 10 Pa and a pressure of 0.5 MPa by Tokyo Electron Ltd., Synapse V).

<< bonding process (Example 19) >>
The first base material on which the temporary adhesive film is formed and the second base material are bonded at a pressure of 10 Pa, a temperature of 300 ° C., and a pressure of 0.5 MPa by a wafer bonding apparatus (520IS manufactured by Evi Group Japan Co., Ltd.). Thermocompression bonding was performed for 3 minutes to obtain a laminate.

<< Back grinding >>
The back surface of the laminate on the side of the base material 2 (the side on which the temporary adhesive film is not provided) was polished to a thickness of 40 μm using a back grinder (manufactured by Disco Co., Ltd., DFG8540) to obtain a thinned laminate. Obtained.

<< CVD (Chemical Vapor Deposition) Processing >>
Using TEOS (tetraethyl orthosilicate) and O ₂ gas on the back surface of the thinned substrate 2 (the side on which the temporary adhesive film is not provided) of the obtained laminate, at 200 ° C. for 20 minutes. An SiO ₂ film was formed by a CVD process. The thickness of the obtained SiO ₂ film was 2 μm.

<< surface evaluation >>
The laminated body subjected to the CVD processing was visually observed, and the number of blisters was evaluated based on the following criteria.
A: No swelling was observed on the substrate 2.
B: Swelling was observed in the base material 2 and less than 5 swollen portions having a length of the longest portion less than 5 mm.
C: Swelling was observed in the base material 2, and swelling with the longest portion of 5 mm or more or swelling with the longest portion of less than 5 mm was observed 5 or more.

<< warp >>
The laminated body subjected to the CVD processing was measured for warpage (radius of curvature) using a thin film stress measurement device (FLX-2320-S, manufactured by Toho Technology Co., Ltd.), and evaluated according to the following criteria. . Note that the evaluation was performed using the absolute value regardless of the direction of the warpage.
A: Warp value is 50 μm or less B: Warp value is more than 50 μm, 100 μm or less C: Warp value is more than 100 μm, 200 μm or less D: Warp value is more than 200 μm

<< Measurement of peeling force >>
A silicon wafer having a diameter of 4 inches (1 inch is 2.54 cm) is used as a base material, and the composition for temporary bonding described in Table 1 is spin-coated (MS-B200, manufactured by Mikasa Corporation) on the surface thereof. ). Using a hot plate, the mixture was heated at 130 ° C. for 3 minutes, and further heated at 190 ° C. for 3 minutes to form a temporary adhesive film on the surface of the first base material. At this time, the thickness of the temporary adhesive film was 15 μm.
A cut is made in the temporary adhesive film of the laminate to a width of 90 mm, and at 25 ° C., at a speed of 300 mm / min, an end of the temporary adhesive film in a direction perpendicular to the surface of the silicon wafer on which the temporary adhesive film is formed. By pulling up, the possibility of peeling was confirmed, and the force applied when pulling up was measured using a force gauge (DS2-20N, manufactured by Imada Co., Ltd.). The unit was indicated by N / m.

<< Peeling evaluation >>
The surface of the laminated body subjected to the CVD process was subjected to the CVD process with the lower side facing down, and the lower silicon wafer was fixed together with a dicing frame to the center of the dicing tape using a dicing tape mounter. Thereafter, using a wafer debonder apparatus (Synapse Z, manufactured by Tokyo Electron Limited), the upper substrate is pulled up at a speed of 3 mm / min. Vertically at 25 ° C. with respect to the lower substrate. Then, it was confirmed whether or not the upper or lower base material could be peeled off without cracking, and evaluated based on the following criteria.
A: Peeling was possible B: Adhesion was weak and part of the periphery of the wafer was floating, but peeling was possible, or the wafer was broken at a pulling speed of 3 mm / min, but peelable at a pulling speed of 2 mm / min Met.
C: No peeling was possible even at a lifting speed of 2 mm / min.

  As is clear from the above results, when the temporary bonding composition of the present invention is used, the substrate can be appropriately peeled from the laminate obtained by temporarily fixing the substrates, and the surface of the processed substrate It was possible to provide a laminate excellent in surface condition (Examples 1 to 19). Furthermore, when the tensile elastic modulus was 1 MPa or more and 100 MPa or less, particularly when the tensile elastic modulus was 1 MPa or more and 60 MPa or less, a laminate with significantly small warpage was obtained (Examples 1 to 17, particularly, Examples 1 to 13 and Examples 15-17).

<Cleaning after peeling (Examples 1 to 18, Comparative Examples 2, 4, 6 to 8)>
The substrate on which the temporary adhesive film (temporary adhesive) after the peeling evaluation was left was sprayed with mesitylene for 180 seconds by rotating the substrate at 200 rpm using a wafer debonder (manufactured by Tokyo Electron, Synapse Z), thereby temporarily removing the substrate. The adhesive film (temporary adhesive) was removed.
In the case of the peeling evaluation "C", cleaning was not performed because cleaning was not possible after peeling.

<Cleaning after peeling (Example 19)>
By spraying cyclopentanone for 180 seconds while rotating the substrate on which the temporary adhesive film after the peeling evaluation was left at 200 rpm by a wafer debonder (manufactured by Tokyo Electron, Synapse Z), the temporary adhesive film was formed. Removed.

(Example 20)
Evaluation was performed in the same manner as in Example 1, except that the solvent was a mixed solvent of 80 parts by weight of mesitylene and 20 parts by weight of tert-butylbenzene (manufactured by Toyo Gosei Co., Ltd.). .

(Example 21)
Evaluation was carried out in the same manner as in Example 1 except that the solvent was 80 parts by mass of mesitylene and 20 parts by mass of pseudocumene (manufactured by Toyo Gosei Kogyo Co., Ltd.).

(Example 22)
A solvent was used as a mixture of 80 parts by mass of mesitylene and 20 parts by mass of cyclohexanone (manufactured by Sankyo Chemical Co., Ltd.), and the solid content was changed to 20%. Same as 1.

(Example 23)
The evaluation was performed in the same manner as in Example 19, except that the solvent was a mixed solvent of 80 parts by weight of mesitylene and 20 parts by weight of cyclopentanone (manufactured by Zeon Corporation).

(Example 24)
When the CVD process was performed in the same manner as in Example 1 except that the conditions were changed to 350 ° C. for 20 minutes, the evaluation was the same as in Example 1.

11, 11a: Temporary adhesive film 12: Carrier base material 60: Device wafer 60a: Thin device wafer 61: Silicon substrate 61a: Front surface 61b, 61b1: Back surface 62: Device chip 63: Structure 70: Tape 100, 100a: Adhesion Carrier base material

Claims (10)

A temporary bonding composition comprising a resin and a polyether-modified silicone A having a ratio represented by the following formula (A) of 80% or more,
The content of the polyether-modified silicone A is Ri 0.001 to 1.0% by mass of the solid content of the preliminary bonding composition,
The resin contains a polystyrene-based elastomer,
A composition for temporary bonding, wherein the content of the polystyrene-based elastomer in the total mass of the resin is 50 to 100% by mass ;
Formula (A) {(MO + EO) / AO} × 100
In the above formula (A), MO is mol% of methylene oxide contained in the polyether structure in the polyether-modified silicone, and EO is mol% of ethylene oxide contained in the polyether structure in the polyether-modified silicone. AO refers to the mole% of alkylene oxide contained in the polyether structure in the polyether-modified silicone. The resin is a polystyrene-poly (ethylene-propylene) diblock copolymer, a polystyrene-poly (ethylene-propylene) -polystyrene triblock copolymer, a polystyrene-poly (ethylene-butylene) -polystyrene triblock copolymer, The temporary bonding composition according to claim 1, wherein the composition is a polystyrene-based elastomer selected from at least one of polystyrene-poly (ethylene / ethylene-propylene) -polystyrene triblock copolymer. The composition for temporary bonding according to claim 1 or 2 , wherein the proportion of the repeating unit derived from styrene in the polystyrene-based elastomer is 55% by mass or less. The composition for temporary bonding according to any one of claims 1 to 3 , wherein the resin has a tensile modulus E of 1 to 60 MPa at 25 ° C according to JIS K 7161: 1994. The composition for temporary adhesion according to any one of claims 1 to 4 , wherein a ratio of the polyether-modified silicone A represented by the formula (A) is 90% or more. Mass loss rate of the polyether-modified silicone A when the temperature is increased from 20 ° C. to 280 ° C. at a rate of 20 ° C./min under a nitrogen flow of 60 mL / min and held at a temperature of 280 ° C. for 30 minutes Is 50% by mass or less, the composition for temporary bonding according to any one of claims 1 to 5 . The composition for temporary adhesion according to any one of claims 1 to 6 , wherein the polyether-modified silicone A is represented by any of the following formulas (101) to (104);
Equation (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. An atom or an alkyl group having 1 to 5 carbon atoms, m11, m12, n1 and p1 are each independently a number of 0 to 20, and x1 and y1 are each independently a number of 2 to 100;
Equation (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 atom having 1 to 5 carbon atoms. M2 and n2 are each independently a number from 0 to 20, and x2 is a number from 2 to 100;
Equation (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. An atom or an alkyl group having 1 to 5 carbon atoms, m31, m32, n3 and p3 are each independently a number of 0 to 20, and x3 is a number of 2 to 100;
Equation (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 of 0 to 20, and x4 and y4 are each independently a number of 2 to 100. The temporary bonding composition according to any one of claims 1 to 7 , wherein the polyether-modified silicone A has a refractive index of 1.440 or less. The temporary bonding composition according to any one of claims 1 to 8 , wherein the temporary bonding composition has a peeling force of 1 to 20 N / m: provided that the temporary bonding composition is a temporary bonding composition. Then, a temporary adhesive film having a thickness of 15 μm is formed on the surface of the silicon wafer, and the temporary adhesive film is formed at 25 ° C. at a speed of 300 mm / min in a direction perpendicular to the surface of the silicon wafer on which the temporary adhesive film is formed. By pulling up the edge of the film, the film can be peeled off, and the force applied when pulling up is measured by using a force gauge. It is a laminated body which has a 1st substrate, a temporary adhesive film, and a 2nd substrate adjacent to each other in the above-mentioned order, and the temporary adhesive film is any one of Claims 1-9. A laminate formed from the composition for temporary bonding of the above.