TW201800539A - Temporary adhesive composition and laminate - Google Patents

Abstract

Provided are: a temporary adhesive composition which temporarily fixes substrates that can subsequently be appropriately peeled off, and which is capable of providing a laminate in which the surface condition of a substrate following processing is satisfactory; and a laminate. The temporary adhesive composition contains a resin and polyether-modified silicone A in which the ratio represented by equation (A) below is at least 80%, wherein the content of the polyether-modified silicone A is 0.001-1.0 mass% of the solid content of the temporary adhesive composition (Equation (A): {(MO+EO)/AO}*100). In the above equation (A), MO represents the mole% of methylene oxide contained in a polyether structure in the polyether-modified silicone, EO represents the mole% of ethylene oxide contained in the polyether structure in the polyether-modified silicone, and AO represents the mole% of alkylene oxide contained in the polyether structure in the polyether-modified silicone.

Description

Composition and laminated body

The present invention relates to a composition for temporary bonding and a laminated body formed using the composition for temporary bonding.

In the manufacturing process of semiconductor elements such as integrated circuits (ICs) or large scale integrated circuits (LSIs), a plurality of IC chips are formed on the element wafers and dicing is performed. And monolithic. With the demand for further miniaturization and high performance of electronic equipment, IC chips mounted on electronic equipment are also required to be further miniaturized and highly integrated. However, the integration of integrated circuits in the in-plane direction of element wafers Hypervolatization is approaching the limit.

As a method of 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 before. However, in order to achieve miniaturization of the IC chip, it has been known in recent years. A method of forming a through hole in an element wafer and connecting a metal plug serving as an external terminal to an integrated circuit in the through hole (a method of forming a through-silicon via (TSV)). However, the method of forming the through-silicon electrodes alone cannot sufficiently meet the demand for further high integration of IC chips in recent years.

In view of the foregoing, there is known a technique for increasing the integration degree per unit area of an element wafer by multilayering an integrated circuit in an IC wafer. However, since the multilayer of the integrated circuit increases the thickness of the IC wafer, it is necessary to reduce the thickness of the components constituting the IC wafer. As a reduction in thickness of such members, for example, the reduction in thickness of element wafers has been studied. The reduction in thickness of element wafers not only leads to miniaturization of IC wafers, but also enables the manufacture of through-holes of element wafers in the manufacture of silicon through electrodes The effort-saving steps are considered promising. In addition, in semiconductor devices such as power devices and image sensors, from the viewpoint of increasing the integration degree or increasing the degree of freedom of the device structure, attempts have been made to reduce the thickness of device wafers.

As element wafers, those having a thickness of about 700 μm to 900 μm are widely known, but in recent years, attempts have been made to reduce the thickness of element wafers to 200 μm or less for purposes such as miniaturization of IC wafers. However, element wafers with a thickness of 200 μm or less are very thin, and components for manufacturing semiconductor elements using the same as substrates are also very thin. Therefore, it is difficult to further process such components or move only such components. Support the component stably and without damage.

In order to solve the above-mentioned problems, it is known to temporarily fix (temporarily adhere) the element wafer and the carrier substrate before thinning by temporarily using a composition, and to grind the back of the element wafer to reduce the thickness. A technique for subsequently peeling (detaching) the carrier substrate from the element wafer. Specifically, Patent Document 1 discloses an adhesive composition for temporarily attaching a substrate to a support that supports the substrate, and includes a thermoplastic resin and a release agent. In addition, Patent Document 2 also describes a wafer laminate including a base material, a semiconductor substrate, and a heat-stable polymer layer, and the heat-stable polymer layer contains 2.5% of the heat-stable polymer. Above surface energy modifier. [Prior Art Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2015-214675 [Patent Document 2] US Patent Publication No. 2014/0178701

[Problems to be Solved by the Invention] Patent Literature 1 and Patent Literature 2 describe that a release agent or a surface energy modifier is formulated in a resin such as a polystyrene elastomer, and the composition is temporarily used. However, the present inventors have conducted studies, and as a result, it has been found that the type or the amount of the release agent or the surface energy modifier can greatly affect the peelability of the composition for temporary adhesion. That is, it can be seen that depending on the type or blending amount of the release agent in the temporary bonding composition, when the substrates (element wafers and carrier substrates) are temporarily fixed using the temporary bonding composition, there is a problem. In some cases, the substrate cannot be properly peeled. Furthermore, it turned out that the surface shape of the base material after a process may worsen. An object of the present invention is to solve the above-mentioned problems, and an object of the present invention is to provide a composition for temporary bonding of a laminated body capable of appropriately peeling a substrate after temporarily fixing the substrates to each other, and capable of providing a laminated body with a good surface planarity of the processed substrate Objects and laminates.

所述式（101）中，R¹¹ 及R¹⁶ 分別獨立地為取代基，R¹² 及R¹⁴ 分別獨立地為二價連結基，R¹³ 及R¹⁵ 為氫原子或碳數1～5的烷基，m11、m12、n1及p1分別獨立地為0～20的數，x1及y1分別獨立地為2～100的數； 式（102） [化2]

所述式（102）中，R²¹ 、R²⁵ 及R²⁶ 分別獨立地為取代基，R²² 為二價連結基，R²³ 為氫原子或碳數1～5的烷基，m2及n2分別獨立地為0～20的數，x2為2～100的數； 式（103） [化3]

所述式（103）中，R³¹ 及R³⁶ 分別獨立地為取代基，R³² 及R³⁴ 分別獨立地為二價連結基，R³³ 及R³⁵ 為氫原子或碳數1～5的烷基，m31、m32、n3及p3分別獨立地為0～20的數，x3為2～100的數； 式（104） [化4]

所述式（104）中，R⁴¹ 、R⁴² 、R⁴³ 、R⁴⁴ 、R⁴⁵ 及R⁴⁶ 分別獨立地為取代基，R⁴⁷ 為二價連結基，R⁴⁸ 為氫原子或碳數1～5的烷基，m4及n4分別獨立地為0～20的數，x4及y4分別獨立地為2～100的數。 ＜9＞ 如＜1＞～＜8＞中任一項所述的暫時接著用組成物，其中，所述聚醚改質矽酮A的折射率為1.440以下。 ＜10＞ 如＜1＞～＜9＞中任一項所述的暫時接著用組成物，其中，暫時接著用組成物的剝離力為1 N/m～20 N/m；其中，所謂剝離力是指：使用暫時接著用組成物而於矽晶圓的表面形成厚度15 μm的暫時接著膜，於25℃下以速度300 mm/min的速度將暫時接著膜的端部向相對於矽晶圓的形成有暫時接著膜的面為垂直的方向拉起，藉此可剝離，且使用測力計對拉起時所施加的力進行測定時的力。 ＜11＞ 一種積層體，其依序相互鄰接而具有第1基材、暫時接著膜、以及第2基材，且所述暫時接著膜是由如＜1＞～＜10＞中任一項所述的暫時接著用組成物而形成。[Means for Solving the Problem] According to the situation described above, the present inventors conducted research and found that the content ratio of methylene oxide or ethylene oxide in the alkylene oxide contained in the polyether structure was adjusted by a small amount in the resin A high polyether modified silicone can solve the problem. Specifically, the above-mentioned problem is solved by the following means <1>, preferably <2> to <11>. <1> A composition for temporary adhesion, comprising: a resin; and a polyether-modified silicone A having a ratio represented by the following formula (A) of 80% or more; and a polyether-modified silicone A The content is 0.001% by mass to 1.0% by mass of the solid content of the composition for temporary bonding; Formula (A) {(MO + EO) / AO} × 100 In Formula (A), MO is a polyether modification Mole% of methylene oxide contained in the polyether structure in silicone, EO is Mole% of ethylene oxide contained in the polyether structure in polyether modified silicone, AO means Molar% of alkylene oxide contained in polyether structure in polyether modified silicone. <2> The temporary bonding composition according to <1>, wherein the resin is a polystyrene-based elastomer. <3> The temporary bonding composition according to <1>, wherein the resin is selected from a polystyrene-poly (ethylene-propylene) diblock copolymer and a polystyrene-poly (ethylene-propylene) -Polystyrene triblock copolymer, polystyrene-poly (ethylene-butene) -polystyrene triblock copolymer, and polystyrene-poly (ethylene / ethylene-propylene) -polystyrene triblock A polystyrene-based elastomer in at least one of the segment copolymers. <4> The composition for temporary bonding according to <2> or <3>, wherein the proportion of the repeating unit derived from styrene in the polystyrene 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 elastic coefficient E at 25 ° C according to JIS K7161: 1994 of 1 MPa to 60 MPa. <6> The composition for temporary adhesion according to any one of <1> to <5>, wherein the ratio represented by formula (A) of the polyether-modified silicone A is 90% or more. <7> The temporary bonding composition according to any one of <1> to <6>, wherein the polyether-modified silicone A is subjected to a nitrogen flow of 60 mL / min at 20 ° C / min. The rate of temperature increase when the temperature was increased from 20 ° C to 280 ° C and held at a temperature of 280 ° C for 30 minutes was a mass reduction rate of 50% by mass or less. <8> The composition for temporary adhesion according to any one of <1> to <7>, wherein the polyether-modified silicone A is any one of the following formulae (101) to (104) Person to express; formula (101) [化 1]

In the formula (101), R ¹¹ and R ¹⁶ are each independently a substituent, R ¹² and R ¹⁴ are each independently a divalent linking group, R ¹³ and R ¹⁵ are a hydrogen atom or an alkane having 1 to 5 carbon atoms. Basis, m11, m12, n1, and p1 are each independently a number from 0 to 20, and x1 and y1 are each independently a number from 2 to 100; Formula (102) [化 2]

In the formula (102), R ²¹ , R ²⁵ and R ²⁶ are each independently a substituent, R ²² is a divalent linking group, R ²³ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and m 2 and n 2 are respectively It is independently a number from 0 to 20, and x2 is a number from 2 to 100; Formula (103) [化 3]

In the formula (103), R ³¹ and R ³⁶ are each independently a substituent, R ³² and R ³⁴ are each independently a divalent linking group, R ³³ and R ³⁵ are a hydrogen atom or an alkane having 1 to 5 carbon atoms. Basis, m31, m32, n3, and p3 are each independently a number from 0 to 20, and x3 is a number from 2 to 100; Formula (104) [化 4]

In the 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 a carbon number of 1 to 5 alkyl groups, 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 adhesion according to any one of <1> to <8>, wherein the refractive index of the polyether-modified silicone A is 1.440 or less. <10> The temporary bonding composition according to any one of <1> to <9>, wherein the peeling force of the temporary bonding composition is 1 N / m to 20 N / m; It means that a temporary bonding film with a thickness of 15 μm is formed on the surface of a silicon wafer by using a temporary bonding composition, and the end of the temporary bonding film is directed to the silicon wafer at a speed of 300 mm / min at 25 ° C. The surface on which the film was temporarily adhered was pulled up in a vertical direction, thereby being peelable, and the force at the time of pulling up was measured using a dynamometer. <11> A laminated body having a first substrate, a temporary adhesive film, and a second substrate adjacent to each other in this order, and the temporary adhesive film is formed by any one of The aforementioned temporary formation is followed by a composition.

[Effects of the Invention] According to the present invention, it is possible to provide a composition for temporary bonding of a laminated body that can be appropriately peeled after temporarily fixing the substrates to each other, and capable of providing a laminated body with a good surface planarity of the processed substrate, and Laminated body.

Hereinafter, the content of this invention is demonstrated in detail. In addition, the numerical range indicated by "~" in this specification means the range which includes the numerical value described before and after "~" as a lower limit and an upper limit. In the description of the group (atomic group) in the present specification, the descriptions that are not substituted and unsubstituted include groups that do not have a substituent, and also include groups that have a substituent. For example, "alkyl" includes not only an alkyl group (unsubstituted alkyl group) having no substituent, but also an alkyl group (substituted alkyl group) having a substituent. The "actinic rays" or "radiation" in this specification include visible rays, ultraviolet rays, extreme ultraviolet rays, electron beams, X-rays, and the like. In this specification, the term "exposure" includes not only exposure using light, but also description using particle beams such as electron beams and ion beams unless otherwise specified. In addition, the light used in the exposure generally includes light such as a bright line spectrum of a mercury lamp, far ultraviolet rays typified by excimer laser light, extreme ultraviolet rays (Extreme Ultraviolet (EUV) light), X-rays, and electron beams. Chemoradiation or radiation. As used herein, the term "total solid content" refers to the total mass of components obtained by removing the solvent from all the components of the composition. In this specification, "(meth) acrylate" means acrylate and methacrylate, "(meth) acrylic" means acrylic and methacrylic, and "(meth) acryl" refers to "acryl" "And" methacrylfluorenyl. " In this specification, weight average molecular weight (Mw) and number average molecular weight (Mn) are defined as polystyrene conversion values measured by gel permeation chromatography (GPC). In this specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) can be, for example, HLC-8220 (manufactured by Tosoh) and TSK gel Super AWM-H (Tosoh ) (Stock), inner diameter (ID) 6.0 mm × 15.0 cm) as a column, and a 10 mmol / L lithium bromide N-methyl pyrrolidone (NMP) solution was used as a washing solution. Out. Furthermore, in the embodiments described below, descriptions of components and the like already described in the drawings referred to are simplified or omitted by using the same or corresponding symbols in the drawings.

The temporary bonding composition according to the present invention is a temporary bonding composition containing a resin and a polyether modified silicone A having a ratio represented by formula (A) of 80% or more, and the polyether modified The content of the high-quality silicone A is 0.001% by mass to 1.0% by mass of the solid content of the composition for temporary bonding. Formula (A) {(MO + EO) / AO} × 100 In the formula (A), MO is the mole% of the methylene oxide contained in the polyether structure in the polyether modified silicone, EO is the mole% of the ethylene oxide contained in the polyether structure in the polyether modified silicone, and AO is the mole% of the alkylene oxide contained in the polyether structure in the polyether modified silicone. . With such a configuration, the substrates can be temporarily fixed to each other as appropriate to form a laminate, and the substrate can be appropriately peeled after processing. At the same time, it is possible to obtain a composition for temporary bonding capable of providing a laminated body having an excellent planar shape on the surface of the substrate after processing. This mechanism is presumed as follows. That is, since the polyether-modified silicone A having a ratio of 80% or more is selectively biased to the interface existing in the temporarily adhered film, the amount of addition is as small as the range described above. The base material can be temporarily fixed appropriately and peeled off appropriately. Furthermore, even if the processing accompanied by heating is performed, the generation of outgass due to decomposition is small, so that the surface of the substrate after processing becomes good. Furthermore, by using the polyether-modified silicone A, a resin having a low tensile elastic modulus, for example, a styrene-based elastomer having a proportion of repeating units derived from styrene of 55% by mass or less can be used as a resin component. , And can effectively suppress warping.

<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 it can achieve various characteristics of the temporary adhesive film. Examples of the resin include a block copolymer, a random copolymer, and a graft copolymer, and a block copolymer is preferable. In the case of a block copolymer, since the flow of the composition for temporary bonding during the heating process can be suppressed, the bonding can be maintained even during the heating process, and the effect that the peelability does not change after the heating process can be expected. The type of the resin is not particularly limited, and polystyrene-based copolymers, polyester-based copolymers, polyolefin-based copolymers, polyurethane-based copolymers, polyamide-based copolymers, and polyacrylic copolymers can be used. Polymers, silicone-based copolymers, polyimide-based copolymers, cycloolefin-based polymers, and the like. In the present invention, the resin is preferably selected from the group consisting of styrene-butadiene-styrene block copolymer, styrene-isoprene-styrene block copolymer, polystyrene-poly (ethylene-propylene) ) Diblock copolymer, polystyrene-poly (ethylene-propylene) -polystyrene triblock copolymer, polystyrene-poly (ethylene-butene) -polystyrene triblock copolymer, polybenzene A thermoplastic resin selected from at least one of an ethylene-poly (ethylene / ethylene-propylene) -polystyrene triblock copolymer, a cycloolefin-based polymer, and a thermoplastic polyfluorene imine resin, more preferably selected from polystyrene- Poly (ethylene-propylene) diblock copolymer, polystyrene-poly (ethylene-propylene) -polystyrene triblock copolymer, polystyrene-poly (ethylene-butene) -polystyrene triblock A polystyrene-based elastomer in at least one of a copolymer and a polystyrene-poly (ethylene / ethylene-propylene) -polystyrene triblock copolymer. Among them, the resin is preferably a block copolymer of styrene and other monomers, and particularly preferably a styrene block copolymer having styrene blocks at one or both ends. The resin is preferably a hydride of a block copolymer. When the resin is a hydride, thermal stability or storage stability is improved. Furthermore, the peelability and the cleaning-removability of the temporary adhesive film after peeling are improved. The hydride is a polymer having a structure in which a block copolymer is hydrogenated.

In this description, the resin is preferably an elastomer. By using an elastomer as the resin, it is also possible to follow the fine unevenness of the carrier substrate or element wafer (the first substrate or the second substrate), and use a moderate anchor effect to form a temporary bond with excellent adhesion. membrane. The elastomer may be used singly or in combination of two or more kinds. In addition, in this specification, an "elastomer" means a polymer compound which shows elastic deformation. That is, it is defined as a polymer compound having the following properties: when an external force is applied, it instantly deforms in response to the external force, and returns to its original shape in a short time when the external force is removed. In addition, in this specification, "adhesiveness" is defined to include not only the performance of "providing a high adhesive force if bonding is performed only under high pressure", but also "the adhesion to low pressure (for example, at 0.4 MPa). Low pressure bonding) also gives a sufficiently high bonding performance.

<< Elastomer> In the present invention, the weight average molecular weight of the elastomer is preferably 2,000 to 200,000, more preferably 10,000 to 200,000, and even more preferably 50,000 to 100,000. An elastomer having a weight average molecular weight in this range has excellent solubility in a solvent. Therefore, after the carrier substrate is peeled from the element wafer, a solvent is used to remove residues derived from the elastomer remaining on the element wafer or the carrier substrate. In this case, the residue is easily dissolved in a solvent and removed. Therefore, there is a medium advantage that the residue does not remain on the element wafer or the carrier substrate.

In the present invention, the elastomer is not particularly limited, and an elastomer (polystyrene-based elastomer), a polyester-based elastomer, a polyolefin-based elastomer, or a polyurethane containing a repeating unit derived from styrene can be used. Ester-based elastomers, polyamide-based elastomers, polyacrylic-based elastomers, silicone-based elastomers, polyimide-based elastomers, and the like. Among them, polystyrene-based elastomers, polyester-based elastomers, and polyamide-based elastomers are preferred. Polystyrene-based elastomers are particularly preferred from the viewpoints of heat resistance and peelability.

In the present invention, the elastomer is preferably a hydride. Particularly preferred is a hydride of a polystyrene-based elastomer. When the elastomer is a hydride, thermal stability or storage stability is improved. Furthermore, the peelability and the cleaning-removability of the temporary adhesive film after peeling are improved. When a hydride of a polystyrene-based elastomer is used, the effect is remarkable. The hydride is a polymer having a structure in which an elastomer is hydrogenated.

In the present invention, the 5% thermal mass reduction temperature when the elastomer is heated from 25 ° C at a temperature increase rate of 20 ° C / min is preferably 250 ° C or more, more preferably 300 ° C or more, and even more preferably 350 ° C or more, especially It is preferably at least 400 ° C. The upper limit value is not particularly limited, but is preferably 1000 ° C or lower, more preferably 800 ° C or lower. According to this aspect, it is easy to form a temporary adhesive film excellent in heat resistance. The elastomer in the present invention preferably has the following properties: when the original size is set to 100%, it can be deformed to 200% by a small external force at room temperature (20 ° C), and when the external force is removed, the Recovery to below 130% in a short time.

<<< Polystyrene-based elastomer >> The polystyrene-based elastomer is not particularly limited, and can be appropriately selected according to the purpose. For example, it is preferably selected from 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-butene) -polystyrene triblock A polystyrene-based elastomer in at least one of a segment copolymer (SEBS) and a polystyrene-poly (ethylene / ethylene-propylene) -polystyrene triblock copolymer (SEEPS).

The proportion of the repeating unit derived from styrene in the polystyrene elastomer is preferably 90% by mass or less, more preferably 50% by mass or less, still more preferably 48% by mass or less, even more preferably 35% by mass or less, It is more preferably 33% by mass or less. The lower limit of the proportion of the styrene-derived repeating unit may be a value exceeding 0% by mass, and may be, for example, 10% by mass or more. By setting it as such a range, the curvature of a laminated body can be suppressed more effectively. The calculation method of the ratio of the repeating unit derived from styrene is based on the method described in the Example mentioned later.

As an embodiment of the polystyrene-based elastomer in the present invention, an elastomer A and an elastomer B may be used in combination, and the elastomer A may be 10% by mass or more and 55% by mass or less in all repeating units. The proportion contains a repeating unit derived from styrene, and the elastomer B contains a repeating unit derived from styrene in a proportion of more than 55% by mass and less than 95% by mass in all the repeating units. By using the elastomer A and the elastomer B in combination, the occurrence of warpage can be effectively suppressed. The mechanism for obtaining such an effect can be presumed to be the following. That is, since the elastomer A is a relatively soft material, it is easy to form a temporary adhesive film having elasticity. Therefore, when a laminated body of a substrate and a support is produced using the composition for temporarily bonding the present invention, and the substrate is polished to be thinned, the film may be elastically deformed temporarily even if the pressure during polishing is locally applied. And easily restored to its original shape. As a result, excellent flat abrasiveness is obtained. In addition, even if the laminated body after the polishing is heated and then cooled, it is possible to effectively suppress the occurrence of warpage by temporarily reducing the internal stress generated during cooling after the film is temporarily adhered. In addition, since the elastomer B is a relatively hard material, by including the elastomer B, a temporary adhesive film having excellent peelability can be produced.

The quality of the elastomer A and the elastomer B when blended is relatively good: Elastomer A: Elastomer B = 1:99 to 99: 1, more preferably 3:97 to 97: 3, and even more preferably 5 : 95 to 95: 5, particularly preferably 10: 90 to 90: 10. If it is the said range, the said effect can be acquired more effectively.

The polystyrene elastomer is preferably a block copolymer of styrene and other monomers, more preferably a block copolymer having styrene blocks at one or both ends, and particularly preferably a styrene block at both ends. Block copolymer. When both ends of the polystyrene-based elastomer are styrene blocks (repeating units derived from styrene), the heat resistance tends to be further improved. The reason is that a repeating unit derived from styrene having high heat resistance exists at the terminal. In particular, it is preferred that the block portion of the repeating unit derived from styrene is a reactive polystyrene hard block, which tends to be more excellent in heat resistance and chemical resistance. Such an elastomer is also more preferred from the viewpoints of solubility in a solvent and resistance to a resist solvent. In addition, if the polystyrene-based elastomer is a hydride, the stability to heat is improved, and deterioration such as decomposition or polymerization is less likely to occur. Furthermore, it is more preferable from a viewpoint of solubility in a solvent, and resistance in a resist solvent. As the amount of unsaturated double bonds of the polystyrene elastomer, from the standpoint of releasability, it is preferably less than 15 mmol, more preferably less than 5 mmol, and most preferably 1 mg of polystyrene elastomer. Less than 0.5 mmol. The amount of unsaturated double bonds described herein does not include the amount of unsaturated double bonds in the benzene ring derived from styrene. The amount of unsaturated double bonds can be calculated by nuclear magnetic resonance (Nuclear Magnetic Resonance, NMR) measurement.

In the present specification, the "repeated unit derived from styrene" refers to a structural unit derived from styrene or a styrene contained in a polymer when a styrene derivative is polymerized, and may have a substituent. Examples of the styrene derivative include α-methylstyrene, 3-methylstyrene, 4-propylstyrene, and 4-cyclohexylstyrene. Examples of the substituent include an alkyl group having 1 to 5 carbons, an alkoxy group having 1 to 5 carbons, an alkoxyalkyl group having 2 to 5 carbons, ethoxyl, carboxyl, and the like.

Examples of commercially available polystyrene-based elastomers include Tufprene A, Tufprene 125, Tufprene 126S, and Solprene. T, Asaprene T-411, Asaprene T-432, Asaprene T-437, Asaprene T-438, Asaprene (Asaprene) T-439, Tuftec H1272, Tuftec P1500, Tuftec H1052, Tuftec H1062, Tuftec M1943, Tuftec M1911, Tuftec H1041, Tuftec MP10, Tuftec M1913, Tuftec H1051, Tuftec (Tuftec) H1053, Tuftec P2000, Tuftec H1043 (above manufactured by Asahi Kasei Chemical Co., Ltd.); Elastomer AR-850C, Elastomer AR- 815C, Elastomer AR-840C, Elastomer AR-830C, Elastomer AR-860C, Elastomer ( Elastomer) AR-875C, Elastomer AR-885C, Elastomer AR-SC-15, Elastomer AR-SC-0, Elastomer AR-SC-5, Elastomer (Elastomer) AR-710, Elastomer AR-SC-65, Elastomer AR-SC-30, Elastomer AR-SC-75, Elastomer AR-SC-45 Elastomer AR-720, Elastomer AR-741, Elastomer AR-731, Elastomer AR-750, Elastomer AR-760, Elastomer ) AR-770, Elastomer AR-781, Elastomer AR-791, Elastomer AR-FL-75N, Elastomer AR-FL-85N, Elastomer AR-FL-60N, Elastomer AR-1050, Elastomer AR-1060, Elastomer AR-1040 (the above are manufactured by Aronkasei); Kraton ( Kraton) D1111, Kraton D1113, Kraton D1114, Kraton D1117, Kraton D1119, Kraton Kraton D1124, Kraton D1126, Kraton D1161, Kraton D1162, Kraton D1163, Kraton D1164, Kraton D1165, Kraton ) D1183, Kraton D1193, Kraton DX406, Kraton D4141, Kraton D4150, Kraton D4153, Kraton D4158, Kraton D4270, Kraton D4271, Kraton D4433, Kraton D1170, Kraton D1171, Kraton D1173, Cariflex IR0307, Calicus (Cariflex) IR0310, Cariflex IR0401, Kraton D0242, Kraton D1101, Kraton D1102, Kraton D1116, Kraton D1118, Ke Kraton D1133, Kraton D1152, Kraton D1153, Kraton D1155, Kraton D1184, Kraton D1186, Kraton D1189, Kraton (Kraton) D1191, Kraton D1192, Kraton DX405, Kraton DX408, Kraton DX410, Kraton DX414, Kraton DX415, Kraton A1535, Kraton A1536, Kraton FG1901 , Kraton FG1924, Kraton G1640, Kraton G1641, Kraton G1642, Kraton G1643, Kraton G1645, Kraton G1633, Kraton G1650, Kraton G1651, Kraton G1652 (G1652MU-1000), Kraton G1654, Kraton G1657, Kraton G1660, Kraton ( Kraton G1726, Kraton G1701, Kraton G1702, Kraton G1730, Kraton G1750, Kraton G1765, Kraton G4609, Kraton ) G4610 (the above are manufactured by Kraton polymer Japan); TR2000, TR2001, TR2003, TR2250, TR2500, TR2601, TR2630, TR2787, TR2827, TR1086, TR1600, SIS5002, SIS5200, SIS5250, SIS5405 , SIS5505, Dynaro n) 6100P, Dynaron 4600P, Dynaron 6200P, Dynaron 4630P, Dynaron 8601P, Dynaron 8630P, Dynaron 8600P, Dynaron 8903P, Dynaron 6201B, Dynaron 1321P, Dynaron 1320P, Dynaron 2324P, Dynaron 9901P ( The above are manufactured by JSR (stock); Denka STR series (manufactured by Electrochemical Industry (stock)); Quintac 3520, Quintac 3433N, Quintac 3421 Quintac 3620, Quintac 3450, Quintac 3460 (above manufactured by ZEON, Japan); TPE-SB series (manufactured by Sumitomo Chemical Co., Ltd.); Labalon (Rabalon) series (manufactured by Mitsubishi Chemical Corporation); Septon 1001, Septon 1020, Septon 2002, Septon 2004, Septon ) 2005, Septon 2006, Septon 2007, (Septon) 2063, Septon 2104, Septon 4033, Septon 4044, Septon 4055, Septon 4077, Septon ( Septon 4099, Septon HG252, Septon 8004, Septon 8006, Septon 8007, Septon 8076, Septon 8104, Septon V9461, Septon V9475, Septon V9827, Hybrar 7311, Hybrar 7125, Hybrar 5127, Hybrar 5125 (above are manufactured by Kuraray (stock)); Sumiflex (made by Sumitomo Bakelite (stock)); Leostomer , Actymer (the above are manufactured by Riken technos (stock)) and so on.

<<< Polyester-based Elastomer >> The polyester-based elastomer is not particularly limited, and can be appropriately selected depending on the purpose. Examples thereof include those obtained by polycondensing a dicarboxylic acid or a derivative thereof with a diol compound or a derivative thereof. Examples of the dicarboxylic acid include aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, and naphthalenedicarboxylic acid (including hydrogen atoms of these aromatic rings substituted with methyl, ethyl, phenyl, etc. Aromatic dicarboxylic acids); aliphatic dicarboxylic acids having 2 to 20 carbon atoms, such as adipic acid, sebacic acid, dodecanedicarboxylic acid; and alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid, etc. . These may be used alone or in combination of two or more. Examples of the diol compound include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,10-decanediol, and 1,4-cyclohexanediene. Aliphatic diols such as alcohols; alicyclic diols; divalent phenol compounds represented by the following formula, and the like.

[Chemical 5]

In the formula, Y ^DO represents 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 ( Benzene rings are straight bonds to each other). 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. In addition, as the polyester-based elastomer, a hard segment component including an aromatic polyester (for example, polybutylene terephthalate) portion, and an aliphatic polyester (for example, polybutylene) may be used. Multi-block copolymers with a soft segment component of the diol) portion. Examples of the multi-block copolymer include those classified into a plurality of grades by the difference in the types, ratios, and molecular weights of the hard segment and the soft segment. Specific examples include Hytrel (manufactured by Toray DuPont); Pelprene (manufactured by Toyobo); Primalloy (Manufactured by Mitsubishi Chemical Corporation); Nouvelan (manufactured by Teijin Corporation); Espel 1612, 1620 (above: manufactured by Hitachi Chemical Industries, Ltd.), etc.

<< Polyolefin-based elastomer> The polyolefin-based elastomer is not particularly limited, and can be appropriately selected depending on the purpose. Examples thereof include copolymers of α-olefins having 2 to 20 carbon atoms such as ethylene, propylene, 1-butene, 1-hexene, and 4-methyl-1-pentene. Examples include ethylene-propylene copolymer (EPR), ethylene-propylene-diene copolymer (EPDM), and the like. Examples include dicyclopentadiene, 1,4-hexadiene, cyclooctadiene, methylene norbornene, ethylidene norbornene, butadiene, isoprene, and the like. 20 is a copolymer of a non-conjugated diene and an α-olefin. In addition, a carboxy-modified nitrile rubber obtained by copolymerizing methacrylic acid and a butadiene-acrylonitrile copolymer is mentioned. Specific examples include ethylene / α-olefin copolymer rubber, ethylene / α-olefin / non-conjugated diene copolymer rubber, propylene / α-olefin copolymer rubber, butene / α-olefin copolymer rubber, and the like. . Examples of commercially available products include: Milastomer (manufactured by Mitsui Chemicals Co., Ltd.); Thermon (manufactured by Mitsubishi Chemical Co., Ltd.); EXACT (manufactured by Exxon mobil) ); EAGNGE (manufactured by Dow Chemical Japan); Espolex (manufactured by Sumitomo Chemical Co., Ltd.); Sarlink (manufactured by Toyobo Co., Ltd.); Newcon (manufactured by Japan Polypropylene); EXCELINK (manufactured by JSR).

<< Polyurethane-based elastomer> There is no particular limitation on the polyurethane-based elastomer, and it can be appropriately selected according to the purpose. For example, an elastomer including a hard segment including a low-molecular-weight diol and a diisocyanate, and a structural unit including a polymer (long-chain) diol and a soft segment of a diisocyanate can be cited. Examples of the polymer (long-chain) diol include polypropylene glycol, polytetramethylene oxide, poly (1,4-butene adipate), and poly (ethylene / 1,4-butene adipate). Acid ester), polycaprolactone, poly (1,6-hexene carbonate), poly (1,6-hexene / neopentene adipate), and the like. The number average molecular weight of the polymer (long-chain) diol is preferably 500 to 10,000. As the low-molecular-weight diol, short-chain diols such as ethylene glycol, propylene glycol, 1,4-butanediol, and bisphenol A can be used. The number-average molecular weight of the short-chain diol is preferably 48 to 500. Examples of commercially available polyurethane-based elastomers include: PANDEX T-2185, T-2983N (the above are manufactured by DIC Corporation); Mirakutton ( Miractran) (manufactured by Miractran (Japan); Elastollan (manufactured by BASF Japan); Resamin (Dainichi Chemical Industry ( Manufacturing); Pellethane (made by Dow Chemical Japan); Ironrubber (made by NOK); Mobilon ( Nisshinbo Chemical Co., Ltd.) and so on.

<<< Polyamine-based elastomer >> Polyamine-based elastomer is not particularly limited, and can be appropriately selected according to the purpose. Examples include hard segments including polyamines such as polyamine-6, 11, 12 and soft chains including at least one of polyethers such as polyoxyethylene, polyoxypropylene, polybutylene glycol, and polyesters. Segment of elastomers, etc. This elastomer can be roughly divided into two types: polyether block amido type and polyether ester block amido type. Examples of commercially available products include: UBESTA XPA (manufactured by Ube Kosan Co., Ltd.), UBE polyamine elastomer; Daiamid (manufactured by Daicel-Evonik, Co., Ltd.); PEBAX (Manufactured by ARKEMA); Grilon ELX (manufactured by EMS Chemie-Japan); Novamid (manufactured by Mitsubishi Chemical Co., Ltd.); Grilux (manufactured by Toyobo); polyetheresteramide PA-200, PA-201, TPAE-12, TPAE-32, polyester amine TPAE-617, TPAE-617C (the above is T & K TOKA (shares ) Manufacturing) etc.

<<< Polyacrylic Elastomer >> The polyacrylic elastomer is not particularly limited, and can be appropriately selected according to the purpose. Examples include ethyl acrylate, butyl acrylate, methoxyethyl acrylate, and ethoxyethyl acrylate, which are mainly composed of acrylate as a monomer material, or acrylate and glycidyl methacrylate. A copolymer obtained by copolymerization of allyl glycidyl ether and the like. Further examples include those obtained by copolymerizing an acrylate with a crosslinking point monomer such as acrylonitrile or ethylene. Specific examples include acrylonitrile-butyl acrylate copolymer, acrylonitrile-butyl acrylate-ethyl acrylate copolymer, acrylonitrile-butyl acrylate-glycidyl methacrylate copolymer, and the like.

<< silicone elastomer >> There is no particular limitation on the silicone elastomer, and it can be appropriately selected according to the purpose. For example, a polydimethylsiloxane type, a polymethylphenylsiloxane type, a polydiphenylsiloxane type, etc. which have an organic polysiloxane as a main component are mentioned. Specific examples of commercially available products include KE series (manufactured by Shin-Etsu Chemical Co., Ltd.); SE series, CY series, and SH series (the above are manufactured by Toray Dow Corning (stock)).

<< Other elastomers >> In the present invention, a rubber-modified epoxy resin (epoxy-based elastomer) can be used as the elastomer. The epoxy-based elastomer can be made of, for example, a bisphenol F-type epoxy resin and a bisphenol A-type epoxy resin by using both terminal carboxylic acid modified butadiene-acrylonitrile rubber and terminal amine modified silicone rubber. 2, salicylaldehyde-type epoxy resin, phenol novolac-type epoxy resin, or cresol novolac-type epoxy resin is obtained by modifying part or all of the epoxy group.

<< Other polymer compounds >> In the present invention, other polymer compounds (also referred to as other polymer compounds) other than the resin may be used as the resin. Other polymer compounds may be used singly or in combination of two or more kinds. Specific examples of other polymer compounds include, for example, hydrocarbon resins, novolac resins, phenol resins, epoxy resins, melamine resins, urea resins, unsaturated polyester resins, alkyd resins, polyamide resins, and thermoplastic polymers. Perylene imine resin, polyfluorene imine 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, polyfluorene resin, polyetherfluorene resin, polyarylate resin, polyetheretherketone resin, and the like. Among these, a hydrocarbon resin, a thermoplastic polyimide resin, and a polycarbonate resin are preferable, and a hydrocarbon resin is more preferable. In the present invention, a resin containing a fluorine atom to be described later may be used as the resin, but a resin containing a fluorine atom (hereinafter also referred to as a fluorine-based resin) is preferably not substantially contained. The fact that the fluorine-based resin is not substantially contained 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, and even more preferably not contained in the total mass of the resin.

<<< Hydrocarbon resin >> In the present invention, any hydrocarbon resin can be used. The hydrocarbon resin refers to a resin that basically contains only carbon atoms and hydrogen atoms. If the basic skeleton is a hydrocarbon resin, other atoms may be contained as side chains. That is, in a hydrocarbon resin containing only carbon atoms and hydrogen atoms, such as acrylic resin, polyvinyl alcohol resin, polyvinyl acetal resin, and polyvinyl pyrrolidone resin, functional groups other than the hydrocarbon group are directly bonded to The case of the main chain is also included in the hydrocarbon resin in the present invention. In this case, the content of the repeating unit in which the hydrocarbon group is directly bonded to the main chain is preferably 30 mol% or more relative to all the repeating units of the resin. . 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, polymerized rosin, polymerized rosin ester, modified rosin, rosin modified phenol resin, alkylphenol resin, aliphatic petroleum resin, aromatic petroleum resin, hydrogenated petroleum resin, modified petroleum resin, alicyclic petroleum resin , Coumarone petroleum resin, indene petroleum resin, polystyrene-polyolefin copolymer, olefin polymer (such as methylpentene copolymer) and cycloolefin polymer (such as norbornene copolymer, dicyclopentadiene Copolymer, tetracyclododecene copolymer) and so on. Among them, the hydrocarbon resin is preferably a terpene resin, rosin, petroleum resin, hydrogenated rosin, polymerized rosin, olefin polymer or cycloolefin polymer, more preferably a terpene resin, rosin, olefin polymer or cycloolefin polymer, and further More preferred is a cycloolefin polymer.

Examples of the cyclic olefin polymer include a norbornene-based polymer, a polymer of a monocyclic cyclic olefin, a polymer of a cyclic conjugated diene, a vinyl alicyclic hydrocarbon polymer, and a polymer of these polymers. Hydride, etc. Preferred examples of the cycloolefin polymer include an addition (co) polymer containing at least one or more repeating units represented by the following formula (II), and further including a repeat represented by the following formula (I) An addition (co) polymer made of at least one or more units. In addition, as another preferable example of the cycloolefin polymer, a ring-opened (co) polymer including at least one cyclic repeating unit represented by the following formula (III) is mentioned.

[Chemical 6]

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, X ¹ to X ³ and Y ¹ to Y ³ each independently represent a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, a halogen atom, 1 to 10 hydrocarbon groups substituted by halogen atoms,-(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,-(CH ₂ ) nW, or X ¹ and Y ¹ , X ² and Y ² and X ³ (-CO) ₂ O or (-CO) ₂ NR ¹⁷ is formed independently of Y ³ . 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), and Z represents a hydrocarbon group or a halogen-substituted hydrocarbon group , W represents SiR ¹⁸ _p D _3-p (R ¹⁸ represents a hydrocarbon group having 1 to 10 carbon atoms, D represents a halogen atom, -OCOR ¹⁸ or -OR ¹⁸ , and p represents an integer of 0 to 3), and n represents 0 to 10 Integer.

The norbornene-based polymer is disclosed in Japanese Patent Laid-Open No. 10-7732, Japanese Patent Laid-Open No. 2002-504184, US Patent Publication No. 2004 / 229157A1, or International Publication No. WO2004-070463A1. A norbornene-based polymer can be obtained by addition polymerization of a norbornene-based polycyclic unsaturated compound with each other. In addition, if necessary, the norbornene-based polycyclic unsaturated compound may be combined with ethylene, propylene, butene, conjugated diene such as butadiene, isoprene, or ethylidene norbornene. Non-conjugated diene undergoes addition polymerization. This norbornene-based polymer is sold by Mitsui Chemicals, Inc. under the trade name Apel, and has different glass transition temperatures (Tg) such as APL8008T (Tg70 ° C), APL6013T (Tg125 ° C), and APL6015T ( Tg145 ℃) and other grades. TOPAS8007, TOPAS5013, TOPAS6013, TOPAS6015 and other pellets are sold by Poly plastic (stock). Furthermore, Appear 3000 is sold by Ferrania.

The hydrides of the norbornene-based polymer can be, for example, Japanese Patent Laid-Open No. 1-240517, Japanese Patent Laid-Open No. 7-176736, Japanese Patent Laid-Open No. 60-26024, and Japanese Patent Laid-Open No. 62-19801. As disclosed in Japanese Unexamined Patent Publication, Japanese Patent Laid-Open No. 2003-1159767, and Japanese Patent Laid-Open No. 2004-309979, the polycyclic unsaturated compound is subjected to hydrogenation after addition polymerization or ring-opening shift polymerization, followed by hydrogenation. Manufacturing. 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 other groups may be appropriately selected. The norbornene-based polymer is sold by JSR (stock) under the trade names of Arton G or Arton F, and is sold by Japan Zeon (share) under Zeonor ZF14 , ZF16, ZEONEX 250, ZEONEX 280, and ZEONEX 480R are commercially available under the trade names, and these can be used.

<<< Thermoplastic polyfluorene imine resin >> As a thermoplastic polyfluorene imine resin, the thing obtained by making condensation reaction of a tetracarboxylic dianhydride and a diamine by a well-known method can be used. As a known method, for example, a method such as mixing an approximately equal mole of tetracarboxylic dianhydride and diamine in an organic solvent, and reacting them at a reaction temperature of 80 ° C. to synthesize a polyamic acid, The obtained polyamidic acid was dehydrated and closed-looped (fluorinated). Here, the term "approximately equal molarity" means that the molar ratio of tetracarboxylic dianhydride to diamine is close to 1: 1. Further, if necessary, the composition ratio of the tetracarboxylic dianhydride to the diamine may be adjusted so that the total of the dicarboxylic acid dianhydride is 1.0 mol and the total of the diamine is 0.5 mol to 2.0 mol. By adjusting the composition ratio of the tetracarboxylic dianhydride to the diamine within the above range, the weight average molecular weight of the thermoplastic polyfluorene imine resin can be adjusted.

Tetracarboxylic dianhydride is not particularly limited, and examples thereof include pyromellitic dianhydride, 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, 2,2', 3,3'- Biphenyltetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propane dianhydride, 1,1 -Bis (2,3-dicarboxyphenyl) ethane dianhydride, 1,1-bis (3,4-dicarboxyphenyl) ethane dianhydride, bis (2,3-dicarboxyphenyl) methane dianhydride Anhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) fluorene dianhydride, 3,4,9,10-fluorenetetracarboxylic dianhydride, bis (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 acid Dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,2,4,5-naphthalenetetracarboxylic dianhydride, 2, 6-Dichloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 2,7-dichloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 2,3,6,7- Tetrachloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, phenanthrene-1,8,9,10-tetracarboxylic dianhydride, pyrazine-2,3,5,6-tetracarboxylic dianhydride Thiophene-2,3,5,6-tetracarboxylic dianhydride, 2,3,3 ', 4' -Biphenyltetracarboxylic dianhydride, 3,4,3 ', 4'-biphenyltetracarboxylic dianhydride, 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) phthalic anhydride, 1,3-bis (3,4-dicarboxyphenyl) -1,1,3,3 -Tetramethyldicyclohexane dianhydride, terephthalic acid (trimellitic anhydride), ethylene tetracarboxylic dianhydride, 1,2,3,4-butanetetracarboxylic dianhydride, decahydronaphthalene- 1,4,5,8-tetracarboxylic dianhydride, 4,8-dimethyl-1,2,3,5,6,7-hexahydronaphthalene-1,2,5,6-tetracarboxylic acid di Anhydride, cyclopentane-1,2,3,4-tetracarboxylic dianhydride, pyrrolidine-2,3,4,5-tetracarboxylic dianhydride, 1,2,3,4-cyclobutane tetracarboxylic acid Acid dianhydride, bis (oxabicyclo [2.2.1] heptane-2,3-dicarboxylic acid) dianhydride, bicyclo [2.2.2] oct-7-ene-2,3,5,6-tetracarboxylic acid Acid dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2'-bis [4- (3,4-dicarboxyphenyl) phenyl] propane dianhydride, 2 , 2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride, 2,2'-bis [4- (3,4-dicarboxyphenyl) phenyl] hexafluoropropane dianhydride, 4, 4'-bis (3,4-dicarboxyl (Phenoxy) diphenylsulfide dianhydride, 1,4-bis (2-hydroxyhexafluoroisopropyl) benzenebis (trimellitic anhydride), 1,3-bis (2-hydroxyhexafluoroisopropyl) ) Benzenebis (trimellitic anhydride), 5- (2,5-dioxotetrahydrofuranyl) -3-methyl-3-cyclohexene-1,2-dicarboxylic dianhydride, tetrahydrofuran-2,3 , 4,5-tetracarboxylic dianhydride, 4,4'-oxydiphthalic dianhydride, 1,2- (extended ethyl) bis (trimellitic anhydride), 1,3- (trimethylene Bis (trimellitic anhydride), 1,4- (tetramethylene) bis (trimellitic anhydride), 1,5- (pentamethylene) bis (trimellitic anhydride), 1,6- (Hexamethylene) bis (trimellitic anhydride), 1,7- (heptamethylene) bis (trimellitic anhydride), 1,8- (octamethylene) bis (trimellitic anhydride), 1,9- (ninemethylene) bis (trimellitic anhydride), 1,10- (decamethylene) bis (trimellitic anhydride), 1,12- (dodecylmethylene) bis (partial Trimellitic anhydride), 1,16- (hexamethylene) bis (trimellitic anhydride), 1,18- (octadecyl methylene) bis (trimellitic anhydride), etc., these can be used alone Or use two or more types in combination. Among these, 3,4,3 ', 4'-benzophenonetetracarboxylic dianhydride, 2,3,2', 3'-benzophenonetetracarboxylic dianhydride, 2,3, 3 ', 4'-benzophenone tetracarboxylic dianhydride, more preferably 3,4,3', 4'-benzophenone tetracarboxylic dianhydride.

The diamine is not particularly limited, and examples thereof include o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 3,3'-diaminodiphenyl ether, and 3,4'-diaminodiphenyl Ether, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, bis (4-amino-3, 5-dimethylphenyl) methane, bis (4-amino-3,5-diisopropylphenyl) methane, 3,3'-diaminodiphenyldifluoromethane, 3,4'- Diaminodiphenyldifluoromethane, 4,4'-diaminodiphenyldifluoromethane, 3,3'-diaminodiphenylphosphonium, 3,4'-diaminodiphenylphosphonium , 4,4'-diaminodiphenylphosphonium, 3,3'-diaminodiphenylsulfide, 3,4'-diaminodiphenylsulfide, 4,4'-diamine Diphenyl sulfide, 3,3'-diaminodiphenyl ketone, 3,4'-diaminodiphenyl ketone, 4,4'-diaminodiphenyl ketone, 3- (4- Aminophenyl) -1,1,3-trimethyl-5-aminoindan, 2,2-bis (3-aminophenyl) propane, 2,2 '-(3,4'-di Amine diphenyl) propane, 2,2-bis (4-aminophenyl) propane, 2,2-bis (3-aminophenyl) hexafluoropropane, 2,2- (3,4'- Diaminodiphenyl) hexafluoropropane, 2,2-bis (4-aminophenyl) hexafluoropropane, 1,3-bis (3-amine Phenylphenoxy) benzene, 1,4-bis (3-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 3,3 '-(1,4- Phenylbis (1-methylethylene)) bisaniline, 3,4 '-(1,4-phenylenebis (1-methylethylene)) bisaniline, 4,4'-(1 , 4-phenylenebis (1-methylethylene)) 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-aminophenylbenzene) (Oxy) phenyl) sulfide, bis (4- (4-aminophenoxy) phenyl) sulfide, bis (4- (3-aminophenoxy) phenyl) fluorene, bis (4- (4-Aminophenoxy) phenyl) fluorene, 3,3'-dihydroxy-4,4'-diaminobiphenyl, 3,5-diaminobenzoic acid and other aromatic diamines, 1 , 3-bis (aminomethyl) cyclohexane, 2,2-bis (4-aminophenoxyphenyl) propane, polyoxypropylene diamine, 4,9-dioxadodecane-1 , 12-diamine, 4,9,14-trioxaheptadecan-1,17-diamine, 1,2-diaminoethane, 1,3-diaminopropane, 1,4-diamine Aminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diamine Aminononane, 1,10-diaminodecane , 1,11-diaminoundecane, 1,12-diaminododecane, 1,2-diaminocyclohexane, 1,3-bis (3-aminopropyl) tetramethyl Disiloxane and so on. These diamines are preferably selected from 3- (4-aminophenyl) -1,1,3-trimethyl-5-aminoindane, 1,3-bis (3-aminopropyl) ) Tetramethyldisilazane, polyoxypropylene diamine, 2,2-bis (4-aminophenoxyphenyl) propane, 4,9-dioxadodecane-1,12-diamine One or more of the group consisting of 1,6-diaminohexane and 4,9,14-trioxaheptadecan-1,17-diamine, more preferably 3- (4-amino Phenyl) -1,1,3-trimethyl-5-aminoindan.

Examples of the solvent used in the reaction between tetracarboxylic dianhydride and diamine include N, N-dimethylacetamide, N-methyl-2-pyrrolidone, and N, N-dimethyl Formamidine. In order to adjust the solubility of raw materials, etc., a non-polar solvent (for example, toluene or xylene) may be used in combination. The reaction temperature of tetracarboxylic dianhydride and diamine is preferably less than 100 ° C, and more preferably less than 90 ° C. In addition, the fluorene imidization of the polyamic acid is performed by performing a heat treatment in a representative inert environment (for example, a vacuum or nitrogen atmosphere). The heat treatment temperature is preferably 150 ° C or higher, and more preferably 180 ° C to 450 ° C.

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

In the present invention, the thermoplastic polyfluorene imide resin is preferably selected from the group consisting of γ-butyrolactone, cyclopentanone, N-methylpyrrolidone, N-ethyl-2-pyrrolidone, and cyclohexanone. The solubility at 25 ° C. of at least one of the solvents Glycol ether, Glycol ether, Dimethyl sulfene, and Tetramethylurea is 10 g / 100 g Solvent or more. Examples of the thermoplastic polyfluorene imide resin having such a solubility include 3,4,3 ', 4'-benzophenonetetracarboxylic dianhydride and 3- (4-aminophenyl) -1, Thermoplastic polyfluorene imine resin obtained by 1,3-trimethyl-5-aminoindan reaction. The thermoplastic polyimide resin is particularly excellent in heat resistance.

As the thermoplastic polyimide resin, a commercially available product can be used. For example: Durimide (registered trademark) 200, 208A, 284 (above are manufactured by Fujifilm (stock)); GPT-LT (made by Qunrong Chemical Industry (stock)); SOXR- S, SOXR-M, SOXR-U, SOXR-C (the above are manufactured by Nippon Kodoshi Industrial Co., Ltd.); EXTEM VH1003, VH1003F, VH1003M, XH1015 (the above are manufactured by Japan SABIC Co., Ltd.).

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

式（1）中，Ar¹ 及Ar² 分別獨立地表示芳香族基，L表示單鍵或二價連結基。[Chemical 7]

In 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, a fluorene ring, a heptalene ring, an indacene ring, and a fluorene ring. , Pentacene ring, acenaphthene ring, phenanthrene ring, anthracene ring, fused tetraphenyl ring, 1,2-benzophenene (chrysene) ring, 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, indazine ring, indole ring, benzofuran ring , Benzothiophene ring, isobenzofuran ring, quinazine ring, quinoline ring, phthalazine ring, naphthyridine ring, quinoxaline ring, quinazoline ring, isoquinoline ring, carbazole ring, morphine ( phenanthridine ring, acridine ring, morpholine ring, thianthrene ring, chromene ring, xanthene ring, phenoxathiin ring, phenothiazine Ring and phenazine ring. Among them, a benzene ring is preferred. These aromatic groups may have a substituent, and preferably have no 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. The carbon number of the alkyl group is preferably 1 to 20, and more preferably 1 to 10. The alkyl group may be any of linear and branched species. In addition, a part or all of the hydrogen atom of the alkyl group may be substituted with a halogen atom. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. A fluorine atom is preferred. The alkoxy group is preferably an alkoxy group having 1 to 30 carbon atoms. The carbon number of the alkoxy group is more preferably 1 to 20, and even more preferably 1 to 10. The alkoxy group may be any of linear, branched, and cyclic types. The aryl group is preferably an aryl group having 6 to 30 carbon atoms, and more preferably an aryl group having 6 to 20 carbon atoms.

The weight average molecular weight (Mw) of the polycarbonate resin is preferably 1,000 to 1,000,000, and more preferably 10,000 to 80,000. If it is the said range, solubility in a solvent and heat resistance will be favorable.

Examples of commercially available polycarbonate resins include PCZ-200, PCZ-300, PCZ-500, and PCZ-800 (the above are manufactured by Mitsubishi Gas Chemical Co., Ltd.); APEC 9379 (Bayer ( Bayer); Panlite L-1225LM (manufactured by Teijin).

<< Tensile Elasticity Coefficient of Resin> The tensile elasticity coefficient E of the resin used in the composition for temporary bonding of the present invention at 25 ° C according to Japanese Industrial Standards (JIS) K7161: 1994 is preferred. 1 MPa or more and 4000 MPa or less, more preferably 1 MPa or more and 100 MPa or less, even more preferably 1 MPa or more and 60 MPa or less, even more preferably 1 MPa or more and 35 MPa or less, even more preferably 1 MPa or more It is preferably 20 MPa or less, more preferably 1 MPa or more and 15 MPa or less, and particularly preferably 3 MPa or more and 10 MPa or less. By setting it as such a range, curvature can be suppressed more effectively. The tensile elasticity coefficient E of the resin can be measured by a method described in Examples described later.

<< Resin compounding amount >> The composition for temporary bonding of the present invention preferably contains the resin in a total solid content of 50.00% to 99.99% by mass, and more preferably 70.00% by mass to 99.99% by mass, particularly preferably from 88.00% by mass to 99.99% by mass. When the content of the resin is within the above range, the adhesiveness and peelability are excellent. In the case where an elastomer is used as the resin, it is preferable to include the elastomer in a proportion of 50.00 mass% to 99.99 mass% in the total solid content of the composition for temporary bonding, and more preferably 70.00 mass% to 99.99 mass%. It is preferably 88.00% to 99.99% by mass. When content of an elastomer is the said range, it is excellent in adhesiveness and peelability. When two or more kinds of elastomers are used, the total is preferably in the range described above. When an elastomer is used as the resin, the content of the elastomer in the total resin mass is preferably 50% to 100% by mass, more preferably 70% to 100% by mass, and even more preferably 80% by mass. It is 100% by mass, particularly preferably 90% by mass to 100% by mass. In addition, the resin may be substantially only an elastomer. The term "resin is essentially 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 particularly preferably containing only an elastomer.

<Polyether Modified Silicone A> The ratio represented by the following formula (A) of the polyether modified silicone A used in the composition for temporary adhesion of the present invention is 80% or more. Formula (A) {(MO + EO) / AO} × 100 In the formula (A), MO is the mole% of the methylene oxide contained in the polyether structure in the polyether modified silicone, EO is the mole% of the ethylene oxide contained in the polyether structure in the polyether modified silicone, and 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, even more preferably 98% or more, particularly preferably 99% or more, and even more preferably 100%.

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

The polyether-modified silicone A used in the composition for temporary connection of the present invention is preferably: under a nitrogen flow of 60 mL / min, the polyether-modified silicone A is heated from 20 ° C at a temperature increase rate of 20 ° C / min. The mass reduction rate when the temperature was raised to 280 ° C and held at a temperature of 280 ° C for 30 minutes was 50% by mass or less. By using such a compound, there is a tendency that the planarity of the substrate after processing accompanying heating increases. The mass reduction rate of the polyether-modified silicone A is more preferably 45% by mass or less, even more preferably 40% by mass or less, even more preferably 35% by mass or less, and even more preferably 30% by mass or less. The lower limit value of the mass reduction rate of the polyether-modified silicone A may be 0% by mass, and even if it is 15% by mass or more, and furthermore 20% by mass, it is a sufficiently practical level. The mass reduction rate in the present invention can be measured by the method described in the examples.

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

所述式（101）中，R¹¹ 及R¹⁶ 分別獨立地為取代基，R¹² 及R¹⁴ 分別獨立地為二價連結基，R¹³ 及R¹⁵ 為氫原子或碳數1～5的烷基，m11、m12、n1及p1分別獨立地為0～20的數，x1及y1分別獨立地為2～100的數。 式（102） [化9]

所述式（102）中，R²¹ 、R²⁵ 及R²⁶ 分別獨立地為取代基，R²² 為二價連結基，R²³ 為氫原子或碳數1～5的烷基，m2及n2分別獨立地為0～20的數，x2為2～100的數。 式（103） [化10]

所述式（103）中，R³¹ 及R³⁶ 分別獨立地為取代基，R³² 及R³⁴ 分別獨立地為二價連結基，R³³ 及R³⁵ 為氫原子或碳數1～5的烷基，m31、m32、n3及p3分別獨立地為0～20的數，x3為2～100的數。 式（104） [化11]

所述式（104）中，R⁴¹ 、R⁴² 、R⁴³ 、R⁴⁴ 、R⁴⁵ 及R⁴⁶ 分別獨立地為取代基，R⁴⁷ 為二價連結基，R⁴⁸ 為氫原子或碳數1～5的烷基，m4及n4分別獨立地為0～20的數，x4及y4分別獨立地為2～100的數。The molecular weight of the polyether modified silicone A used in the temporary bonding composition of the present invention is preferably 500 or more. In the present invention, particularly preferred is a polyether-modified silicone represented by any one of the following formulae (101) to (104). Formula (101)

In the formula (101), R ¹¹ and R ¹⁶ are each independently a substituent, R ¹² and R ¹⁴ are each independently a divalent linking group, R ¹³ and R ¹⁵ are a hydrogen atom or an alkane having 1 to 5 carbon atoms. The basis, m11, m12, n1, and p1 are each independently a number from 0 to 20, and x1 and y1 are each independently a number from 2 to 100. Formula (102)

In the formula (102), R ²¹ , R ²⁵ and R ²⁶ are each independently a substituent, R ²² is a divalent linking group, R ²³ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and m 2 and n 2 are respectively Independently, it is a number from 0 to 20, and x2 is a number from 2 to 100. Formula (103)

In the formula (103), R ³¹ and R ³⁶ are each independently a substituent, R ³² and R ³⁴ are each independently a divalent linking group, R ³³ and R ³⁵ are a hydrogen atom or an alkane having 1 to 5 carbon atoms. Basis, m31, m32, n3, and p3 are each independently a number from 0 to 20, and x3 is a number from 2 to 100. Formula (104)

In the 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 a carbon number of 1 to 5 alkyl groups, 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 formula (101), R ¹¹ and R ¹⁶ are each independently a substituent, preferably an alkyl group or a phenyl group having 1 to 5 carbon atoms, and more preferably a methyl group. In the formula (101), R ¹² and R ¹⁴ are each independently a divalent linking group, and are preferably 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 alkenyl group having 2 to 8 carbon atoms, an alkynyl group having 2 to 5 carbon atoms, and an arylene group having 6 to 10 carbon atoms, more preferably an oxygen atom. 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 1 to 3 carbon atoms. Alkyl.

In the formula (102), R ²¹ , R ^25, and R ²⁶ are each independently a substituent, and have the same meaning as R ¹¹ and R ¹⁶ in the formula (101), and preferred ranges are also the same. In the formula (102), R ^{2 2} is a divalent linking group, and has the same meaning as R ¹² and R ¹⁴ in the formula (101), and the preferred ranges are also the same. In the formula (102), R ^{2 3} is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and has the same meaning as R ^{1 3} and R ^{1 5} in the formula (101), and preferred ranges are also the same.

In the formula (103), R ^{3 1} and R ^{3 6} are each independently a substituent, and have the same meaning as R ¹¹ and R ¹⁶ in the formula (101), and the preferred ranges are also the same. In the formula (103), R ^{3 2} and R ^{3 4} are each independently a divalent linking group, and have the same meaning as R ¹² and R ¹⁴ in the formula (101), and their preferred ranges are also the same. In the formula (103), R ^{3 3} and R ^{3 5} are a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and have the same meaning as R ^{1 3} and R ^{1 5} in the formula (101), and the preferred ranges are also the same. .

In the formula (104), R ^{4 1} , R ⁴² , R ⁴³ , R ⁴⁴ , R ^45, and R ⁴⁶ are each independently a substituent, and have the same meaning as R ¹¹ and R ¹⁶ in the formula (101), preferably The range is the same. In the formula (104), R ⁴⁷ is a divalent linking group, and has the same meaning as R ¹² and R ¹⁴ in the formula (101), and the preferred ranges are 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 ^{1 3} and R ^{1 5} in the formula (101), and preferred ranges are also the same.

Among formulas (101) to (104), formula (103) or formula (104) is preferred, and formula (104) is more preferred.

The content rate of the polyoxyalkylene group in the polyether-modified silicone A used in the temporary bonding composition of the present invention is not particularly limited, and it is desirable that the content rate of the polyoxyalkylene group exceeds 1%. The content of polyoxyalkylene is determined by "((formula of polyoxyalkylene in polyether modified silicone A molecule) / molecular weight of polyether modified silicone A molecule) × 100" To define.

As the polyether-modified silicone A used in the temporary adhesive composition of the present invention, a commercially available product may be used. For example, a mold release agent having a ratio represented by formula (A) of 80% or more in the following commercially available products can be used. ADVALON FA33, FLUID L03, FLUID L033, FLUID L051, FLUID L053, FLUID L060, FLUE Germany (FLUID) L066, IM22, WACKER-Belsil DMC 6038 (the above is manufactured by Asahi Kasei Wacker Silicone Co., Ltd.); KF-352A, KF-353, KF-615A, KP-112, KP -341, X-22-4515, KF-354L, KF-355A, KF-6004, KF-6011, KF-6011P, KF-6012, KF-6013, KF-6015, KF-6016, KF-6017, KF -6017P, KF-6020, KF-6028, KF-6028P, KF-6038, KF-6043, KF-6048, KF-6123, KF-6204, KF-640, KF-642, KF-643, KF-644 , KF-945, KP-110, KP-355, KP-369, KS-604, Polon SR-Conc, X-22-4272, X-22-4952 (the above is Shin-Etsu Chemical Industrial (stock) manufacturing); 8526 Additive (ADDITIVE), FZ-2203, FZ-5609, L-7001, SF 8410, 2501 Cosmetic Wax (COSMETIC WAX), 5200 Formulation Aid (FORMULATION AID), 57 Additive (ADDITIVE) , 8019 additive (ADDITIVE), 8029 additive (ADDITIVE), 8054 additive (ADDITIVE) BY16-036, BY16-201, ES-5612 Formulation Aid, FZ-2104, FZ-2108, FZ-2110, FZ-2123, FZ-2162, FZ-2164, FZ-2191, FZ-2207 , FZ-2208, FZ-2222, FZ-7001, FZ-77, L-7002, L-7604, SF8427, SF8428, SH 28 PAINR ADDITIVE, SH3749, SH3773M, SH8400, SH8700 (The above are East Toray Dow Corning (manufactured); BYK-378, BYK-302, BYK-307, BYK-331, BYK-345, BYK-3455, BYK-347, BYK-348, BYK-349, BYK -377 (the above is manufactured by BYK-Chemie Japan); Silwet L-7001, Silwet L-7002, Silwet L-720 , Silwet L-7200, Silwet L-7210, Silwet L-7220, Silwet L-7230, Silwet 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-7602, Silwet L-7604, Silwet L-7607, Silwet L-7608, Silwet L-7622, Silwet L-7650, Silwet L-7657, Silwet L-77, Silwet L-8500, Silwet L-8610, TSF4440, TSF4441, TSF4450, TSF4460 (the above are manufactured by Momentive Performance Materials Japan).

The content of the polyether modified silicone A in the temporary bonding composition of the present invention is 0.001% by mass 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 mass% or more, more preferably 0.006 mass% or more, still more preferably 0.008 mass% or more, and even more preferably 0.009 mass% or more. 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, even more preferably 0.15% by mass or less, and even more preferably 0.09 mass% or less. The composition for temporary bonding of the present invention may include only one type of polyether modified silicone A, or may include two or more types. When two or more types are included, the total amount is preferably in the range.

<Other Release Agents> The composition for temporary bonding of the present invention may contain release agents other than the polyether modified silicone A described above. Examples of the other release agent include fluorine-based liquid compounds and silicone compounds other than those mentioned above. When other mold release agents are contained, the content is preferably in the range of 0.001% by mass to 0.005% by mass of the solid content of the composition for temporary bonding. The other release agents may include only one kind, or may include two or more kinds. When two or more types are included, the total amount is preferably in the range. Moreover, in this invention, it can be set as the structure which does not contain another release agent substantially. The fact that the other release agent is not substantially contained means that the content of the other release agent is 1% by mass or less of the content of the polyether modified silicone A.

<Plasticizer> The composition for temporary bonding of this invention may contain a plasticizer as needed. By blending the plasticizer, a temporary adhesive film that satisfies the various properties can be formed. As the plasticizer, a phthalate, a fatty acid ester, an aromatic polycarboxylic acid ester, a polyester, or the like can be used.

Examples of phthalates include: DMP, DEP, DBP, # 10, BBP, DOP, DINP, DIDP (the above is manufactured by Da Ya Chemical Industry Co., Ltd.); PL-200, DOIP (the above is CG CG Ester (manufactured by KK); Sansocizer DUP (manufactured by Nippon Physico-chemical Co., Ltd.), etc. Examples of fatty acid esters include butyl stearate, Unistar M-9676, Unistar M-2222SL, Unistar H-476, and Unistar ) H-476D, Panasate 800B, Panasate 875, Panasate 810 (the above are manufactured by Japan Petroleum Corporation); DBA, DIBA, DBS, DOA, DINA, DIDA, DOS, BXA, DOZ, DESU (the above are manufactured by Big Eight Chemical Industry (stock)). Examples of the aromatic polycarboxylic acid esters include: TOTM, Monocizer W-705 (above manufactured by Da Ya Chemical Industry Co., Ltd.); UL-80, UL-100 (above: ADEKA ) (Shares) manufacturing) and so on. Examples of polyesters include: Polycizer TD-1720, Polycizer S-2002, Polycizer S-2010 (the above are manufactured by DIC) BAA-15 (manufactured by Da Ya Chemical Industry Co., Ltd.), etc. Among the plasticizers, preferred are DIDP, DIDA, TOTM, Unistar M-2222SL, Polycizer TD-1720, more preferably DIDA, TOTM, and particularly preferably TOTM. The plasticizer may be used alone or in combination of two or more.

From the viewpoint of preventing sublimation during heating, when the weight change is measured under a nitrogen gas flow based on a heating rate of a fixed rate of 20 ° C / min, the temperature at which the weight of the plasticizer is reduced by 1% by mass is preferably 250 ° C or more. The temperature is more preferably 270 ° C or higher, and particularly preferably 300 ° C or higher. The upper limit is not particularly limited, and may be, for example, 500 ° C or lower.

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

<Antioxidant> The composition for temporary bonding of this invention may contain an antioxidant. As the antioxidant, a phenol-based antioxidant, a sulfur-based antioxidant, a phosphorus-based antioxidant, a quinone-based antioxidant, an amine-based antioxidant, or the like can be used. Examples of the phenolic antioxidant include p-methoxyphenol, 2,6-di-tert-butyl-4-methylphenol, Irganox 1010, and Irganox 1330. , Irganox 3114, Irganox 1035 (the above are manufactured by BASF Japan), Sumilizer MDP-S, Sumilizer ) GA-80 (above are manufactured by Sumitomo Chemical Co., Ltd.) and so on. Examples of the sulfur-based antioxidant include 3,3'-thiodipropionate distearyl, Sumilizer TPM, Sumilizer TPS, and Sumilizer ) TP-D (the above are manufactured by Sumitomo Chemical Co., Ltd.) and so on. Examples of the phosphorus-based antioxidant include tris (2,4-di-third-butylphenyl) phosphite, bis (2,4-di-third-butylphenyl) pentaerythritol diphosphite, Poly (dipropylene glycol) phenylphosphite, diphenylisodecylphosphite, 2-ethylhexyldiphenylphosphite, triphenylphosphite, Irgafos 168, easy Irgafos 38 (above manufactured by BASF Japan). 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. The antioxidant is preferably Irganox 1010, Irganox 1330, 3,3'-distearyl thiodipropionate, Sumilizer TP-D, More preferred is Irganox 1010, Irganox 1330, and particularly preferred is Irganox 1010. Among the antioxidants, it is preferable to use a phenol-based antioxidant and a sulfur-based antioxidant or a phosphorus-based antioxidant in combination, and it is most preferable to use a phenol-based antioxidant and a sulfur-based antioxidant in combination. 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 setting it as such a combination, the effect which can suppress the deterioration of the resin by an oxidation reaction efficiently can be expected. When a phenol-based antioxidant and a sulfur-based antioxidant are used in combination, the quality of the phenol-based antioxidant and the sulfur-based antioxidant is better: phenol-based antioxidant: sulfur-based antioxidant = 95: 5 to 5:95, more preferably 25:75 to 75:25. As a combination of antioxidants, Irganox 1010 and Sumilizer TP-D, Irganox 1330 and Sumilizer TP-D and Su Sumilizer GA-80 and Sumilizer TP-D, more preferably Irganox 1010 and Sumilizer TP-D, Irganox ) 1330 and Sumilizer TP-D, especially preferred is 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 0.001% to 20.0% by mass, and more preferably 0.005% to 10.0% by mass, relative to the total solid content of the composition for temporary bonding. . The antioxidant may be only one kind, or two or more kinds. When there are two or more antioxidants, it is preferable that the total thereof is within the above range.

<Solvent> The composition for temporary bonding of the present invention preferably contains a solvent. A known solvent can be used without limitation, and an organic solvent is preferred. As an organic solvent, ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, Butyl butyrate, methyl lactate, ethyl lactate, alkyl alkoxyacetate (e.g. methyl alkoxyacetate, ethyl alkoxyacetate, butyl alkoxyacetate (e.g. methyl methoxyacetate) , Ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.)), alkyl 3-alkoxypropionates (such as 3-alkoxy Methyl propionate, ethyl 3-alkoxypropionate, etc. (e.g. methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-ethyl Ethyloxypropionate, etc.)), alkyl 2-alkoxypropionates (e.g. methyl 2-alkoxypropionate, ethyl 2-alkoxypropionate, 2-alkoxypropionic acid Propyl esters (e.g. methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, 2-ethoxy Ethyl propionate)), methyl 2-alkoxy-2-methylpropionate and ethyl 2-alkoxy-2-methylpropionate (Such as methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, ethyl甲酯 Methyl acetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, 1-methoxy-2-propyl acetate, ethyl carbitol acetate Esters, esters such as butyl carbitol acetate; diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve Agent acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monoethyl ether Ethers such as propyl ether acetate, propylene glycol methyl ether, propylene glycol methyl ether acetate; methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, N-methyl-2 -Ketones such as pyrrolidone, γ-butyrolactone; pyrrolidones such as N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone; toluene, xylene, anisole, Mesitylene, pseudocumene, ethylbenzene, propylbenzene, cumene, n-butyl Benzene, second butylbenzene, isobutylbenzene, third butylbenzene, pentylbenzene, isoamylbenzene, (2,2-dimethylpropyl) benzene, 1-phenylhexane, 1- Phenylheptane, 1-phenyloctane, 1-phenylnonane, 1-phenyldecane, cyclopropylbenzene, cyclohexylbenzene, 2-ethyltoluene, 1,2-diethylbenzene, O-isopropyltoluene, indane, 1,2,3,4-tetrahydronaphthalene, 3-ethyltoluene, m-isopropyltoluene, 1,3-diisopropylbenzene, 4-ethyltoluene , 1,4-diethylbenzene, p-isopropyltoluene, 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-third butyl-m-xylene, 3,5-di-third butyl toluene, 1,2, Aromatic hydrocarbons such as 3,5-tetramethylbenzene, 1,2,4,5-tetramethylbenzene, pentamethylbenzene, decahydronaphthalene; ethyl cyclohexane, limonene, p-menthane , Nonane, decane, dodecane, decalin and other aliphatic hydrocarbons.

From the viewpoint of improving the coating surface, these solvents are also preferably in the form of a mixture of two or more. In this case, it is particularly preferable that the mixed solution contains a material selected from the group consisting of mesitylene, third butylbenzene, pseudocumene, p-menthane, γ-butyrolactone, and N-ethyl-2-pyrrolidine. Ketone, anisole, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve 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 ethyl Two or more of the acid esters.

In the case where the composition for temporary bonding of the present invention has a solvent, the content of the solvent of the composition for temporary bonding is preferably 5 mass% from the viewpoint of coating properties, and the total solid content concentration of the composition for temporary bonding is 5 mass%. The amount of ∼80% by mass is more preferably a total solid content concentration of the composition for temporary bonding to be 5% to 70% by mass, and even more preferably the total solid content of the composition for temporary temporary bonding is 10% by mass to 60% by mass. The solvent may be only one kind, or two or more kinds. When there are two or more solvents, it is preferable that the total thereof is within the above range.

<Surfactant> The composition for temporary bonding of the present invention preferably contains a surfactant. As the surfactant, any of anionic, cationic, nonionic, or amphoteric may be used. A preferred surfactant is a nonionic surfactant. Preferred examples of the nonionic surfactant include polyoxyethylene higher alkyl ethers, polyoxyethylene higher alkylphenyl ethers, and higher fatty acid diesters of polyoxyethylene glycols.

When the composition for temporary bonding of the present invention has a surfactant, from the viewpoint of coating properties, the content of the surfactant for the temporary bonding composition is smaller than the total solid content of the temporary bonding composition. It is preferably 0.001% by mass to 5% by mass, more preferably 0.005% by mass to 1% by mass, and still more preferably 0.01% by mass to 0.5% by mass. The surfactant may be only one kind, or two or more kinds. When there are two or more kinds of surfactants, it is preferable that the total thereof is within the above range.

<Other additives> As long as the effect of the present invention is not impaired, the composition for temporary bonding of the present invention can be adjusted with various additives, such as hardener, hardening catalyst, filler, adhesion promoter, and ultraviolet absorber, as needed. , Anti-coagulant and so on. In the case of blending these additives, it is preferable that the total blending amount thereof is 3% by mass or less of the total solid content of the composition to be temporarily adhered.

The composition for temporary bonding of the present invention is preferably free of impurities such as metals. The content of impurities contained in these materials is preferably 1 mass ppm or less (parts per million), more preferably 100 mass ppt or less (parts per trillion). It is further more preferably 10 mass ppt or less, and particularly preferably not substantially contained (below the detection limit of the measurement device). As a method of removing impurities such as metals from the composition for the time being, for example, filtration using a filter may be mentioned. The filter pore diameter is preferably 10 nm or less, more preferably 5 nm or less, and even more preferably 3 nm or less. The material of the filter is preferably polytetrafluoroethylene, polyethylene, or nylon. The filter may be previously cleaned with an organic solvent. In the filter filtration step, various filters can be used in series or in parallel. When multiple filters are used, filters with different pore sizes and / or materials can be used in combination. In addition, various materials may be filtered multiple times, and the step of multiple filtering may also be a cyclic filtering step. In addition, as a method for reducing impurities such as metals contained in the temporary bonding composition, methods such as selecting a raw material with a small metal content as a raw material constituting the temporary bonding composition, and selecting a raw material constituting the temporary bonding composition Filtering is performed; distillation is performed under conditions that minimize contamination by forming a lining or the like in a device using Teflon (registered trademark). The preferable conditions in the filter filtration of the raw materials constituting the composition to be temporarily followed by the composition are the same as those described above. In addition to filter filtration, impurities can be removed using an adsorbent, or a combination of filter filtration and removal of impurities using an adsorbent can be implemented. As the adsorbent, a known adsorbent can be used, and for example, an inorganic adsorbent such as silica gel and zeolite, and an organic adsorbent such as activated carbon can be used.

<Formation of a temporary bonding film> The temporary bonding film can be formed on the surface of at least one of a 1st base material and a 2nd base material using the temporary bonding composition of this invention. A temporary adhesive film may be formed on only one of the first substrate and the second substrate and bonded to the other substrate, or a temporary adhesive film may be provided on both substrates to bond the two. In the formation of the temporary bonding film, a conventionally known spin coating method, spray method, slit coating method, roll coating method, flow coating method, doctor blade coating method, dipping method, etc. can be used for the temporary bonding composition. . Then, usually, the composition contains a solvent for a while, and therefore, the solvent is heated to volatilize the solvent. The heating temperature is preferably a temperature higher than the boiling point of the solvent, more preferably 110 ° C or higher, still more preferably 130 ° C to 200 ° C, and particularly preferably 160 ° C to 190 ° C.

<Preparation of composition for temporary adhesion> The composition for temporary adhesion of this invention can be prepared by mixing each said component. Mixing of each component is performed normally in the range of 0 degreeC-100 degreeC. Moreover, after mixing each component, it is preferable to filter with a filter, for example. Filtration can be performed in multiple stages or iteratively. Alternatively, the filtered liquid may be refiltered. The filter can be used without particular limitation as long as it has been used for filtering purposes and the like. Examples include the use of fluororesins such as polytetrafluoroethylene (PTFE), polyamide resins such as nylon-6 and nylon-6,6, polyolefin resins such as polyethylene and polypropylene (including polypropylene) Density, ultra-high molecular weight polyolefin resin) and other raw material filters. Among these raw materials, polypropylene (including high-density polypropylene) and nylon are preferred. The pore diameter of the filter is preferably about 0.003 μm to 5.0 μm, for example. By setting it as this range, clogging of a filter can be suppressed, and the fine foreign matter, such as an impurity and an aggregate, contained in a composition can be removed reliably. When using filters, different filters can be combined. In this case, the filtration using the first filter may be performed only once, or may be performed twice or more. When two or more filtrations are performed by combining different filters, it is preferable that the pore diameters of the second and subsequent pores are the same as or smaller than those of the first filtration. In addition, the first filters having different pore sizes may be combined within the above range. The pore size here can refer to the nominal value of the filter manufacturer. As commercially available filters, for example, Pall (Japan), Advantec Toyo (Japan), Entegris (Japan), or Kitza Microfilter ) (Shares), etc. to choose from the various filters provided.

<Peeling force of composition for temporary adhesion> The peeling force of the composition for temporary adhesion of the present invention is preferably 1 N / m to 20 N / m, and more preferably 1 N / m to 25 N / m. The lower limit of the peeling force is more preferably 3.0 N / m or more. The upper limit of the peeling force is more preferably 20 N / m or less, even more preferably 15 N / m or less, even more preferably 10 N / m or less, and even more preferably 9 N / m or less. By setting it as such a range, the effect which can peel off a processed base material more effectively is 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 by using a temporary adhesive composition, and the end of the film is temporarily bonded at a speed of 300 mm / min at 25 ° C. It can be peeled by pulling up in a direction perpendicular to the surface on which the temporary bonding film is formed on the silicon wafer, and the force at the time of pulling up is measured using a dynamometer. Specifically, the method is described in the examples described later.

Laminated Body In addition, the present invention discloses a laminated body having a first base material, a temporary adhesive film, and a second base material, which are sequentially adjacent to each other. The temporary bonding film is formed from the temporary bonding composition of the present invention. The laminated body of this invention uses the said composition for temporary adhesion, and temporarily uses a 1st base material and a 2nd base material.

Method for Manufacturing Semiconductor Device <First Embodiment> Hereinafter, an embodiment of a method for manufacturing a semiconductor device that has undergone the steps of manufacturing a laminated body will be described with reference to FIGS. 1 (A) to (E). The present invention is not limited to the following embodiments. (A) to (E) of FIG. 1 are schematic cross-sectional views for explaining the temporary continuation of a carrier substrate and an element wafer, respectively ((A) and (B) of FIG. 1), and are diagrams for temporarily adhering to the carrier substrate. A state where the element wafer is thinned (FIG. 1 (C)), a state where the carrier substrate and the element wafer are peeled off (FIG. 1 (D)), and a state where the film is temporarily removed from the element wafer ( (E) of FIG. 1 is a schematic sectional view.

In this embodiment, as shown in FIG. 1 (A), first, an adhesive carrier substrate 100 in which a film 11 is temporarily adhered to a carrier substrate 12 is prepared. The temporary bonding film 11 can be formed using the temporary bonding composition of the present invention. It is preferable that the temporarily adhered film 11 be substantially free of a solvent. The element wafer 60 is formed by providing a plurality of element wafers 62 on the surface 61 a of the silicon substrate 61. The thickness of the silicon substrate 61 is preferably, for example, 200 μm to 1200 μm. The element wafer 62 is preferably a metal structure, for example, and its height is preferably 10 μm to 100 μm. In the process of forming the temporary adhesive film, a step of cleaning the carrier substrate and the back surface of the element wafer with a solvent may be provided. Specifically, by using a solvent that dissolves the temporary adhesive film, the residue of the temporary adhesive film adhered to the end surface or the back surface of the substrate or the wafer is removed, thereby preventing the device from being contaminated and reducing the total thickness of the thin element wafer. Variation (Total Thickness Variation, TTV). As the solvent used in the step of cleaning the back surface of the carrier substrate and the element wafer with the solvent, the solvent contained in the temporary bonding composition can be used.

Next, as shown in FIG. 1 (B), the adhesive carrier substrate and the element wafer 60 are pressure-bonded, so that the carrier substrate 12 and the element wafer 60 are temporarily adhered. The temporary bonding film 11 preferably covers the element wafer 62 completely. When the height of the element wafer is X μm and the thickness of the temporary bonding film is Y μm, the relationship “X + 100 ≧ Y> X” is preferably satisfied. The case where the film 11 completely covers the element wafer 62 temporarily is effective when it is desired to further reduce the TTV of the thin element wafer (that is, when it is desired to further improve the flatness of the thin element wafer). That is, when thinning the element wafer, the plurality of element wafers 62 are protected by the temporary adhesive film 11, so that the uneven shape can be substantially eliminated on the contact surface with the carrier substrate 12. Therefore, even if the thickness is reduced while being supported in this manner, the risk that the shapes derived from the plurality of element wafers 62 are transferred to the back surface 61b1 of the thin element wafer is reduced, and as a result, the resulting reduction in thickness can be further reduced. TTV of the component wafer.

Next, as shown in FIG. 1 (C), the back surface 61b of the silicon substrate 61 is subjected to a mechanical or chemical treatment (it is not particularly limited, for example, thin film processing such as sliding grinding or chemical mechanical polishing (CMP)) , Chemical vapor growth (Chemical Vapor Deposition, CVD) or physical vapor growth (Physical Vapor Deposition, PVD) and other high temperature and vacuum processing, using organic solvents, acidic or alkaline treatment chemicals and other chemicals Treatment, plating treatment, irradiation of actinic rays, heating treatment, cooling treatment, etc.). In (C) of FIG. 1, the thickness of the silicon substrate 61 is reduced (for example, the thickness is reduced to the thickness described above), and a thin element wafer 60 a is obtained.

After thinning the element wafer, a step of cleaning the temporary adhesive film beyond the area of the base material surface of the element wafer to the outside with a solvent may be provided in a stage before processing under high temperature and vacuum. Specifically, after thinning the element wafer, the excess temporary adhesive film is removed by using a solvent that dissolves the temporary adhesive film, thereby preventing the temporary adhesive film caused by directly performing a high temperature and vacuum treatment on the temporary adhesive film. Deformation and deterioration. As the solvent used in the step of temporarily bonding the film beyond the area of the base material surface of the carrier base material or the base material surface of the element wafer to the outside using a solvent, the temporary bonding may be used. The solvent contained in the composition. That is, in the present invention, the area of the film surface of the temporary adhesion film is preferably smaller than the area of the substrate surface of the carrier substrate. In the present invention, the diameter of the substrate surface of the carrier substrate is C μm, the diameter of the substrate surface of the element wafer is D μm, and the diameter of the film surface temporarily adhered to the film is T μm. When, it is better to satisfy (C-200) ≧ T ≧ D. Furthermore, when the diameter of the substrate surface of the carrier substrate is set to C μm, the diameter of the substrate surface of the element wafer is set to D μm, and the diameter of the film surface on the side of the film which is temporarily in contact with the carrier substrate is set It is T _C μm, and when the diameter of the film surface on the side where the film is in contact with the element wafer temporarily adhered to the film is T _D μm, it is preferable to satisfy (C-200) ≧ T _C > T _D ≧ D. By adopting such a configuration, it is possible to further suppress the deformation and deterioration of the temporary bonding film caused by directly performing the treatment under high temperature and vacuum on the temporary bonding film. The area of the film surface temporarily adhering to the film refers to the area when viewed from a direction perpendicular to the carrier base material, and does not take into account the unevenness of the film surface. The same applies to the substrate surface of the element wafer. That is, the base material surface of the element wafer described herein is, for example, a surface corresponding to the 61a surface of (A) to (E) in FIG. 1, and is a surface on the side where the element wafer is provided. The same applies to the diameter of the film surface or the like that temporarily adheres to the film. In addition, the diameter T of the film surface of the temporary bonding film means that when the diameter of the film surface on the side of the film temporarily contacting the carrier substrate is set to T _C μm, When the diameter of the film surface is set to 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 element wafer refer to the diameter of the surface on the side in contact with the temporarily adhered film. In addition, although the carrier substrate and the like are defined as "diameter", the carrier substrate and the like do not necessarily have to be circular (perfect circles) in a mathematical sense, as long as they are approximately circular. When it is not a perfect circle, the diameter when converted into a perfect circle of the same area is the diameter. In addition, as a mechanical or chemical treatment, after the thin film processing, a through-hole (not shown) that penetrates the silicon substrate from the back surface 61b1 of the thinned element wafer 60a may be formed in the through-hole. A through silicon electrode (not shown) is formed. In the step (B) of the figure, the heat treatment may be performed in a period after the carrier base material 12 and the element wafer 60 are temporarily bonded and before the peeling. As an example of the heat treatment, heating is performed when performing a mechanical or chemical treatment. The maximum temperature reached during the heat treatment is preferably 80 ° C to 400 ° C, more preferably 130 ° C to 400 ° C, and even more preferably 180 ° C to 350 ° C. The highest temperature reached during the heat treatment is preferably set to a temperature lower than the decomposition temperature of the temporarily adhered film. The heat treatment is preferably heating for 30 seconds to 30 minutes at the highest reaching temperature, and more preferably heating for 1 minute to 10 minutes at the highest reaching temperature. Among them, irrespective of the decomposition temperature of the components included in the temporary bonding composition, it can be used satisfactorily as long as it does not cause swelling or voids in the temporary bonding film after the heat treatment. The generation of voids can be detected by observation with an ultrasonic microscope.

Next, as shown in FIG. 1D, the carrier substrate 12 is peeled from the thinned element wafer 60 a. The temperature at the time of peeling is preferably 40 ° C or lower, and may be 30 ° C or lower. The lower limit value of the temperature at the time of peeling is, for example, 0 ° C or higher, and preferably 10 ° C or higher. By using the composition for temporary adhesion of this invention, it is high in the point which can peel at normal temperature of about 15 degreeC-about 35 degreeC. The method of peeling is not particularly limited, and it is preferred that the thin element wafer 60 a is fixed and lifted from the end portion of the carrier base material laminate in a direction perpendicular to the thin element wafer 60 a to perform peeling. At this time, the peeling interface is preferably peeled at the interface between the carrier substrate 12 and the temporary adhesive film 11. The pulling speed at the time of peeling is preferably a speed of 30 mm / min to 100 mm / min, and more preferably a speed of 40 mm / min to 80 mm / min. In this case, the adhesion strength A of the interface between the carrier substrate 12 and the temporary adhesion film 11 and the adhesion strength B of the element wafer surface 61 a and the temporarily adhesion film 11 preferably satisfy the following formulas. A <B Formula (A1) Moreover, the force at the time of pulling up the edge part 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 value is preferably 0.07 N / mm or more. The force at this time can be measured using a dynamometer.

Further, as shown in FIG. 1 (E), by temporarily removing the film 11 from the thinned element wafer 60 a, a thinned element wafer can be obtained. The method of removing the temporary adhesive film 11 includes, for example, a method of peeling and removing the temporarily adhesive film, and a method of removing the temporary adhesive film by using a release solution (after the temporary adhesive film is swelled with the release solution, the adhesive is removed Removal method; method of spraying peeling liquid on the film for temporary removal and destruction; method of dissolving and removing the temporary adhesive film by dissolving in the peeling liquid; etc.); temporarily bonding the film by actinic radiation, radiation, or heat Decomposition, gasification and removal methods. From the viewpoint of reducing the amount of the peeling liquid, it is preferable to perform peeling and removal in a state where the film (film-like) is temporarily adhered. From the viewpoint of reducing damage to the surface of the element wafer, dissolution removal is preferred. The method of peeling and removing the film while temporarily adhering to the film refers to peeling the film itself (film-like) in a state of temporarily adhering to the film without performing a chemical treatment with a peeling liquid or the like. In the case where the film is peeled off while the film is temporarily adhered, mechanical peeling is preferred. In order to peel and remove the film while being temporarily adhered (film-like), it is preferable that the adhesion strength B between the surface of the element wafer 61 a and the temporarily adhered film 11 satisfies the following formula (B1). B ≦ 4 N / cm… Formula (B1) When the temporary protective film is removed by a release liquid, the following release liquid can be preferably used.

<< Peeling Liquid> As the peeling liquid, water and a solvent (organic solvent) can be used. The peeling liquid is preferably an organic solvent that dissolves the film 11 temporarily. Examples of the organic solvent include aliphatic hydrocarbons (hexane, heptane, Isopar E, H, G (produced by ESSO Chemical Co., Ltd.), limonene, p-menthane, nonyl Alkanes, decane, dodecane, decalin, etc.), aromatic hydrocarbons (toluene, xylene, anisole, mesitylene, pseudocumene, ethylbenzene, propylbenzene, cumene, n-butane Phenylbenzene, second butylbenzene, isobutylbenzene, third butylbenzene, pentylbenzene, isoamylbenzene, (2,2-dimethylpropyl) benzene, 1-phenylhexane, 1 -Phenylheptane, 1-phenyloctane, 1-phenylnonane, 1-phenyldecane, cyclopropylbenzene, cyclohexylbenzene, 2-ethyltoluene, 1,2-diethylbenzene , O-isopropyltoluene, indane, 1,2,3,4-tetrahydronaphthalene, 3-ethyltoluene, m-isopropyltoluene, 1,3-diisopropylbenzene, 4-ethyl Toluene, 1,4-diethylbenzene, p-isopropyltoluene, 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-triisopropyl Benzene, 5-tert-butyl-m-xylene, 3,5-tert-butyl-toluene, 1,2,3,5-tetramethylbenzene, 1,2,4,5-tetramethylbenzene , Pentamethylbenzene, etc.), halogenated hydrocarbons (dichloromethane, dichloroethane, trichloroethylene, 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, 1-nonanol, 1-decanol, benzyl alcohol, ethylene glycol monomethyl ether, 2-ethoxyethanol, diethylene glycol monoethyl ether, diethylene glycol Monohexyl ether, triethylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether, polyethylene glycol monomethyl ether, polypropylene glycol, tetraethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monobenzyl Ether, ethylene glycol monophenyl ether, propylene glycol monophenyl ether, methylphenyl methanol, n-pentanol, methylpentanol, etc.), ketones (acetone, methyl ethyl ketone, ethyl butyl ketone, Methyl isobutyl ketone, cyclohexanone, cyclopentanone, etc.), esters (ethyl acetate, propyl acetate, butyl acetate, pentyl acetate, benzyl acetate, methyl lactate, butyl lactate, ethyl acetate Glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, diethylene glycol acetate, diethyl phthalate, butyl acetoacetate, etc.), others (triethyl phosphate Ester, tricresyl phosphate, N-phenylethanolamine, N- Diethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, 4- (2-hydroxyethyl) morpholine, N, N-dimethylacetamidamine, N-methylpyrrolidone, N -Ethyl-2-pyrrolidone, etc.).

Furthermore, from a viewpoint of peelability, a peeling liquid may contain an alkali, an acid, and a surfactant. When these components are blended, the blending amounts are preferably from 0.1% by mass to 5.0% by mass of the peeling liquid. Furthermore, from the standpoint of releasability, a form in which two or more organic solvents and water, two or more kinds of bases, an acid, and a surfactant are mixed is also preferable.

Examples of the base include trisodium phosphate, tripotassium phosphate, triammonium phosphate, disodium phosphate, dipotassium phosphate, diammonium phosphate, sodium carbonate, potassium carbonate, ammonium carbonate, sodium bicarbonate, potassium bicarbonate, and ammonium bicarbonate. , Sodium borate, potassium borate, ammonium borate, sodium hydroxide, ammonium hydroxide, potassium hydroxide and lithium hydroxide and other inorganic alkaline agents, or monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, Triethylamine, monoisopropylamine, diisopropylamine, triisopropylamine, n-butylamine, monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, ethyleneimine, ethylenediamine, pyridine , Tetramethylammonium hydroxide and other organic alkaline agents. These alkali agents can be used alone or in combination of two or more.

As the acid, inorganic acids such as halogenated hydrocarbons, sulfuric acid, nitric acid, phosphoric acid, and boric acid, or alkylsulfonic acid, benzenesulfonic acid, alkylbenzenesulfonic acid, p-toluenesulfonic acid, trifluoromethanesulfonic acid, acetic acid, and citric acid can be used. , Formic acid, gluconic acid, lactic acid, oxalic acid, tartaric acid and other organic acids.

As the surfactant, an anionic, cationic, nonionic, or zwitterionic surfactant can be used. In this case, the content of the surfactant is preferably 1% to 20% by mass, and more preferably 1% to 10% by mass with respect to the total amount of the alkaline aqueous solution. When the content of the surfactant is within the above range, there is a tendency that the peelability of the temporarily adhering film 11 and the thinned element wafer 60 a can be further improved.

The anionic surfactant is not particularly limited, and examples thereof include fatty acid salts, rosinates, hydroxyalkane sulfonates, alkane sulfonates, dialkylsulfosuccinates, and linear alkylbenzenes. Sulfonates, branched alkyl benzene sulfonates, alkyl naphthalene sulfonates, alkyl diphenyl ether (di) sulfonates, alkylphenoxy polyoxyethylene alkyl sulfonates Type, polyoxyethylene alkyl sulfophenyl ether salts, N-alkyl-N-olenyl taurine sodium, N-alkyl sulfosuccinic acid monoammonium disodium salt, petroleum sulfonic acid Salts, sulfated castor oil, sulfated tallow oil, sulfate salts of fatty acid alkyl esters, alkyl sulfate salts, polyoxyethylene alkyl ether sulfate salts, fatty acid monoglyceride sulfate salts, Polyoxyethylene alkyl phenyl ether sulfates, polyoxyethylene styryl phenyl ether sulfates, alkyl phosphate salts, polyoxyethylene alkyl ether phosphate salts, polyoxyethylene alkyl Phenyl ether phosphate esters, partially saponified styrene-maleic anhydride copolymers, partially saponified olefin-maleic anhydride copolymers Naphthalene sulfonate formaldehyde condensates and the like. Among them, alkylbenzenesulfonates, alkylnaphthalenesulfonates, and alkyldiphenyl ether (di) sulfonates are particularly preferably used.

The cationic surfactant is not particularly limited, and a conventionally known one can be used. Examples include alkylamine salts, quaternary ammonium salts, alkylimidazolium salts, polyoxyethylene alkylamine salts, and polyethylene polyamine derivatives.

The nonionic surfactant is not particularly limited, and examples thereof include polyethylene glycol type higher alcohol ethylene oxide adduct, alkylphenol ethylene oxide adduct, and alkylnaphthol ethylene oxide adduct. Product, phenol ethylene oxide adduct, naphthol ethylene oxide adduct, fatty acid ethylene oxide adduct, polyol fatty acid ester ethylene oxide adduct, higher alkylamine epoxy Ethane adduct, fatty acid amine ethylene oxide adduct, ethylene oxide adduct of oil and fat, polypropylene glycol ethylene oxide adduct, dimethylsiloxane-ethylene oxide block Copolymers, dimethylsiloxane- (propylene oxide-ethylene oxide) block copolymers, fatty acid esters of glycerol of polyhydric alcohol type, fatty acid esters of pentaerythritol, sorbitol and sorbitan Fatty acid esters, fatty acid esters of sucrose, alkyl ethers of polyhydric alcohols, fatty acid amides of alkanolamines, and the like. Among them, those having an aromatic ring and an ethylene oxide chain are preferable, and an alkyl substituted or unsubstituted phenol ethylene oxide adduct or an alkyl substituted or unsubstituted naphthol epoxy is more preferable. Ethane adduct.

The zwitterionic surfactant is not particularly limited, and examples thereof include amine oxides such as alkyldimethylamine oxide, betaines such as alkylbetaine, and amino acids such as sodium alkylamino fatty acid. 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 may be preferably used. Specifically, the compound shown in the formula (2) of paragraph number 0256 of Japanese Patent Laid-Open No. 2008-203359, and the formula (I) and formula of paragraph number 0028 of Japanese Patent Laid-Open No. 2008-276166 can be used. (II), a compound represented by formula (VI), and a compound represented by paragraph numbers 0022 to 0029 of Japanese Patent Laid-Open No. 2009-47927.

Further, if necessary, additives such as a defoamer and a hard water softener may be contained.

When the carrier base material 12 is peeled from the thinned element wafer 60a, it is preferable that the end of the thinned element wafer 60a is pulled up from the end of the thinned element wafer 60a in a direction perpendicular to the element wafer without any treatment. The method of temporarily removing the film 11 from the surface of the element wafer 61 a is preferably removed in a film-like state. If the adhesion strength of the interface between the carrier substrate 12 and the temporary adhesive film 11 is set to A, and the adhesion strength of the element wafer surface 61a and the temporary adhesive film 11 is set to B, then both of the above formula (A1) and In the formula (B1), the carrier substrate 12 and the film 11 can be removed from the element wafer in the state described above. After the carrier base material 12 is peeled from the thinned element wafer 60a, various known processes are performed on the thinned element wafer 60a as necessary to manufacture a semiconductor device having the thinned element 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. Examples of the method for removing the temporarily adhered film include a physical removal method of applying a brush, ultrasonic waves, ice particles, and aerosol in a film-like state, and dissolving it in an aqueous solution or an organic solvent. Dissolution and removal methods; chemical removal methods such as decomposition and gasification by irradiation with actinic rays, radiation, and heat can be performed using previously known removal methods depending on the carrier substrate. For example, when a silicon substrate is used as a carrier substrate, a conventionally known method for cleaning a silicon wafer can be used. Examples of the aqueous solution or organic solvent that can be used for chemical removal include strong acids, strong alkalis, Specific examples of strong oxidants or mixtures thereof include acids such as sulfuric acid, hydrochloric acid, hydrofluoric acid, nitric acid, and organic acids; bases such as tetramethylammonium, ammonia, and organic bases; oxidants such as hydrogen peroxide; or A mixture of ammonia and hydrogen peroxide, a mixture of hydrochloric acid and hydrogen peroxide water, a mixture of sulfuric acid and hydrogen peroxide water, a mixture of hydrofluoric acid and hydrogen peroxide water, a mixture of hydrofluoric acid and ammonium fluoride, and the like.

In the case where a regenerated carrier substrate is used, as a method for temporarily adhering the film, a method using a carrier substrate cleaning liquid is preferred from the viewpoint of adhesiveness. The carrier substrate cleaning solution 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 can be selected from inorganic acids such as hydrogen iodide, perchloric acid, hydrogen bromide, hydrogen chloride, nitric acid, and sulfuric acid, or organic acids such as alkylsulfonic acids and arylsulfonic acids. From the viewpoint of the cleanability of the film temporarily adhered to the carrier substrate, an inorganic acid is preferred, and sulfuric acid is most preferred.

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

<Second Embodiment> A second embodiment of a semiconductor manufacturing method that has undergone the steps of manufacturing a laminated body will be described with reference to FIGS. 2 (A) to (E). The same reference numerals are given to the same parts as those of the first embodiment, and the descriptions thereof are omitted. (A)-(E) of FIG. 2 are schematic cross-sectional views explaining the temporary continuation of a carrier substrate and an element wafer, respectively ((A) and (B) of FIG. 2), showing The state where the element wafer is thinned (FIG. 2 (C)), the carrier substrate and the element wafer are peeled off (FIG. 2 (D)), and the state where the film is temporarily removed from the element wafer is removed ( FIG. 2 (E)) is a schematic cross-sectional view. In this embodiment, as shown in FIG. 2 (A), a temporary adhesive film is formed on the surface 61a of the element wafer, which is different from the first embodiment. In the case where the temporary bonding film 11a is provided on the surface 61a of the element wafer 60, the temporary bonding composition can be applied (preferably coated) on the surface of the surface 61a of the element wafer 60 and then applied. Formed by drying (baking). The drying can be performed at, for example, 60 ° C to 150 ° C for 10 seconds to 2 minutes. Then, as shown in FIG. 2 (B), the carrier base material 12 and the element wafer 60 are pressure-bonded, so that the carrier base material 12 and the element wafer 60 are temporarily adhered. Then, as shown in FIG. 2 (C), a mechanical or chemical treatment is performed on the back surface 61b of the silicon substrate 61. As shown in FIG. 2 (C), the thickness of the silicon substrate 61 is reduced to obtain a thin type.化 Element wafer 60a. Then, as shown in FIG. 2 (D), the carrier substrate 12 is peeled from the thinned element wafer 60 a. Then, as shown in FIG. 2 (E), the temporary bonding film 11 a is removed from the thinned element wafer 60 a.

<Previous embodiment> Next, the previous embodiment will be described. FIG. 3 is a schematic cross-sectional view illustrating the release of a temporary bonding state between a conventional adhesive carrier substrate and a component wafer. In the previous embodiment, as shown in FIG. 3, as the adhesive carrier substrate, an adhesive carrier substrate formed by using the temporary adhesive film 11b formed of the previous temporary adhesive composition on the carrier substrate 12 was used. Except for the material 100a, the adhesive carrier base material 100a and the element wafer are temporarily bonded in the same manner as described with reference to FIGS. 1 (A) to (E), and the silicon in the element wafer is processed. The thin film processing of the substrate 61 is followed by peeling the thinned element wafer 60 a from the adhesive carrier substrate 100 a in the same manner as described above.

However, according to the previous temporary bonding composition, the element wafer is temporarily supported by a high bonding force, and it is difficult to easily release the temporary support for the element wafer without causing damage to the element wafer. For example, in order to make the temporary bonding of the element wafer and the carrier substrate sufficient, if the temporary bonding composition with high adhesion among the previous temporary bonding compositions is used, the temporary bonding of the element wafer and the carrier substrate will be achieved. Excessive tendency. Therefore, in order to release the excessively strong temporary bonding, for example, as shown in FIG. 3, a tape (for example, a dicing tape) 70 is attached to the back surface of the thin element wafer 60 a, and the thinness is peeled from the adhesive carrier substrate 100 a In the case of the element wafer 60 a, the structure body 63 is peeled from the element wafer 62 on which the structure body 63 is provided, and the defect such as damage to the element wafer 62 easily occurs. On the other hand, if the temporary bonding composition with low adhesiveness in the previous temporary bonding composition is used, the temporary support for the element wafer can be easily released, and the temporary bonding of the element wafer and the carrier substrate can be easily passed. Weak, it is easy to cause a failure that the element wafer cannot be reliably supported by the carrier substrate.

In contrast, the laminated body of the present invention exhibits sufficient adhesiveness, and the temporary bonding of the element wafer 60 and the carrier substrate 12 can be easily released. That is, according to the laminated body of the present invention, the element wafer 60 can be temporarily adhered by a high adhesive force, and the temporary reduction of the thin element wafer 60a can be easily released without causing damage to the thin element wafer 60a. then.

The method for manufacturing a semiconductor device of the present invention is not limited to the above-mentioned embodiment, and can be appropriately modified, improved, and the like. In addition, in the above-mentioned embodiment, a silicon substrate is cited as the element wafer, but the invention is not limited to this. In the method for manufacturing a semiconductor device, it may be any one that can be mechanically or chemically processed. Processing component. Moreover, in the said embodiment, as a mechanical or chemical process with respect to an element wafer (silicon substrate), the thin film process of an element wafer, and the formation process of a silicon through-electrode are mentioned, It is not limited to these In the method of manufacturing a semiconductor device, any required processing may be enumerated. In addition, the shape, size, number, arrangement position, and the like of the element wafer among the element wafers exemplified in the embodiment are not limited. In addition, as another embodiment, the following configuration may be adopted. The composition for temporary bonding is applied to a carrier made of glass, silicon, or metal to form a temporary bonding film, and the diced wafer is then continued thereon. The bonding temperature at this time is preferably in the range of 10 ° C to 250 ° C. Furthermore, the bonded wafer is sealed with a molding resin, and the molding resin in which the wafer is embedded is peeled from the adhesive carrier substrate in the same manner as described above, thereby removing the temporary bonding film. [Example]

Hereinafter, the present invention will be further described in detail through examples. As long as the gist of the present invention is not exceeded, the present invention is not limited to the following examples. In addition, unless otherwise specified, "part" and "%" are quality standards.

<Preparation of Composition for Temporary Adhesion> As shown below, after mixing the components of the tentative admixture to make a homogeneous solution, it was filtered using a polytetrafluoroethylene filter having a pore size of 5 μm to thereby Preparation is followed by a composition.

<<< Composition of composition for temporary bonding >> Resin shown in Table 1: Amount described in Table 1 Additive described in Table 1: Amount described in Table 1 Solvent described in Table 1: Table 1 Recorded amount <<< All the ingredients blended in the composition for temporary adhering use >>> ・ Irganox 1010 (manufactured by BASF Japan): 1 part by mass (Sumilizer) TP-D (manufactured by Sumitomo Chemical Co., Ltd.): 1 part by mass

[Table 1]

In Table 1, E represents the tensile elastic modulus of the resin at 25 ° C in accordance with JIS K7161: 1994.

The styrene ratio (proportion of repeating units derived from styrene, mass%) is calculated by dissolving in a trichlorobenzene / deuterated benzene after forming a film with a composition on the wafer and peeling it off. At 80/20 (vol.%), H-NMR (JEOL-JSX400, manufactured by Nippon Electronics Co., Ltd.) was used to measure the integrated intensity of the signals of the styrene and other copolymerized components subordinate to the resin, and the Multiply the specific gravity.

於所述表中，所謂COP是指環烯烴系聚合物，所謂TPI是指熱塑性聚醯亞胺樹脂。The compounds described in Table 1 are as follows. [Table 2]

In the table, COP refers to a cycloolefin-based polymer, and TPI refers to a thermoplastic polyimide resin.

[table 3]

<<< Measurement method of mass reduction rate of polyether-modified silicone after heating at 280 ° C for 30 minutes >> The "280 ° C, 30-minute mass reduction rate" described in the table is using a thermogravimetry device (TGA -50, manufactured by Shimadzu Corporation), heated from 20 ° C to 280 ° C at a heating rate of 20 ° C / min under a nitrogen flow of 60 mL / min, and maintained at 280 ° C for 30 minutes, based on the following To calculate. Mass reduction rate (% by mass) = {(mass at 20 ° C-mass after holding at 280 ° C for 30 minutes) / mass at 20 ° C} × 100

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

<<< Measurement method of ratio represented by formula (A) >> The ratio represented by formula (A) is a measurement of hydrogen inherent in methylene oxide, ethylene oxide, and propylene oxide using nuclear magnetic resonance (NMR). The atomic peaks are calculated from the respective area ratios.

[Table 4]

<Formation of laminated body> <<< Formation of laminated body (Example 1 to Example 16, Example 18 to Example 19, Comparative Example 1 to Comparative Example 8)> As a first substrate, a 12-inch diameter was used. A silicon wafer (2.54 cm in 1 inch) was manufactured using a wafer bonding device (manufactured by Tokyo Electron Co., Ltd., Synapse V). A film is formed on the surface. Using a hot plate, heating was performed at 130 ° C. for 3 minutes and further at 190 ° C. for 3 minutes, thereby forming a temporary adhesive film on the surface of the first substrate. The thickness of the temporary adhesive film at this time was 60 μm.

<<< Formation of Laminate (Example 17) >> A 12-inch diameter silicon wafer was used as the first substrate, and a wafer bonding apparatus (manufactured by Tokyo Electron Co., Ltd.) was used. Synapse) V) The temporary bonding composition is applied to the surface and formed into a film. Using a hot plate, heating was performed at 130 ° C for 3 minutes, and further at 190 ° C for 3 minutes, thereby forming a temporary adhesive film on the surface of the first substrate. The thickness of the temporary bonding film at this time was 30 μm. A 12-inch diameter silicon wafer was used as the second substrate, and the temporary bonding composition was applied using a wafer bonding apparatus (manufactured by Tokyo Electron Co., Ltd., Synapse V). A film is formed on the surface. By using a hot plate, heating was performed at 130 ° C for 3 minutes and further at 190 ° C for 3 minutes, thereby forming a temporary adhesive film on the surface of the second substrate. The thickness of the temporary bonding film at this time was 30 μm.

<< Joining Process (Examples 1 to 18, Comparative Examples 1 to 8)> Using a wafer bonding apparatus (manufactured by Tokyo Electron Co., Ltd., Synapse V), The first substrate and the second substrate forming the temporary adhesive film, or the first substrate and the second substrate forming the temporary adhesive film were formed at a pressure of 10 Pa and a temperature of 200 ° C and 0.5 MPa. The substrate was subjected to thermal compression bonding for 5 minutes to obtain a laminated body.

＜< Joining process (Example 19) ＞ Using a wafer bonding apparatus (manufactured by EV Group Japan, Ltd., 520IS), the pressure was adjusted at a pressure of 10 Pa and a temperature of 300 ° C and a pressure of 0.5 MPa. The first base material and the second base material forming the temporary adhesive film were subjected to thermal compression bonding for 3 minutes to obtain a laminated body.

<< Back grind processing >> The back surface of the substrate 2 side of the laminated body (without provision of a temporary adhesive film is not provided) using a back grinder (manufactured by DISCO (DFG8540)) On one side) to a thickness of 40 μm to obtain a thin laminate.

<< CVD (chemical vapor deposition) processing >> At 200 ° C for 20 minutes, using tetraethyl orthosilicate (TEOS) and O ₂ gas, The back surface of the thinned substrate 2 (the side where the film is not temporarily attached) is formed with a SiO ₂ film by a CVD process. The thickness of the obtained SiO ₂ film was 2 μm.

<<< Planarity evaluation >> The laminated body which performed the said CVD process was observed with the naked eye, and the number of swellings was evaluated based on the following criteria. A: No swelling was observed on the substrate 2. B: Swelling was observed on the substrate 2. The length of the longest part of the swelling was less than 5 mm and swelling was less than five. C: Swelling was observed in the base material 2 and the swelling of the longest part was 5 mm or more in length, or the swelling longest part was less than 5 mm in swelling number of 5 or more.

<<< Warpage> The warpage (radius of curvature) was measured on the laminated body subjected to the CVD process using a thin film stress measuring device (FLX-2320-S, manufactured by Toho Technology (Stock)). And evaluated by the following criteria. In addition, regardless of the direction of warpage, evaluation was performed in absolute values. A: The value of warpage is 50 μm or less B: The value of warpage is more than 50 μm and 100 μm or less C: The value of warpage is more than 100 μm and 200 μm or less D: The value of warpage is more than 200 μm

<< Measurement of Peeling Force> A silicon wafer having a diameter of 4 inches (1 inch is 2.54 cm) was used as a base material, and a spin coater (Mikasa (Mikasa), MS-B200) was used. The composition for temporary adhesion described in Table 1 was applied to the surface and formed into a film. Using a hot plate, heating was performed at 130 ° C. for 3 minutes and further at 190 ° C. for 3 minutes, thereby forming a temporary adhesive film on the surface of the first substrate. The thickness of the temporary bonding film at this time was 15 μm. A 90 mm width of the temporary adhesive film was cut into the slit in the laminated body, and the end of the temporary adhesive film was directed at a speed of 300 mm / min at 25 ° C toward the surface of the silicon wafer where the temporary adhesive film was formed. It was pulled up in a vertical direction, thereby confirming whether or not it was peeled off, and the force applied at the time of pulling up was measured using a dynamometer (Imada (stock), DS2-20N). The unit is expressed in N / cm.

<< Peel Evaluation >> The CVD-processed surface of the CVD-processed laminate is set to the lower side, and the lower silicon wafer and the dicing frame are fixed to the center of the dicing tape using a dicing tape holder. Then, using a wafer de-bonder device (manufactured by Tokyo Electron Co., Ltd., Synapse Z), the substrate on the upper side was directed to the lower side at 25 ° C. The substrate was pulled up at a speed of 3 mm / min in a vertical direction, and it was confirmed whether or not the substrate could be peeled off without breaking the substrate on the upper side or the lower side, and evaluated based on the following criteria. A: Peelable. B: The adhesive force is weak and the wafer periphery partly floats but can be peeled off, or the wafer breaks at a pulling speed of 3 mm / min but peels off at a pulling speed of 2 mm / min. C: Even if the pull-up speed is set to 2 mm / min, peeling cannot be performed.

[table 5]

From the above results, it is clear that when the composition for temporary bonding of the present invention is used, the substrate can be appropriately peeled from the laminated body obtained by temporarily fixing the substrates to each other, and the surface of the processed substrate can be provided A laminated body having excellent planarity (Examples 1 to 19). Furthermore, when the tensile modulus of elasticity is 1 MPa or more and 100 MPa or less, and particularly when 1 MPa or more and 60 MPa or less, a laminated body having significantly small warpage can be obtained (Examples 1 to 17). In particular, Examples 1 to 13 and 15 to 17).

<Cleaning After Peeling (Examples 1 to 18, Comparative Example 2, Comparative Example 4, Comparative Example 6 to Comparative Example 8)> After the peeling evaluation, there was a substrate that temporarily adhered to the film (temporary adhesive). Materials, using a wafer release adapter device (manufactured by Tokyo Electron, Synapse Z) while spraying mesitylene for 180 seconds while rotating at 200 rpm, thereby removing the temporary adhesive film (Temporary adhesive). Moreover, regarding the said peeling evaluation to "C", since it was originally not the state which can wash | clean after peeling, cleaning was not performed.

<Cleaning after Peeling (Example 19)> For the substrate remaining with a temporary film after the peeling evaluation, a wafer release adapter device (manufactured by Tokyo Electron), Synapse ) Z) Cyclopentan was sprayed for 180 seconds while rotating at 200 rpm, thereby removing the temporary adhesive film.

Example 20 A solvent was mixed in the same manner as in Example 1 except that the solvent was a mixed solvent of 80 parts by mass of mesitylene and 20 parts by mass of third butylbenzene (manufactured by Toyo Synthetic Industry Co., Ltd.). The results were the same as those of Example 1.

(Example 21) A mixed solvent of 80 parts by mass of mesitylene and 20 parts by mass of pseudocumene (manufactured by Toyo Kogyo Kogyo Co., Ltd.) was used. The same procedure as in Example 1 was performed except that the solvent was a mixed solvent. The evaluation was the same as in Example 1.

Example 22 The solvent was a mixed solvent of 80 parts by mass of mesitylene and 20 parts by mass of cyclohexanone (manufactured by Sankyo Chemical Co., Ltd.), and the solid content concentration was changed to 20%. It implemented similarly to Example 1, and the result evaluation was the same as Example 1.

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

(Example 24) Except that the CVD process was changed to the conditions of 350 ° C and 20 minutes, it was performed in the same manner as in Example 1, and the evaluation results were the same as in Example 1.

11, 11a ‧ ‧ ‧ film temporarily
12‧‧‧ carrier substrate
60‧‧‧component wafer
60a‧‧‧ Thin wafer
61‧‧‧ silicon substrate
61a‧‧‧ surface
61b, 61b1‧‧‧ back
62‧‧‧component chip
63‧‧‧ Structure
70‧‧‧Tape
100, 100a‧‧‧ Adhesive carrier substrate

FIGS. 1A to 1E are schematic diagrams showing a first embodiment of a method of manufacturing a semiconductor device. FIGS. 2A to 2E are schematic diagrams showing a second embodiment of a method of manufacturing a semiconductor device. FIG. 3 is a schematic cross-sectional view illustrating the release of a temporary bonding state between a conventional adhesive carrier substrate and a component wafer.

11‧‧‧ temporarily adhere to the film

12‧‧‧ carrier substrate

60‧‧‧component wafer

60a‧‧‧ Thin wafer

61‧‧‧ silicon substrate

61a‧‧‧ surface

61b, 61b1‧‧‧ back

62‧‧‧component chip

100‧‧‧ Adhesive carrier substrate

Claims (11)

A composition for temporary adhesion, comprising: a resin; and a polyether-modified silicone A having a ratio represented by the following formula (A) of 80% or more; and a content of the polyether-modified silicone A is as follows: 0.001% by mass to 1.0% by mass of the solid content of the composition is temporarily used; Formula (A) {(MO + EO) / AO} × 100 In Formula (A), MO is a polyether modified silicone Mole% of methylene oxide contained in the polyether structure, EO is Mole% of ethylene oxide contained in the polyether structure in polyether modified silicone, AO means polyether modified Molar% of alkylene oxide contained in the polyether structure of the high-quality silicone. The composition for temporary bonding according to item 1 of the scope of patent application, wherein the resin is a polystyrene-based elastomer. The composition for temporary bonding according to item 1 of the scope of patent application, wherein the resin is selected from the group consisting of polystyrene-poly (ethylene-propylene) diblock copolymer, polystyrene-poly (ethylene-propylene) -Polystyrene triblock copolymer, polystyrene-poly (ethylene-butene) -polystyrene triblock copolymer, and polystyrene-poly (ethylene / ethylene-propylene) -polystyrene triblock A polystyrene-based elastomer in at least one of the segment copolymers. The composition for temporary bonding according to item 2 or item 3 of the scope of patent application, wherein the proportion of repeating units derived from styrene in the polystyrene elastomer is 55% by mass or less. The composition for temporary bonding according to item 1 or item 2 of the scope of patent application, wherein the resin has a tensile elasticity coefficient E at 25 ° C according to Japanese Industrial Standard K7161: 1994 of 1 MPa to 60 MPa. . The composition for temporary bonding according to item 1 or item 2 of the scope of patent application, wherein the ratio represented by formula (A) of the polyether modified silicone A is 90% or more. The composition for temporary bonding according to item 1 or item 2 of the scope of patent application, wherein the polyether-modified silicone A is heated at a temperature of 20 ° C / min under a nitrogen flow of 60 mL / min. The mass reduction rate when the temperature was raised from 20 ° C to 280 ° C and held at a temperature of 280 ° C for 30 minutes was 50% by mass or less. The composition for temporary continuation according to item 1 or item 2 of the patent application scope, wherein the polyether modified silicone A is represented by any one of the following formulae (101) to (104); Formula (101)

In the formula (101), R ¹¹ and R ¹⁶ are each independently a substituent, R ¹² and R ¹⁴ are each independently a divalent linking group, R ¹³ and R ¹⁵ are a hydrogen atom or an alkane having 1 to 5 carbon atoms. Base, m11, m12, n1, and p1 are each independently a number from 0 to 20, and x1 and y1 are each independently a number from 2 to 100; Formula (102)

In the formula (102), R ²¹ , R ²⁵ and R ²⁶ are each independently a substituent, R ²² is a divalent linking group, R ²³ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and m 2 and n 2 are respectively Independently is a number from 0 to 20, and x2 is a number from 2 to 100; Formula (103)

In the formula (103), R ³¹ and R ³⁶ are each independently a substituent, R ³² and R ³⁴ are each independently a divalent linking group, R ³³ and R ³⁵ are a hydrogen atom or an alkane having 1 to 5 carbon atoms. Base, m31, m32, n3, and p3 are each independently a number from 0 to 20, and x3 is a number from 2 to 100; Formula (104)

In the 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 a carbon number of 1 to 5 alkyl groups, 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 composition for temporary bonding according to item 1 or item 2 of the scope of patent application, wherein the refractive index of the polyether-modified silicone A is 1.440 or less. The composition for temporary bonding according to item 1 or 2 of the scope of patent application, wherein the peeling force of the temporary bonding composition is 1 N / m to 20 N / m; wherein the so-called peeling force means: use A composition was used to form a temporary adhesive film with a thickness of 15 μm on the surface of the silicon wafer. The end of the temporary adhesive film was temporarily formed at a speed of 300 mm / min at 25 ° C. relative to the formation of the silicon wafer. Then, the surface of the film was pulled up in a vertical direction, thereby being peelable, and the force at the time of pulling up was measured using a dynamometer. A laminated body having a first substrate, a temporary adhesive film, and a second substrate sequentially adjacent to each other, and the temporary adhesive film is prepared by any one of items 1 to 10 of the scope of patent application. The aforementioned temporary formation is followed by a composition.