TW201724294A - Method for producing semiconductor element and method for producing laminate - Google Patents

Abstract

Provided are: a method for producing a semiconductor element, which effectively suppresses die shift and exhibits excellent separation properties between a temporary adhesive layer and a molding layer; and a method for producing a laminate. A method for producing a semiconductor element, wherein a member that has a temporary adhesive layer on a carrier substrate and a die that has a circuit on at least one surface thereof are pressure-bonded with each other at a temperature T1 in such a manner that the temporary adhesive layer is in contact with the die, and after forming a molding layer at a temperature T2 on a surface of the die, said surface being on the reverse side of the surface in contact with the temporary adhesive layer, the carrier substrate is separated at a temperature of 40 DEG C or less. In this connection, the temperature T1 is a temperature at which the melt viscosity of the temporary adhesive layer as measured at a measurement frequency of 10 Hz is from 4,000 Pa.s to 10,000 Pa.s (inclusive); and the temperature T2 is a temperature at which the melt viscosity of the temporary adhesive layer as measured at a measurement frequency of 10 Hz is 4,000 Pa.s or more.

Description

Method for manufacturing semiconductor device and method for manufacturing laminated body

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

The semiconductor element may be formed by forming a molding layer on a crystal grain having a circuit on the surface and encapsulating it. As one of the methods for producing such an encapsulated semiconductor device, there is known a method of forming a temporary adhesive layer on a carrier substrate and arranging crystal grains on the formed temporary adhesive layer, and further A molding layer is formed on the subsequent layer, and the carrier substrate is peeled off (for example, Patent Documents 1 to 4). [Prior Art Document] [Patent Literature]

[Patent Document 1] US Pat. No. 7,202,107 [Patent Document 2] US Patent No. 9082806 [Patent Document 3] Japanese Patent Laid-Open Publication No. Hei.

[Problems to be Solved by the Invention] However, it has been found that, as described in the above-mentioned patent documents, crystal grains are arranged on the surface of the temporary adhesive layer and a molding layer is formed on the surface of the temporary adhesive layer. The grain displacement when the particles are pressure-bonded to the temporary adhesive layer becomes a problem, or there is a problem in the peelability of the temporary adhesive layer and the formed layer. The present invention has been made to solve the above problems, and an object of the invention is to provide a method for producing a semiconductor device and a method for producing a laminate, which are excellent in suppressing grain displacement and having excellent release property between a temporary adhesive layer and a molding layer. [Means for solving the problem]

Based on the above, the inventors of the present invention conducted research, and as a result, it was found that the cause of the grain displacement or the peeling property is that the temporary adhesive layer is caused by the pressure bonding of the crystal grains or the heating at the time of forming the molding layer. Melt. Further, it has been found that the problem can be solved by increasing the melt viscosity of the temporary adhesive layer during the pressure bonding of the crystal grains or during the molding of the molding layer. Specifically, the above problem is solved by <2> to <7> by the following paragraph <1>. <1> A method of manufacturing a semiconductor device, wherein a member having a temporary adhesive layer on a carrier substrate and a die having a circuit on at least one surface are connected to the die by the temporary adhesive layer at a temperature T1 Pressing down, and forming a molding layer at a temperature T2 on the surface on the opposite side of the side of the crystal grain that is in contact with the temporary adhesive layer, and then peeling the carrier substrate at a temperature below 40 ° C; The temperature T1 is a temperature at which the melt viscosity of the temporary adhesive layer measured at a measurement frequency of 10 Hz is 4000 Pa·s or more and 10000 Pa·s or less, and the temperature T2 is the temporary measured at a measurement frequency of 10 Hz. The melt viscosity of the subsequent layer becomes a temperature of 4,000 Pa·s or more. <2> The method for producing a semiconductor device according to <1>, wherein the heat treatment at 100 ° C or higher is performed after the formation of the formed layer. The method for producing a semiconductor device according to the above aspect, wherein after the carrier substrate is peeled off at a temperature of 40 ° C or lower, the temporary adhesive layer is further removed at 40 ° C or lower. . The method for producing a semiconductor device according to any one of the above aspects, wherein the temporary adhesive layer comprises a thermoplastic elastomer having a styrene structure, a cycloolefin polymer, and acrylic acid. At least one of the resins. The method for producing a semiconductor device according to any one of the above aspects, wherein the molding layer comprises an epoxy resin. The method of manufacturing a semiconductor device according to any one of <1> to <5> wherein the position before the pressure bonding at the temperature T1 of the crystal grain and the pressure at the temperature T1 of the crystal grain The moving distance of the connected position is less than 100 μm. The method for producing a semiconductor device according to any one of the above aspects, wherein the temporary adhesive layer contains at least one of a fluorine atom and a germanium atom. [Effects of the Invention]

According to the present invention, it is possible to provide a method for producing a semiconductor device, a method for producing a laminate, and a method for producing a laminate, which are excellent in suppressing grain displacement and having excellent release property between a temporary adhesive layer and a molding layer.

Hereinafter, the contents of the present invention will be described in detail. In the present specification, the term "~" is used in the sense that the numerical values described before and after are included as the lower limit and the upper limit. In the expression of the group (atomic group) in the present specification, the substituted and unsubstituted expressions are not described as including a group having no substituent (atomic group), and also a group having a substituent (atomic group). For example, the "alkyl group" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group). In the present specification, "(meth)acrylate" means acrylate and methacrylate, "(meth)acrylic" means acrylic acid and methacrylic acid, and "(meth)acryloyl group" means "acryloyl fluorenyl group". And "methacryl oxime". In the present specification, the weight average molecular weight and the number average molecular weight are defined as polystyrene-converted values measured by Gel Permeation Chromatography (GPC). In the present specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) can be, for example, by using HLC-8220 (manufactured by Tosoh), using TSKgel Super AWM-H (Tosoh) (manufactured by Ltd.), 6.0 mm (inner diameter) × 15.0 cm) was used as a column, and a solution of N-methyl pyrrolidinone (NMP) of 10 mmol/L of lithium bromide was used as a washing liquid. The thickness or the like in the present invention is assumed to mean the average thickness unless otherwise specified.

A method of manufacturing a semiconductor device according to the present invention is characterized in that a member having a temporary adhesive layer on a carrier substrate and a die having a circuit on at least one surface are in contact with the die by the temporary adhesive layer The metal layer is crimped under T1, and a molding layer is formed on the surface on the opposite side to the side where the temporary adhesive layer is in contact with the temporary adhesive layer, and then the carrier substrate is peeled off at a temperature of 40 ° C or lower. Here, the temperature T1 is a temperature at which the melt viscosity of the temporary adhesive layer measured at a measurement frequency of 10 Hz is 4000 Pa·s or more and 10000 Pa·s or less, and the temperature T2 is measured at a measurement frequency of 10 Hz. The melt viscosity of the temporary adhesive layer is 4,000 kPa or more. Such a laminate can be provided with a rewiring (redistribution layer) region having a larger wafer size, and thus can be preferably used for a fan-out wafer level characterized by no substrate formation and low profile. In the package (Fan-out Wafer Level Package, FOWLP). With such a configuration, it is possible to provide a semiconductor element or a method for producing a laminate which is excellent in releasability. In other words, a laminate in which a semiconductor element or the like is formed on the surface of the temporary adhesive layer has been used. However, it has been known that the peelability of the temporary adhesive layer and the molded layer is deteriorated in the conventional production method. The inventors of the present invention have studied the reason why the molding layer is formed after the provision of the temporary adhesive layer, but the temporary adhesive layer is melted by the heating at the time of formation of the molding layer, and the molding layer is formed. The resin is mixed with the resin constituting the temporary adhesive layer on the surface layer. Therefore, in the present invention, this point is avoided by setting the melt viscosity of the temporary adhesive layer when the molded layer is formed to 4000 Pa·s or more. Further, it has been found that a crystal grain having a circuit is provided between the temporary adhesive layer and the molding layer, but in the case where the crystal grain array is pressure-bonded to the surface of the temporary adhesive layer, there is a case where the crystal grain is crimped to the temporary surface. The subsequent heating of the agent layer causes a situation in which the temporary adhesive layer is melted and the crystal grains are displaced. In the present invention, the member having the temporary adhesive layer on the carrier substrate and the die having the circuit on at least one surface are bonded to the die at a temperature T1 in such a manner that the temporary adhesive layer is in contact with the die. Suppress grain shift. By suppressing the grain displacement, the pitch of the crystal grains is less likely to vary, and the semiconductor element can be manufactured with high precision. Further, when a molding layer is formed, a large pressure is applied, but pressure is uniformly applied to the crystal grains and the temporary adhesive layer of the portion having no crystal grains, so that it is presumed that there is almost no grain shift at the time of formation of the molding layer. The impact. Hereinafter, the method for producing a semiconductor device of the present invention will be described as an example, but the same applies to the method for producing a layered body of the present invention.

The method of manufacturing the semiconductor device of the present invention will be described using (A1) to (A5) of FIG. 1 . First, as shown in (A1) of FIG. 1, a temporary adhesive layer 20 is provided on the carrier substrate 10.

The carrier substrate 10 is not particularly limited, and examples thereof include a ruthenium substrate, a glass substrate, a metal substrate, and a compound semiconductor substrate. Among them, a tantalum substrate is preferred. The thickness of the carrier substrate is not particularly limited, and is, for example, preferably 300 μm to 100 mm, and more preferably 300 μm to 10 mm.

The temporary adhesive layer 20 can be formed using a temporary adhesive composition which will be described later. Examples of the application method of the temporary adhesive composition include a spin coating method, a spray method, a roll coating method, a flow coating method, a knife coating method, a screen printing method, and a dip coating method. Further, a method in which the temporary adhesive composition is applied from the slit-shaped opening by pressure to apply the temporary adhesive composition onto the carrier substrate 10 may be employed. In the case of (A1) to (A5) of FIG. 1, the temporary adhesive layer 20 is formed on the entire surface of one surface of the carrier substrate 10, but the temporary adhesive layer 20 may not be formed on the entire surface of the carrier substrate 10. . Alternatively, the temporary adhesive composition may be film-formed in advance, and the film may be formed on the carrier substrate 10 by lamination. Further, the temporary adhesive layer may be only one layer or two or more layers. For example, the laminate in the present invention may have a structure including a carrier substrate/first temporary adhesive layer/second temporary adhesive layer/die formation layer.

The application amount of the temporary adhesive composition is preferably, for example, an application amount of the average thickness of the temporary adhesive layer after drying of from 0.1 μm to 1000 μm. The lower limit is preferably 1.0 μm or more, and more preferably 10.0 μm or more. The upper limit is preferably 300 μm or less, more preferably 200 μm or less.

It is preferred to dry after applying the temporary adhesive composition. The drying conditions are, for example, preferably carried out at 50 ° C to 250 ° C for 10 seconds to 1000 seconds. The drying temperature is more preferably from 90 ° C to 220 ° C, and still more preferably from 100 ° C to 200 ° C. The drying time is more preferably from 20 seconds to 600 seconds, and still more preferably from 30 seconds to 300 seconds. Drying can be carried out in two stages and the temperature is increased stepwise.

In the above-described embodiment, the member having the temporary adhesive layer on the carrier substrate may have other layers within the range not departing from the gist of the invention. As another layer, a layer called a release layer, a peeling layer, and a separation layer can be illustrated. As the peeling layer, for example, the description of paragraph 0025 to paragraph 0055 of Japanese Patent Laid-Open No. 2014-212292 is incorporated herein by reference. Further, as the separation layer, reference is made to the description of paragraph 0069 to paragraph 0124 of the manual of WO2013-065417, which is incorporated in the specification. However, in the present invention, it is preferred to have a temporary adhesive layer on the surface of the carrier substrate.

Next, as shown in (A2) of FIG. 1, the die 30 is pressure-bonded to the temporary adhesive layer 20. The die 30 is a circuit having at least one surface, preferably a circuit having only one surface. Examples of the crystal grains include wafer wafers containing ruthenium, sapphire, tantalum carbide (SiC), gallium arsenide (GaAs), gallium phosphide (GaP), gallium nitride (GaN), and the like.

In the present invention, it is preferable that the pressure bonding of the crystal grains 30 is performed at a temperature T1 at a temperature T1 of 4,000 Pa·s or less and a melt viscosity of the temporary adhesive layer measured at a measurement frequency of 10 Hz. . The temperature T1 is preferably such that the melt viscosity of the temporary adhesive layer is 4300 Pa·s to 9800 Pa·s, and more preferably the melt viscosity of the temporary adhesive layer is 4500 Pa·s to 9700 Pa·s. The temperature of the temperature T1 is not particularly limited, and may be 100 to 300 ° C (the lower limit is preferably 130 ° C or higher, more preferably 160 ° C or higher, and the upper limit is preferably 260 ° C or lower, more preferably 240 ° C or lower, and further Good range of 180 ° C or less).

The pressure bonding is preferably carried out under the conditions that the pressure applied to the crystal grains 30 is from 0.001 MPa to 10 MPa, more preferably from 0.01 MPa to 5 MPa. The crimping time is preferably from 0.1 second to 15 seconds, more preferably from 0.5 second to 10 seconds.

Next, as shown in (A3) of FIG. 1, a molding layer is formed at a temperature T2 on the surface on the side opposite to the side where the temporary adhesive 20 is in contact with the temporary bonding agent 20. As shown in Figure 1, the shaped layer is disposed on the die and on the surface of the temporary adhesive layer. The shaped layer is preferably covered in such a manner as to seal the crystal grains, but it is of course also included in the scope of the present invention. Further, the molded layer does not have to be a complete layer, and for example, a surface which is provided on the surface of the temporary adhesive layer so as to cover the crystal grains is also included in the scope of the present invention. The temperature T2 at the time of forming the molded layer is performed at a temperature at which the melt viscosity of the temporary adhesive layer measured at a measurement frequency of 10 Hz is 4,000 Pa·s or more. When the temperature T2 is a temperature at which the melt viscosity of the temporary adhesive layer is 4,000 Pa·s or more, the upper limit of the melt viscosity is not particularly limited, and it is preferable that the melt viscosity of the temporary adhesive layer is 4300 Pa·s to 15000 Pa·s. The temperature is more preferably such that the melt viscosity of the temporary adhesive layer is from 4,500 Pa·s to 12,000 Pa·s. The temperature T2 is not particularly limited, and is preferably 20 ° C to 300 ° C (preferably 100 ° C to 260 ° C, more preferably 130 ° C to 260 ° C, still more preferably 160 ° C to 240 ° C). Further, in the present invention, it is preferable that the melt adhesiveness of the temporary adhesive layer at the temperature T1 is higher than the melt viscosity of the temporary adhesive layer at the temperature T2, and preferably the melt viscosity of the temporary adhesive layer at the temperature T1 is higher than the temperature. The temporary adhesive layer under T2 has a high melt viscosity of 30 Pa·s or more. By setting it as such a range, it is more difficult to cause a grain shift, and it is preferable. Further preferably, the melt viscosity of the temporary adhesive layer at the temperature T1 is preferably 30 Pa·s to 600 Pa·s higher than the melt viscosity of the temporary adhesive layer at the temperature T2.

The die, also referred to as a wafer, has circuitry on at least one side. The crystal grains are usually provided with circuits on the surface of the substrate. The substrate can be exemplified by a tantalum substrate or the like. The crystal grain is, for example, a square having a surface area of a crystal having a square shape of about 1 mm ² to 500 mm ² . The quadrilateral here is intended to include a substantially quadrangular shape in addition to the square in the mathematical sense. In addition, the quadrilateral is usually rectangular. It is usually obtained by cutting and separating a substrate formed on a semiconductor wafer such as a germanium wafer.

The molding layer 40 is not particularly limited. For example, it is preferable to contain a resin, and it is more preferable to contain a curable resin. Further, the molded layer preferably contains at least one of an inorganic filler and a curing agent, and may further contain other components.

Examples of the curable resin include a phenol novolak resin, a cresol novolak resin, a novolac type phenol resin such as a bisphenol A novolak resin, a phenol resin such as a resole type phenol resin, and a phenol novolac resin. Type epoxy resin, phenol novolak type epoxy resin and other novolac type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin and other bisphenol type epoxy resin, hydroquinone type ring Oxygen resin, biphenyl type epoxy resin, stilbene type epoxy resin, trisphenol methane type epoxy resin, alkyl modified trisphenol methane type epoxy resin, triazine core containing epoxy resin, dicyclopentylene Diene modified phenol type epoxy resin, naphthol type epoxy resin, naphthalene type epoxy resin, phenol aralkyl type epoxy resin having a stretching phenyl group and/or a biphenyl group extending, having a phenyl group and / Epoxy resin such as an aralkyl type epoxy resin such as a naphthol aralkyl type epoxy resin having a biphenyl skeleton, a resin having a triazine ring such as urea (urea) resin or melamine resin, or an unsaturated polyester Resin, bis-xenylenediamine resin, polyamine Ester resin, diallyl phthalate resin, a silicone resin, a ketone, a resin having a benzoxazine ring, cyanate ester resins, those which may be used alone or in admixture. Here, the term "epoxy resin" as used herein means a monomer, an oligomer, and a polymer having two or more epoxy groups in one molecule. Among these, epoxy resins are preferred. This can improve electrical characteristics. Further, even if a large amount of inorganic filler is added, the fluidity which can be formed can be maintained. In particular, as a preferred embodiment, an epoxy resin is used as the resin which is the main component of the molding layer 40, and a styrene-based elastomer is used as the main component of the temporary adhesive layer 20. By using such a combination, it is possible to achieve high peelability of the laminate. In addition, the resin of the main component herein refers to a component having the largest content of the resin component contained in the molding layer 40 or the temporary adhesive layer 20, and is usually 80% by mass or more of the resin component.

The content of the resin is not particularly limited, but is preferably from 3% by mass to 30% by mass based on the entire molded layer, and particularly preferably from 5% by mass to 20% by mass. When the content is at least the lower limit value, the decrease in fluidity can be suppressed, and the sealing of the crystal grains 30 can be further improved. Further, by setting it as the upper limit or less, it is possible to effectively suppress a decrease in solder heat resistance. The resin may be used singly or in combination of two or more.

As the hardener, for example, an aliphatic polyamine such as diethylene triamine (DETA), triethylene tetramine (TETA), meta-xylylene diamine (MXDA), or a diamine group Other than aromatic polyamines such as diamino diphenyl methane (DDM), m-phenylene diamine (MPDA), and diamino diphenyl sulfone (DDS), An amine-based curing agent such as a polyamine compound such as dicyandiamide (DICY) or an organic acid dioxime; a phenolic curing agent such as a novolac type phenol resin or a phenol polymer (a curing agent having a phenolic hydroxyl group), Heterocyclic fatty acid anhydride (liquid anhydride) such as hexahydrophthalic anhydride (HHPA), methyl tetrahydrophthalic anhydride (MTHPA), trimellitic anhydride (TMA) ), aromatic acid such as pyromellitic dianhydride (PMDA), benzophenone tetracarboxylic dianhydride (BTDA) An acid anhydride hardener such as an anhydride, a polyamide resin or a polysulfide resin. In the case where the epoxy resin is used as the resin, the curing agent is not particularly limited, and a curing agent having a phenolic hydroxyl group is preferably used. The hardener having a phenolic hydroxyl group can easily control the reaction of the resin as compared with other hardeners, and thus can secure good fluidity when manufacturing a semiconductor element. Further, since the curing agent having a phenolic hydroxyl group is easily controlled by the reactivity, it is also possible to achieve high filling of the inorganic filler. Therefore, excellent reliability of the semiconductor element can be ensured. Here, the curing agent having a phenolic hydroxyl group is a monomer, an oligomer, or a polymer having two or more phenolic hydroxyl groups in one molecule, and the molecular weight and molecular structure thereof are not particularly limited. Specific examples thereof include a phenol novolak type phenol resin such as a phenol novolak resin and a cresol novolak resin, and a modification of a trisphenol methane type phenol resin, a terpene modified phenol resin, and a dicyclopentadiene modified phenol resin. a phenol resin, a phenol aralkyl resin having a phenyl group and/or a biphenyl group, a aralkyl phenol resin such as a naphthol aralkyl resin having a phenyl group and/or a phenyl group extending, double Phenolic compounds, etc., which may be used singly or in combination.

The content of the curing agent is not particularly limited, but is preferably 2% by mass to 10% by mass based on the entire molded layer, and particularly preferably 4% by mass to 7% by mass. The hardener may be used singly or in combination of two or more. Further, in the case where the resin is an epoxy resin, as the curing agent, a hardener having a phenolic hydroxyl group can be preferably used, in which case the epoxy group of the epoxy resin and the hardening having a phenolic hydroxyl group are used. The equivalent ratio (epoxy group/phenolic hydroxyl group) of the phenolic hydroxyl group of the agent is not particularly limited, but is preferably 0.5 to 2.0, and particularly preferably 0.7 to 1.5. When the equivalent ratio is within the above range, the hardenability and the moisture resistance reliability are particularly excellent.

It is preferred to contain an inorganic filler in the shaped layer. Examples of the inorganic filler include talc, calcined clay, uncalcined clay, mica, glass, etc., titanium oxide, aluminum oxide, molten cerium oxide (spherical molten cerium oxide, broken molten oxidized矽), oxides such as cerium oxide powder such as crystalline cerium oxide, carbonates such as calcium carbonate, magnesium carbonate, and hydrotalcite; hydroxides such as aluminum hydroxide, magnesium hydroxide, and calcium hydroxide; barium sulfate and calcium sulfate; Sulfate or sulfite such as calcium sulfite, borate such as zinc borate, barium metaborate, aluminum borate, calcium borate or sodium borate; nitride such as aluminum nitride, boron nitride or tantalum nitride. The inorganic fillers may be used singly or in combination. Among these, cerium oxide powder such as molten cerium oxide or crystalline cerium oxide is preferable, and spherical molten cerium oxide is particularly preferable. Thereby, heat resistance, moisture resistance, strength, and the like can be improved. The shape of the inorganic filler is not particularly limited, but is preferably a spherical shape, and preferably has a broad particle size distribution. Thereby, the fluidity of the molded resin composition can be particularly improved. Further, the surface of the inorganic filler may be surface-treated by a coupling agent.

The content of the inorganic filler contained in the molded layer is not particularly limited, but is preferably 20% by mass to 95% by mass based on the entire molded resin composition, and particularly preferably 30% by mass to 90% by mass. When the content is at least the lower limit value, the decrease in moisture resistance is suppressed, and when the content is at most the upper limit value, good fluidity can be maintained. The inorganic filler may be used singly or in combination of two or more.

Further, in the range which does not impair the object of the present invention, a diazabicycloalkene such as 1,8-diazabicyclo[5,4,0]undecene-7 and a derivative thereof may be added to the shaped layer. An amine compound such as tributylamine or benzyl dimethylamine; an imidazole compound such as 2-methylimidazole; an organic phosphine such as triphenylphosphine or methyl diphenylphosphine; tetraphenylphosphonium tetraphenyl borate; Tetrasubstituted tetraphenylphosphonium tetracarboxylic acid borate, tetraphenylphosphonium tetradecanoic acid borate, tetraphenylphosphonium tetramethylammonium decyloxyborate, tetraphenylphosphonium tetradecyloxyborate a hardening accelerator such as a tetra-substituted borate, a decane coupling agent such as an epoxy decane, a mercapto decane, an amino decane, an alkyl decane, a ureido quinane or a vinyl decane, or a titanate coupling agent or an aluminum coupling agent. , coupling agent such as aluminum/zirconium coupling agent, coloring agent such as carbon black, iron oxide (bengala), natural wax such as carnauba wax, synthetic wax such as polyethylene wax, higher fatty acid such as stearic acid or zinc stearate and its metal Salt, paraffin and other mold release agents, low stress components such as eucalyptus oil and bismuth rubber, brominated epoxy resin or antimony trioxide, hydrogen peroxide Additive magnesium hydroxide, zinc borate, zinc molybdate, phosphazene flame retardants, bismuth oxide hydrate inorganic ion exchanger and so on. These components may be used alone or in combination of two or more.

As a commercially available product of the molded layer, Sumikon EME-G750 series manufactured by Sumitomo Bakelite, Sumikon EME-G760 series, and Sumikon EME- are mentioned. G770 series, Sumikon EME-G790 series, CEL series manufactured by Hitachi Chemical Co., Ltd., R4000 series manufactured by Nagase chemteX, GR series manufactured by Henkel, manufactured by Kyocera Chemical KE series and so on.

The thickness of the molding layer 40 is preferably 100 μm or more, and more preferably 1000 μm or more in the thinnest portion. Further, the upper limit of the thickness is preferably 3000 μm or less, and more preferably 5000 μm or less in the thinnest portion.

Examples of the method for forming the molding layer 40 include a method of laminating a film-form molding resin composition, a method of forming a paste-form molding resin composition by screen printing or a dispenser, and a liquid molding resin composition. A method of baking and a method of heating using a solid compression-molded resin composition.

Further, in the present invention, in the case of forming the molding layer 40, a state in which a molten resin is used may be employed. In this case, the viscosity of the molded resin composition when covering the crystal grains 30 is preferably about 3.0 Pa·s to 20.0 Pa·s. In the case of using a molten resin, the molded resin composition is sufficiently and uniformly mixed with a raw material, for example, by a mixer or the like, and further melt-kneaded by a kneading machine such as a hot roll, a kneader or an extruder, and then cooled and pulverized. obtain. The viscosity at the time of sealing by the molding resin composition is not particularly limited, and is, for example, 3.0 Pa·s or more, and more preferably 5.0 Pa·s or more. On the other hand, the viscosity is preferably 30.0 Pa·s or less, more preferably 20.0 Pa·s or less. Thereby, the generation of voids can be suppressed. The viscosity can be obtained, for example, by a high-pressure flow tester or the like. After sealing with a molding resin composition, the molding resin composition is cured. Examples of the method of curing the molded resin composition include a method of heating, a method of performing light irradiation, and the like.

The molding layer 40 can also be formed by molding using a solid compression-molded resin composition. That is, the solid molded compression-molded resin composition may be molded by heat and pressure in a mold to form the molded layer 40. Here, as a solid compression-molding resin composition, resin pellets obtained by melt-kneading the molten resin, cooling, and then pelletizing the resin may be exemplified. Further, the molding layer does not have to use a "die", a method of laminating a film-form molding resin composition, a method of forming a paste-form molding resin composition by screen printing or a dispenser, or a coating liquid-like molding resin. The case where the composition is hardened and the like are also included in the scope of the present invention.

In the method for producing a semiconductor device of the present invention, a temporary adhesive layer can be formed by a so-called non-reactive method which does not cure the temporary adhesive layer by a reaction.

In the method for producing a semiconductor device of the present invention, heat treatment at 100 ° C or higher can be performed after the formation of the formed layer. Although heat treatment of 100 ° C or higher is sometimes performed in the manufacturing process of the semiconductor element, the present invention can withstand such high temperature treatment, and is high in value at this point. The heat treatment may be performed before the peeling of the carrier substrate, or after the peeling and removal of the carrier substrate or the temporary adhesive layer. Further, the heat treatment temperature is preferably 100 ° C or higher, more preferably 110 ° C or higher, and still more preferably 140 ° C or higher. The upper limit is preferably 260 ° C or lower, more preferably 220 ° C or lower. By further heat-treating the molding layer 40, for example, when a thermosetting resin (preferably an epoxy resin) is used as the molding resin composition, the curing of the thermosetting resin can be sufficiently performed. The heat treatment time can be exemplified by 10 minutes to 10 hours.

Next, as shown in FIG. 1 (A4), the carrier substrate 10 is peeled off from the laminated body (the peeling described herein is intended to include separation and separation). The method of peeling off the carrier substrate 10 is not particularly limited, and it is preferable that the carrier substrate 10 is peeled off from the laminate by mechanical treatment at a temperature of 40 ° C or lower. In this case, only the carrier substrate may be peeled off, or one or two or more temporary adhesive layers 20 may be peeled off together with the carrier substrate. The peeling position can be adjusted by adjusting the blending amount of the highly releasable component blended in the two or more temporary adhesive layers. For example, in the case where peeling is to be performed between the carrier substrate and the temporary adhesive layer that is in contact with the carrier substrate, the release agent having a high release property can be more frequently disposed in the temporary adhesive layer that is in contact with the carrier substrate. ingredient. In particular, it is effective if the component having high mold release property has a biased existence. It is possible to appropriately stipulate at a position of the laminated body according to the use or the like. Preferably, the peeling is performed at the interface between the carrier substrate and the temporary adhesive layer. Regarding the peeling, for example, it is preferred that the molding layer is pulled up in the vertical direction from the end portion of the carrier substrate to perform peeling without any treatment. At this time, it is also preferable to perform the peeling after cutting the slit in the gap between the carrier substrate and the temporary adhesive layer by a sharp jig such as a cutter. The speed at the time of separation is preferably from 30 mm/min to 120 mm/min, more preferably from 40 mm/min to 100 mm/min. The temperature at the time of peeling is preferably 40 ° C or lower, more preferably 10 ° C to 40 ° C, still more preferably 20 ° C to 30 ° C. In addition to the above, in the peeling of the carrier substrate, the temporary adhesive layer may be dissolved using a peeling liquid to peel the carrier substrate from the laminate. As the peeling liquid in this case, a solvent (organic solvent) can be used.

When one or two or more temporary adhesive layers are left on the laminated body of the peeled carrier substrate, the temporary adhesive layer is usually removed. The removal of the temporary adhesive layer is preferably carried out at 40 ° C or lower. The means for removing the temporary adhesive layer is not particularly limited, and the temporary adhesive layer is mechanically removed at a temperature of 40 ° C or lower in the laminate of the peeled carrier substrate. The term "mechanical property" as used herein refers to peeling without chemical treatment or the like, and also includes the purpose of peeling off by hand. The temperature at which the temporary adhesive layer is removed is preferably 40 ° C or lower, more preferably 10 ° C to 40 ° C, and still more preferably 20 ° C to 30 ° C. In order to improve the peelability, a part of the adhesive layer may be deteriorated by irradiating radiation or heating. Further, the temporary adhesive layer may be peeled off using a solvent (organic solvent).

When the temporary adhesive layer 20 is attached to the carrier substrate 10, the carrier substrate 10 can be regenerated by removing the temporary adhesive layer 20 from the carrier substrate 10. As a method of removing the temporary adhesive layer 20, in the form of a film, a physical removal method by blowing a brush, an ultrasonic wave, an ice particle, or an aerosol can be mentioned; A method of dissolving and removing an organic solvent; a chemical removal method such as a method of decomposing and vaporizing by actinic rays, radiation, or heat; and a conventionally known cleaning method can be used depending on the carrier substrate. For example, in the case of using an element substrate as a carrier substrate, a previously known cleaning method of a germanium wafer can be used, for example, as an aqueous solution or an organic solvent which can be used for chemical removal, and examples thereof include strong acid, strong alkali, and strong The oxidizing agent or a mixture thereof may specifically be an acid such as sulfuric acid, hydrochloric acid, hydrofluoric acid, nitric acid or an organic acid; an alkali such as tetramethylammonium, ammonia or an organic base; an oxidizing agent such as hydrogen peroxide; or ammonia. a mixture with 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.

From the viewpoint of the adhesion in the case of using the regenerated carrier substrate, it is preferred to use a carrier substrate cleaning solution. 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 may be selected from inorganic acids such as hydrogen iodide, perchloric acid, hydrogen bromide, hydrogen chloride, nitric acid, sulfuric acid, or the like, or an organic acid such as an alkylsulfonic acid or an arylsulfonic acid. From the viewpoint of the cleaning property of the temporary adhesive layer on the carrier substrate, a mineral acid is preferred, and sulfuric acid is preferred.

As the hydrogen peroxide, 30% by mass of hydrogen peroxide water can be preferably used, and the mixing ratio of the strong acid to 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 the best is 3:1 to 5:1.

Next, in the method for producing a semiconductor device of the present invention, a temporary adhesive composition for forming a temporary adhesive will be described.

<Temporary Adhesive Composition> The temporary adhesive layer used in the present invention can be usually formed using a temporary adhesive composition. The temporary adhesive composition preferably contains a resin, and more preferably contains a resin and a solvent. The temporary adhesive composition further preferably contains a compound containing at least one of a fluorine atom and a ruthenium atom.

<<Resin>> The resin used in the present invention is preferably an elastomer. By using an elastomer, it is possible to follow the fine unevenness of the carrier substrate, and to form a temporary adhesive excellent in adhesion by an appropriate anchor effect. Further, when the carrier substrate is peeled off from the laminate, the carrier substrate can be peeled off from the laminate without applying stress to the laminate, and the laminate can be prevented from being damaged or peeled off. In the present specification, the elastomer is a polymer compound which exhibits elastic deformation. That is, it is defined as a polymer compound having a property that when an external force is applied, deformation occurs instantaneously in response to the external force, and when the external force is removed, the original shape is restored in a short time. The resin contained in the temporary adhesive agent may, for example, be a thermoplastic elastomer having a styrene structure, a thermoplastic siloxane polymer, a cycloolefin polymer, an acrylic resin, a polycarbonate, a polyether oxime, or a thermoplastic polyamide. The thermoplastic polyimide, preferably comprising at least one of a thermoplastic elastomer having a styrene structure, a thermoplastic siloxane polymer, a cycloolefin polymer, an acrylic resin, and a thermoplastic polyimide, more preferably comprising At least one of a thermoplastic elastomer having a styrene structure, a cycloolefin polymer, various block copolymers, and an acrylic resin, and more preferably at least one of a thermoplastic elastomer having a styrene structure and a cycloolefin polymer. It is particularly preferred to include a thermoplastic elastomer having a styrene structure.

<<<The thermoplastic elastomer having a styrene structure>>> The temporary adhesive composition preferably contains a thermoplastic elastomer having a styrene structure. The thermoplastic elastomer having a styrene structure is not particularly limited, and a known styrene-based elastomer can be used. A preferred embodiment of the thermoplastic elastomer having a styrene structure used in the present invention is an elastomer X containing a repeating unit derived from styrene in a ratio of 50% by mass or more and 95% by mass or less in all the repeating units. The example further includes the case where the elastomer Y containing a repeating unit derived from styrene is contained in a ratio of 10% by mass or more and less than 50% by mass in all the repeating units. By using the elastomer X and the elastomer Y in combination, the flatness of the polished surface of the processed substrate (hereinafter also referred to as flat polishing property) is excellent, and the warpage of the processed substrate after polishing can be effectively suppressed. produce. The mechanism for obtaining such an effect can be presumed to be the following. That is, since the elastomer X is a relatively hard material, by including the elastomer X, a temporary adhesive layer having excellent releasability can be produced. Further, since the elastomer Y is a relatively soft material, it is easy to form a temporary adhesive layer having elasticity. Further, even if the laminated body after polishing is subjected to heat treatment and then cooled, the internal stress generated during cooling can be relaxed by the temporary adhesive, whereby the occurrence of warpage can be effectively suppressed. For example, in the process of cooling the laminated body to room temperature after forming the formed layer, the warpage of the laminated body is reduced by stress relaxation, and a flat laminated body can be obtained by the present invention. In addition, even if the elastomer Y is blended in the elastomer X, there is a region where the elastomer X is phase-separated, and the excellent releasability by the elastomer X can be sufficiently achieved.

The thermoplastic elastomer having a styrene structure is not particularly limited and may be appropriately selected depending on the purpose. For example, styrene-butadiene-styrene block copolymer (SBS), styrene-isoprene-styrene block copolymer (SIS), styrene-ethylene-butylene-styrene embedded Segment copolymer (SEBS), styrene-butadiene-butene-styrene copolymer (SBBS) and these hydrides, styrene-ethylene-propylene-styrene block copolymer (SEPS), styrene - an ethylene-ethylene-propylene-styrene block copolymer or the like.

The thermoplastic elastomer having a styrene structure preferably has a weight average molecular weight of 2,000 to 200,000, more preferably 10,000 to 200,000, still more preferably 50,000 to 100,000. By being in this range, the thermoplastic elastomer having a styrene structure is excellent in solubility in a solvent, and coatability is improved. Further, after the processed substrate is peeled off from the carrier substrate, when the remaining temporary adhesive is removed, the solubility in the solvent is also excellent, so that there is an advantage that the residue does not remain on the processed substrate or the carrier substrate.

In the present invention, as the thermoplastic elastomer having a styrene structure, a block copolymer, a random copolymer, a graft copolymer, preferably a block copolymer, more preferably a single terminal or a benzene at both ends is exemplified. A block copolymer of ethylene, particularly preferably a block copolymer in which both ends are styrene. When the both ends of the thermoplastic elastomer having a styrene structure are a block copolymer of styrene (a repeating unit derived from styrene), thermal stability tends to be further improved. The reason for this is that a repeating unit derived from styrene having high heat resistance exists at the terminal. In particular, a block portion derived from a repeating unit derived from styrene is a reactive polystyrene-based hard block, and heat resistance and chemical resistance are more preferable, and it is preferable. Further, it is considered that when these are block copolymers, phase separation is performed between the hard block and the soft block at 200 ° C or higher. It is considered that the shape of the phase separation contributes to suppression of generation of irregularities on the surface of the processed substrate of the element wafer. Further, it is more preferably such a resin from the viewpoint of solubility in a solvent and resistance in a resist solvent.

In the present invention, the thermoplastic elastomer having a styrene structure is preferably a hydride. If the thermoplastic elastomer having a styrene structure is a hydride, thermal stability or storage stability is improved. Further, the peeling property and the cleaning and removal property of the temporary adhesive after peeling are improved. Further, the term "hydride" means a polymer having a structure in which an elastomer is hydrogenated.

The 5% thermal mass reduction temperature of the thermoplastic elastomer having a styrene structure at a temperature of 20 ° C/min from 25 ° C is preferably 250 ° C or higher, more preferably 300 ° C or higher, and still more preferably 350 ° C or higher, and particularly preferably 400. Above °C. Further, the upper limit is not particularly limited, and is, for example, preferably 1000 ° C or lower, more preferably 800 ° C or lower. According to this aspect, it is easy to form a temporary adhesive agent excellent in heat resistance. Further, by providing a temporary adhesive having excellent heat resistance, heat resistance can be imparted to the laminated body after the formation of the molded layer, and the laminated body itself can be heat-treated, and then peeled off. The thermoplastic elastomer having a styrene structure preferably has such a property that when the original size is set to 100%, it can be deformed to 200% with a small external force at room temperature (20 ° C), and when the external force is removed When it is restored to less than 130% in a short time.

The amount of the unsaturated double bond of the thermoplastic elastomer having a styrene structure is preferably less than 15 mmol/g, more preferably 7 mmol/g or less, and still more preferably from the viewpoint of the releasability after the processing step. Less than 5 mmol/g, particularly preferably less than 0.5 mmol/g. The lower limit is not particularly limited and may be, for example, 0.001 mmol/g or more. Furthermore, the amount of unsaturated double bonds described herein does not comprise unsaturated double bonds in the benzene ring derived from styrene. The amount of unsaturated double bonds can be calculated by nuclear magnetic resonance (NMR) measurement.

In the present specification, the "repeating unit derived from styrene" is a constituent unit derived from styrene or styrene contained in the polymer when the 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 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an alkoxyalkyl group having 2 to 5 carbon atoms, an ethoxy group, and a carboxyl group.

As a commercial item of the thermoplastic elastomer having a styrene structure, for example, Tufprene A, Tufprene 125, Tufprene 126S, Solupron ( Solprene) T, Asaprene T-411, Asaprene T-432, Asaprene T-437, Asaprene T-438, Asa Asaprene T-439, Tuftec H1272, Tuftec P1500, Tuftec H1052, Tuftec H1062, Taftec ( Tuftec) M1943, Tuftec M1911, Tuftec H1041, Tuftec MP10, Tuftec M1913, Tuftec H1051, tower Tuftec H1053, Tuftec P2000, Tuftec H1043 (above trade name, manufactured by Asahi Kasei); Elastomer AR-850C, elastomer ( Elastomer) AR-815C, Elastomer AR-840C, Elastomer AR-830C, Elastomer AR-860C, Elastomer AR-875C, Elastomer AR-885C, Elastomer AR-SC-15, Elastomer AR-SC-0, Elastomer AR -SC-5, Elastomer AR-710, Elastomer AR-SC-65, Elastomer AR-SC-30, Elastomer AR-SC-75, Elastomer ( 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 (above trade name, Aronkasei) ))) Kraton D1111, Kraton D1113, Kraton D1114, Kraton D1117, Kraton (Kraton) D1119, Kraton D1124, Kraton D1126, Kraton D1161, Kraton D1162, Kraton D1163, Kraton D1164, Kraton 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, Kalicus Cariflex) IR0307, Cariflex IR0310, Cariflex IR0401, Kraton D0242, Kraton D1101, Kraton D1102, Kraton D1116, Kraton D1118, Kraton D1133, Kraton D1152

Kraton D1153, Kraton D1155, Kraton D1184, Kraton D1186, Kraton D1189, Kraton D1191, Kraton D1192 Kraton DX405, Kraton DX408, Kraton DX410, Kraton DX414, Kraton DX415, Kraton A1535, Kraton A1536, Kraton (Kraton) FG1901, Kraton FG1924, Kraton G1640, Kraton G1641, Kraton G1642, Kraton G1643, Kraton G1645, Kraton Kraton) G1633, Kraton G1650, Kraton G1651, Kraton G1652, Kraton G1654, Kraton G1657, Kraton G1660, Kraton ) G1726, Kraton G1701, Kraton G1702, Kraton G1730, Kraton G1750, Kraton G1765, Kraton G4609, Kraton G4610 (above is the trade name, manufactured by Kraton); TR200 0, TR2001, TR2003, TR2250, TR2500, TR2601, TR2630, TR2787, TR2827, TR1086, TR1600, SIS5002, SIS5200, SIS5250, SIS5405, SIS5505, Dynaron 6100P, Dynaron 4600P, Dana Dynaron 6200P, Dynaron 4630P, Dynaron 8601P, Dynaron 8630P, Dynaron 8600P, Dynaron 8903P, Danalong (Dynaron) Dynaron) 6201B, Dynaron 1321P, Dynaron 1320P, Dynaron 2324P, Dynaron 9901P (above trade name, JSR); (Denka) STR series (above the trade name, electrochemical industry (stock)); Quintac 3520, Quintac 3433N, Quintac 3421, Quintac 3620, Quintac 3450, Quintac 3460 (made by Japan's ZEON); TPE-SB series (above trade name, Sumitomo Chemical Co., Ltd.); Rabalon Series (above is the trade name, three Chemical (stock) manufacturing); Septon 1001, Septon 8004, Septon 4033, Septon 2104, Septon 8007, Saipton (Septon) 2007, Septon 2004, Septon 2063, Septon HG252, Septon 8076, Septon 2002, Septon (Septon) 1020, Septon 8104, Septon 2005, Septon 2006, Septon 4055, Septon 4044, Septon 4077 , Septon 4099, Septon 8006, Septon V9461, Septon V9475, Septon V9827, Hybrar 7311, Sea Hybrar 7125, Hybrar 5127, Hybrar 5125 (above trade name, Kuraray); Sumiflex (above trade name, Sumitomo) Sumitomo Bakelite (manufactured by the stock); Leostomer, Akutama (Actymer) (The above is the trade name, manufactured by Riken Ethylene Industry).

Next, a specific preferred range of "elastomer X" will be described. The elastomer X is an elastomer containing a repeating unit derived from styrene in a ratio of 50% by mass or more and 95% by mass or less in all the repeating units, and the content of the repeating unit derived from styrene is preferably more than 50% by mass. 95% by mass or less, more preferably 50% by mass to 90% by mass, still more preferably 50% by mass to 80% by mass, particularly preferably 55% by mass to 75% by mass, particularly preferably 56% by mass to 70% by mass. The hardness of the elastomer X is preferably 83 or more, more preferably 85 or more, still more preferably 90 or more. The upper limit is not particularly specified, and is, for example, 99 or less. Further, the hardness is a value measured by a method of JIS (Japanese Industrial Standard) K6253 and measured by a type A durometer.

Next, a specific preferred range of "elastomer Y" will be described. The elastomer Y is an elastomer containing a repeating unit derived from styrene in a ratio of 10% by mass or more and less than 50% by mass in all the repeating units, and the content of the repeating unit derived from styrene is preferably 10% by mass to 45%. The mass% is more preferably 10% by mass to 40% by mass, still more preferably 12% by mass to 35% by mass, particularly preferably 13% by mass to 33% by mass. The hardness of the elastomer Y is preferably 82 or less, more preferably 80 or less, still more preferably 78 or less. The lower limit is not particularly specified, but is 1 or more. Further, the difference between the hardness of the elastomer X and the hardness of the elastomer Y is preferably from 5 to 40, more preferably from 10 to 35, still more preferably from 15 to 33, still more preferably from 17 to 29. By setting it as such a range, the effect of this invention is exhibited more effectively.

In the present invention, an elastomer other than the elastomer X and the elastomer Y may be blended. As the other elastomer, a polyester elastomer, a polyolefin elastomer, a polyurethane elastomer, a polyamide elastomer, a polyacryl elastomer, an anthrone elastomer, and a polyfluorene can be used. An imide elastomer or the like.

The total amount of the elastomer X, the elastomer Y, and the other elastomer in the temporary adhesive composition used in the present invention is preferably from 50.00% by mass to 99.99% by mass based on the mass of the temporary adhesive composition other than the solvent. More preferably, it is 70.00% by mass to 99.99% by mass, particularly preferably 88.00% by mass to 99.99% by mass. When the content of the elastomer is in the above range, the adhesion and the releasability are more excellent. Further, the elastomer X, the elastomer Y, and other elastomers in the temporary adhesive composition used in the present invention may each be in various combinations.

In the content of the elastomer contained in the temporary adhesive composition used in the present invention, the total amount of the elastomer X and the elastomer Y is preferably 90% by mass or more, and more preferably 95% by mass or more. Particularly good is 98% by mass or more. In the case of blending the elastomer Y, the mass of the elastomer X and the elastomer Y is preferably an elastomer X: an elastomer Y = 5: 95 to 95: 5, more preferably 20: 80 to 90: 10, especially good for 40:60 ~ 85:15. If it is the said range, it is more effective in suppressing warpage and obtaining peeling property.

<<<Thermoplastic siloxane polymer>>> A thermoplastic siloxane polymer can be used as the resin component for the temporary adhesive composition. The thermoplastic siloxane polymer is a monovalent hydrocarbon group or a hydroxyl group having R ²¹ R ²² R ²³ SiO _1/2 units (R ²¹ , R ²² and R ²³ are respectively unsubstituted or substituted carbon atoms having 1 to 10 carbon atoms) And an organic _polyoxane having a molar ratio of 0.6 to 1.7 of the SiO _4/2 unit and the R ²¹ R ²² R ²³ SiO _1/2 unit/SiO _4/2 unit and represented by the following formula (1) The organopolyoxyalkylene is partially dehydrated and condensed, preferably the ratio of the dehydrated condensed organopolyoxane to the organopolyoxane is from 99:1 to 50:50, and The weight average molecular weight is from 200,000 to 1,500,000. [Chemical 1] (wherein R ¹¹ and R ¹² each represent an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, and n is 5,000 to 10,000)

When it is such a thermoplastic siloxane, it is excellent in adhesiveness and heat resistance, and it is preferable.

In the above formula (1), the organic substituents R ¹¹ and R ¹² are an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, specifically: methyl group, ethyl group, n-propyl group. An alkyl group such as isopropyl, n-butyl, tert-butyl, n-pentyl, cyclopentyl or n-hexyl; a cycloalkyl group such as a cyclohexyl group; a hydrocarbon group such as an aryl group such as a phenyl group or a tolyl group; A group in which a part or all of an atom is substituted with a halogen atom; preferably a methyl group and a phenyl group.

The thermoplastic organic polyoxyalkylene has a weight average molecular weight of 200,000 or more, more preferably 350,000 or more, and 1,500,000 or less, more preferably 1,000,000 or less. Further, the content of the low molecular weight component having a molecular weight of 740 or less is preferably 0.5% by mass or less, more preferably 0.1% by mass or less. As a commercial item, SILRES 604 (Asahi Kasei Wacker Silicone) can be exemplified.

<<<Cycloolefin polymer>>> Examples of the cycloolefin polymer include a norbornene-based polymer, a monocyclic cyclic olefin polymer, a cyclic conjugated diene polymer, and a vinyl group. An alicyclic hydrocarbon polymer, a hydride of the polymers, and the like. Preferable examples of the cycloolefin polymer include an addition (co)polymer containing at least one repeating unit represented by the following formula (II), and further including a formula represented by the formula (I) An addition (co)polymer of at least one of the repeating units. Further, as another preferable example of the cycloolefin polymer, a ring-opening (co)polymer containing at least one cyclic repeating unit represented by the formula (III) can be mentioned.

[Chemical 2]

In the formula, m represents an integer of 0-4. R ¹ to R ⁶ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and X ¹ to X ³ and Y ¹ to Y ³ each independently represent a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, a halogen atom, and a halogen atom. a hydrocarbon group having 1 to 10 carbon 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 , -(CH ₂ )nOZ, -(CH ₂ )nW, or consist of X ¹ and Y ¹ , X ² and Y ² or X ³ and Y ³ (-CO) ₂ O, (-CO) ₂ NR ¹⁷ . R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ and R ¹⁷ each 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, SiR ¹⁸ _p D _3-p (R ¹⁸ represents a hydrocarbon group having 1 to 10 carbon atoms, D represents a halogen atom and represents -OCOR ¹⁸ or -OR ¹⁸ , and p represents an integer of 0 to 3). n represents an integer of 0 to 10.

The norbornene-based polymer is disclosed in Japanese Patent Laid-Open No. Hei 10-7732, Japanese Patent Publication No. 2002-504184, No. 2004/229157 A1, and WO2004/070463A1. The norbornene-based polymer can be obtained by subjecting a norbornene-based polycyclic unsaturated compound to addition polymerization with each other. Further, if desired, the norbornene-based polycyclic unsaturated compound may be similar to ethylene, propylene, butylene, a conjugated diene such as butadiene or isoprene, such as ethylidene norbornene. The non-conjugated diene is subjected to addition polymerization. The norbornene-based polymer is sold by Mitsui Chemicals Co., Ltd. under the trade name of Apel, and has a glass transition temperature (Tg) such as APL8008T (Tg70 °C), APL6013T (Tg125 °C) or APL6015T ( Tg145 ° C) and other grades. POPs (TOP) 8007, TOPAS 5013, TOPAS 6013, TOPAS 6015 and other pellets are sold by Poly plastic. Further, Appear 3000 is sold by Ferrania.

The hydride of the norbornene-based polymer can be as disclosed in Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. As disclosed in Japanese Laid-Open Patent Publication No. 2003-1159767 or Japanese Patent Application Publication No. 2004-309979, the hydrogenation is carried out by addition polymerization or ring-opening shift polymerization of a polycyclic unsaturated compound. Manufacturing. In the above formula (III), R ⁵ and R ^{6 are} preferably a hydrogen atom or a methyl group, and X ³ and Y ^{3 are} preferably a hydrogen atom, and other groups can be appropriately selected. The norbornene-based polymer is sold by JSR (share) under the trade name of Arton G or Arton F, and by Zeonor ZF14, ZF16, by ZEON, Japan. The trade names of Zeonex 250, Zeonex 280, and Zeonex 480R are commercially available and can be used.

The polystyrene-equivalent weight average molecular weight obtained by gel permeation chromatography (GPC) of the cycloolefin polymer is preferably 10,000 to 1,000,000, preferably 50,000 to 500,000, more preferably 100,000 to 300,000. In addition, as the cycloolefin polymer to be used in the present invention, a cycloolefin polymer described in paragraph 0039 to paragraph 0052 of JP-A-2013-241568 may be exemplified, and the contents are incorporated herein. In the manual.

<<<Acrylic Resin>>> The acrylic resin in the present invention is a resin obtained by polymerizing a (meth) acrylate monomer. Examples of the (meth) acrylate monomer include 2-ethylhexyl (meth)acrylate, ethyl (meth)acrylate, methyl (meth)acrylate, and n-propyl (meth)acrylate. Isopropyl (meth)acrylate, amyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate, isodecyl (meth)acrylate, (meth)acrylic acid Butyl ester, isobutyl (meth)acrylate, hexyl (meth)acrylate, n-decyl (meth)acrylate, isoamyl (meth)acrylate, n-decyl (meth)acrylate, (methyl) Isodecyl acrylate, dodecyl (meth)acrylate, isobornyl (meth)acrylate, cyclohexyl (meth)acrylate, phenyl (meth)acrylate, methyl (acrylic acid) benzyl A base ester and 2-methylbutyl (meth)acrylate. Further, other monomers may be copolymerized within a range not exceeding the gist of the invention. In the case of copolymerizing other monomers, it is preferably 10 mol% or less of all the monomers.

Further, in the present invention, an acrylic resin having an organic polyoxyalkylene in a side chain is also preferred. The resin which has an organopolysiloxane in a side chain is represented by the following formula (3). Formula (3) [Chemical 3] In the formula (3), when R ¹ is plural, it may be the same or different, and represents CH ₃ , C ₂ H ₅ , CH ₃ (CH ₂ ) ₂ or CH ₃ (CH ₂ ) ₃ . When R ² has a plurality of, it may be the same or different and represents H, CH ₃ , C ₂ H ₅ , CH ₃ (CH ₂ ) ₂ or CH ₃ (CH ₂ ) ₃ . When R ³ has a plurality of, it may be the same or different and represents H or CH ₃ . When R ⁴ has a plurality of, it may be the same or different, and represents H, CH ₃ , C ₂ H ₅ , CH ₃ (CH ₂ ) ₂ , CH ₃ (CH ₂ ) ₃ , or selected from an epoxy group. A C 1-6 alkyl group substituted with at least one functional group in the group consisting of a hydroxyl group, a carboxyl group, an amine group, an alkoxy group, a vinyl group, a stanol group, and an isocyanate group. a is 50 to 150, b is 50 to 150, and c is 80 to 600. In addition, m is 1 to 10. Specific examples of the acrylic resin having an organic polysiloxane in the side chain include an anthrone-grafted acrylic resin manufactured by Shin-Etsu Chemical Co., Ltd., trade names: X-24-798A, X-22-8004 ( R ⁴ : C ₂ H ₄ OH, functional group equivalent: 3250 (g/mol)), X-22-8009 (R ⁴ : alkyl group containing Si(OCH ₃ ) ₃ , functional group equivalent: 6200 (g/mol) )), X-22-8053 (R ⁴ : H, functional group equivalent: 900 (g/mol)), X-22-8084, X-22-8084EM, X-22-8195 (R ⁴ : H, functional Base equivalent: 2700 (g/mol)); Symac series (US-270, US-350, US-352, US-380, US-413, US-450, etc.) manufactured by East Asia Synthetic Co., Ltd. ), Rezeta GS-1000 series (GS-1015, GS-1302, etc.). Further, in addition to the above, an acrypet MF 001 manufactured by Mitsubishi Rayon Co., Ltd., or the like can be exemplified.

The temporary adhesive composition used in the present invention is preferably a resin of 50% by mass to 100% by mass of the solid content, more preferably 70% by mass to 100% by mass of the resin. The temporary adhesive composition used in the present invention may contain only one type of resin, or may contain two or more types. In the case where two or more types are contained, it is preferred that the total amount is the above range.

<<Solvent>> The temporary adhesive composition used in the present invention preferably contains a solvent. In the case where the temporary adhesive layer is formed by applying the temporary adhesive composition used in the present invention, it is preferred to formulate a solvent. The solvent can be used without any limitation, and is preferably an organic solvent. The organic solvent may preferably be exemplified by ethyl acetate, n-butyl acetate, isobutyl acetate, amyl acetate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, Ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, alkyl alkyl oxyacetate (eg methyl alkyl oxyacetate, ethyl alkyl oxyacetate, alkyl oxy acetic acid) Butyl ester (such as methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.), 3-alkyloxypropionic acid Alkyl esters (for example: methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc. (for example, methyl 3-methoxypropionate, ethyl 3-methoxypropionate) , methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.), alkyl 2-alkyloxypropionate (for example: methyl 2-alkyloxypropionate, Ethyl 2-alkyloxypropionate, propyl 2-alkyloxypropionate, etc. (for example, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, 2-methoxypropene) Acid propyl ester, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate), 2-alkane Methyl oxy-2-methylpropanoate and ethyl 2-alkyloxy-2-methylpropanoate (eg methyl 2-methoxy-2-methylpropanoate, 2-ethoxy-) Ethyl 2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetate, ethyl acetate, methyl 2-oxobutanoate, 2-oxo Ethyl butyrate, 1-methoxy-2-propyl acetate, etc.; diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl fibril Acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, An ether such as propylene glycol monoethyl ether acetate or propylene glycol monopropyl ether acetate; methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone, N-methyl-2-pyrrolidone, γ Ketones such as butyrolactone; toluene, xylene, anisole, mesitylene, ethylbenzene, propylbenzene, cumene, n-butylbenzene, second butylbenzene, isobutylbenzene, third Butylbenzene, pentylbenzene, isoamylbenzene, (2,2-dimethylpropyl)benzene, 1-phenylhexane, 1-phenylheptane 1-phenyloctane, 1-phenyldecane, 1-phenyldecane, cyclopropylbenzene, cyclohexylbenzene, 2-ethyltoluene, 1,2-diethylbenzene, o-isopropyl Toluene, 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-tert-butyl-m-xylene, 3,5-di-t-butyltoluene, 1,2,3,5-tetra Aromatic hydrocarbons such as methylbenzene, 1,2,4,5-tetramethylbenzene, pentamethylbenzene; hydrocarbons such as limonene, p-menthane, decane, decane, dodecane, decahydronaphthalene, etc. . Preferred among these are mesitylene, tert-butylbenzene, 1,2,4-trimethylbenzene, p-menthane, γ-butyrolactone, anisole, and methyl 3-ethoxypropionate. , 3-ethoxypropionate ethyl ester, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone And cyclohexanone, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether, and propylene glycol methyl ether acetate, more preferably mesitylene.

From the viewpoint of improving the surface properties of the coating, etc., it is preferred that the solvents are mixed in two or more forms. In this case, a mixed solution selected from the group consisting of mesitylene, tert-butylbenzene, 1,2,4-trimethylbenzene, p-menthane, γ-butyrolactone, and benzoic acid is particularly preferred. Ether, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, 3-methyl Two or more of methyl oxypropionate, 2-heptanone, cyclohexanone, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether, and propylene glycol methyl ether acetate .

The boiling point of the solvent contained in the temporary adhesive composition in 1013.25 hPa is preferably from 110 ° C to 250 ° C, more preferably from 140 ° C to 190 ° C. By using such a solvent, a temporary adhesive which is more excellent in in-plane uniformity can be obtained. In the case where two or more solvents are used, the boiling point of the solvent having the highest boiling point is defined as the boiling point.

When the temporary adhesive composition has a solvent, the content of the solvent of the temporary adhesive composition is preferably from 5% by mass to 80% by mass of the total solid content of the temporary adhesive composition from the viewpoint of coatability. The amount of % is more preferably 10% by mass to 50% by mass, particularly preferably 15% by mass to 40% by mass. The solvent may be used alone or in combination of two or more. When the solvent is two or more, it is preferred that the total is in the above range. The solvent content in the temporary adhesive is preferably 1% by mass or less, more preferably 0.1% by mass or less, and particularly preferably not contained.

<<Compound containing at least one of a fluorine atom and a ruthenium atom>> The temporary adhesive composition used in the present invention preferably contains a compound containing at least one of a fluorine atom and a ruthenium atom. By blending such a component, peeling of the carrier substrate and the processed substrate becomes easier. Further, in the compound containing at least one of a fluorine atom and a ruthenium atom, since the ruthenium atom or the fluorine atom is likely to be present in the vicinity of the surface layer of the temporary adhesive layer, the amount of the compound is relative to the temporary adhesive composition. A resin or the like is small, and a temporary adhesive agent excellent in peelability to a processed substrate or a carrier substrate can be formed.

<<<Compound having a fluorine atom>>> The temporary adhesive composition used in the present invention preferably contains a compound having a fluorine atom.

As an embodiment of the compound having a fluorine atom, a liquid compound can be exemplified. The liquid is a compound having fluidity at 25 ° C, and is, for example, a compound having a viscosity at 25 ° C of 1 mPa·s to 100,000 mPa·s. The viscosity at 25 ° C of the compound having a fluorine atom is, for example, more preferably 10 mPa·s to 20,000 mPa·s, still more preferably 100 mPa·s to 15,000 mPa·s. When the viscosity of the compound having a fluorine atom is in the above range, the compound having a fluorine atom tends to be biased toward the surface of the temporary adhesive.

In the present invention, a compound having a fluorine atom or a compound of any form of a monomer, an oligomer or a polymer can be preferably used. Alternatively, it may be a mixture of an oligomer and a polymer. Alternatively, it may be a mixture of oligomers and/or polymers and monomers. From the viewpoint of heat resistance and the like, the compound having a fluorine atom is preferably an oligomer, a polymer, and a mixture thereof. Examples of the oligomer and the polymer include a radical polymer, a cationic polymer, an anionic polymer, and the like, and any of them can be preferably used. Among them, a (meth)acrylic polymer is particularly preferred. By using a compound having a fluorine atom of a (meth)acrylic polymer, it is expected that a compound having a fluorine atom is likely to be biased toward the surface of the temporary adhesive to have an excellent peeling property. Further, in the present invention, the oligomer is defined as a compound having a weight average molecular weight of 500 or more and less than 2,000. Further, the polymer is defined as a compound having a weight average molecular weight of 2,000 or more. The weight average molecular weight of the compound having a fluorine atom is preferably from 500 to 100,000, more preferably from 1,000 to 50,000, still more preferably from 2,000 to 20,000.

In the present invention, the compound having a fluorine atom is preferably a compound which does not undergo modification when the substrate for temporary storage is treated. For example, it is preferably a compound which can be present in a liquid form even after heating at 250 ° C or higher or treating the substrate with various chemical solutions. As a specific example, after heating to 250 ° C under the temperature rising condition of 10 ° C / min from the state of 25 ° C, the viscosity at 25 ° C after cooling to 25 ° C is preferably from 1 mPa·s to 100,000 mPa·s. It is preferably from 10 mPa·s to 20,000 mPa·s, particularly preferably from 100 mPa·s to 15,000 mPa·s. As the liquid compound having a fluorine atom having such characteristics, a non-thermosetting compound having no reactive group is preferable. The reactive group as used herein refers to the entire group of the reaction which is reacted by heating at 250 ° C, and examples thereof include a polymerizable group and a hydrolyzable group. Specific examples thereof include a (meth)acryl group, an epoxy group, and an isocyanate group. As the non-thermosetting compound, a polymer containing one or two or more kinds of fluorine-containing monofunctional monomers can be preferably used. More specifically, a fluorine-containing resin or the like selected from at least one of the following polymers selected from the group consisting of tetrafluoroethylene, hexafluoropropylene, tetrafluoroethylene oxide, hexafluoropropylene oxide, and perfluoroalkylethylene may be mentioned. Homopolymer of one or two or more fluorine-containing monofunctional monomers of a vinyl ether, chlorotrifluoroethylene, vinylidene fluoride, a perfluoroalkyl group-containing (meth) acrylate or copolymerization of the monomers A copolymer of one or two or more copolymers of fluorine, a fluorine-containing monofunctional monomer and ethylene, or one or more of fluorine-containing monofunctional monomers and chlorotrifluoroethylene.

The non-thermosetting compound is preferably a perfluoroalkyl-containing (meth)acrylic copolymer which can be synthesized from a (meth) acrylate containing a perfluoroalkyl group.

From the viewpoint of the releasability, in addition to the (meth) acrylate containing a perfluoroalkyl group, the (meth)acrylic copolymer containing a perfluoroalkyl group may optionally be a copolymerization component. Examples of the radically polymerizable compound capable of forming a copolymerization component include acrylates, methacrylates, N,N-2 substituted acrylamides, and N,N-2 substituted methacrylamides. A radically polymerizable compound in styrene, acrylonitrile, methacrylonitrile or the like.

More specifically, for example, an acrylate such as an alkyl acrylate (preferably having an alkyl group having 1 to 20 carbon atoms) (for example, methyl acrylate, ethyl acrylate, propyl acrylate or butyl acrylate) , amyl acrylate, ethylhexyl acrylate, octyl acrylate, trioctyl acrylate, chloroethyl acrylate, 2,2-dimethylhydroxypropyl acrylate, 5-hydroxypentyl acrylate, trishydroxyl Propane monoacrylate, pentaerythritol monoacrylate, glycidyl acrylate, benzyl acrylate, methoxybenzyl acrylate, decyl acrylate, tetrahydrofurfuryl acrylate, etc.; aryl acrylate (eg acrylic acid) a methacrylate such as a phenyl ester or the like; an alkyl methacrylate (preferably having an alkyl group having 1 to 20 carbon atoms) (for example, methyl methacrylate, ethyl methacrylate, methyl group) Propyl acrylate, isopropyl methacrylate, amyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, chlorobenzyl methacrylate, octyl methacrylate Methacrylic acid-4 -hydroxybutyl ester, 5-hydroxypentyl methacrylate, 2,2-dimethyl-3-hydroxypropyl methacrylate, trimethylolpropane monomethacrylate, pentaerythritol monomethacrylate , glycidyl methacrylate, decyl methacrylate, tetrahydrofurfuryl methacrylate, etc.; aryl methacrylate (eg phenyl methacrylate, cresyl methacrylate, A) Nylyl acrylate, etc.; styrene, alkylstyrene, etc. (such as methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, diethyl styrene, isopropyl Styrene, butyl styrene, hexyl styrene, cyclohexyl styrene, mercaptophenethyl, benzyl styrene, chloromethyl styrene, trifluoromethyl styrene, ethoxymethyl styrene, Ethyloxymethylstyrene, etc., alkoxystyrene (such as methoxystyrene, 4-methoxy-3-methylstyrene, dimethoxystyrene, etc.), halogenated styrene ( For example, chlorostyrene, dichlorostyrene, trichlorostyrene, tetrachlorostyrene, pentachlorostyrene, bromophenyl , dibromostyrene, iodine styrene, fluorostyrene, trifluorostyrene, 2-bromo-4-trifluoromethylstyrene, 4-fluoro-3-trifluoromethylstyrene, etc.; acrylonitrile; A radically polymerizable compound containing a carboxylic acid (acrylic acid, methacrylic acid, itaconic acid, crotonic acid, methacrylic acid, maleic acid, p-carboxystyrene, and a metal salt or an ammonium salt compound of the acid group) Wait). From the viewpoint of the releasability, a (meth) acrylate having a hydrocarbon group having 1 to 24 carbon atoms is particularly preferable, and examples thereof include methyl ester, butyl ester, 2-ethylhexyl ester of (meth)acrylic acid, and laurel. The base ester, stearyl ester, glycidyl ester or the like is preferably a (meth) acrylate of a higher alcohol such as 2-ethylhexyl, lauryl or stearyl, and particularly preferably an acrylate.

In the present invention, the 10% thermal mass reduction temperature at which the compound having a fluorine atom is heated at 25 ° C/min at 25 ° C is preferably 250 ° C or higher, more preferably 280 ° C or higher. Further, the upper limit is not particularly limited, and is, for example, preferably 1000 ° C or lower, more preferably 800 ° C or lower. According to this aspect, it is easy to form a laminate for temporary use which is excellent in heat resistance. In addition, the 10% thermal mass reduction temperature means that the temperature before the measurement is reduced by 10% by measurement under the nitrogen gas flow rate under a nitrogen gas flow rate.

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

The alkyl group may, for example, be a linear alkyl group, a branched alkyl group or a cyclic alkyl group. The carbon number of the linear alkyl group is preferably from 2 to 30, more preferably from 4 to 30, still more preferably from 6 to 30, particularly preferably from 12 to 20. The number of carbon atoms of the branched alkyl group is preferably from 3 to 30, more preferably from 4 to 30, still more preferably from 6 to 30, particularly preferably from 12 to 20. The cyclic alkyl group may be a single ring or a polycyclic ring. The number of carbon atoms of the cyclic alkyl group is preferably from 3 to 30, more preferably from 4 to 30, still more preferably from 6 to 30, most preferably from 12 to 20. Specific examples of the linear alkyl group or the branched alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a decyl group, a decyl group, and a dodecyl group. , tetradecyl, octadecyl, isopropyl, isobutyl, t-butyl, tert-butyl, 1-ethylpentyl, 2-ethylhexyl. Specific examples of the cyclic alkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, an adamantyl group, a norbornyl group, a borneyl group, and a nonenyl group. , decahydronaphthyl, tricyclodecyl, tetracyclodecyl, indenyl, dicyclohexyl, nonenyl. The alkyl group may have a substituent. Examples of the substituent include a halogen atom, an alkoxy group, and an aromatic group. The halogen atom may, for example, be a chlorine atom, a fluorine atom, a bromine atom or an iodine atom, and is preferably a fluorine atom. The alkoxy group preferably has 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, still more preferably 1 to 10 carbon atoms. The alkoxy group is preferably a linear alkoxy group or a branched alkoxy group.

The aromatic group may be a single ring or a polycyclic ring. The carbon number of the aromatic group is preferably from 6 to 20, more preferably from 6 to 14, most preferably from 6 to 10. The aromatic group preferably has no hetero atom (for example, a nitrogen atom, an oxygen atom, a sulfur atom or the like) in the element constituting the ring. Specific examples of the aromatic ring include a benzene ring, a naphthalene ring, a pentylene ring, an anthracene ring, an anthracene ring, a heptene ring, a benzodioxan ring, an anthracene ring, a fused pentabenzene ring, an anthracene ring, and Philippine ring, anthracene ring, thick tetraphenyl ring, Ring, extended triphenyl ring, anthracene ring, biphenyl ring, pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, pyridazine Ring, anthracene ring, benzofuran ring, benzothiophene ring, isobenzofuran ring, quinolizine ring, quinoline ring, pyridazine ring, naphthyridine ring, quinoxaline ring, quinazoline ring, isoquine A porphin ring, an oxazole ring, a phenazin ring, an acridine ring, a phenanthroline ring, a thioindole ring, a benzopyran ring, a xanthene ring, a morphine ring, a phenothiazine ring, and a phenazine ring. The aromatic group may have the substituent.

The compound having a fluorine atom may be a compound containing only one lipophilic group, or may contain two or more kinds. Further, the lipophilic group may also contain a fluorine atom. That is, the compound having a fluorine atom may be a compound containing only a fluorine atom in a lipophilic group. Further, it may be a compound containing a group having a fluorine element (also referred to as a fluorine group) in addition to the lipophilic group. Preferred are compounds containing a lipophilic group and a fluorine-containing group. In the case where the compound having a fluorine atom is a compound containing a lipophilic group and a fluorine-containing group, the lipophilic group may contain a fluorine atom or may not contain a fluorine atom, and preferably the lipophilic group does not contain a fluorine atom. The compound having a fluorine atom has one or more lipophilic groups in one molecule, preferably from 2 to 100, particularly preferably from 6 to 80.

As the fluorine-containing group, a known fluorine group can be used. For example, a fluorine-containing alkyl group, a fluorine-containing alkylene group, etc. are mentioned. Further, those having a function as a lipophilic group in the fluorine-containing group are contained in the lipophilic group. The fluorine-containing alkyl group preferably has 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, still more preferably 1 to 15 carbon atoms. The fluorine-containing alkyl group may be any of a straight chain, a branched chain, and a cyclic chain. In addition, it may have an ether bond. Further, the fluorine-containing alkyl group may be a perfluoroalkyl group in which all of the hydrogen atoms are substituted with a fluorine atom. The fluorine-containing alkylene group preferably has 1 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, still more preferably 2 to 15 carbon atoms. The fluorine-containing alkylene group may be any of a straight chain, a branched chain, and a cyclic chain. In addition, it may have an ether bond. Further, the fluorine-containing alkylene group may be a perfluoroalkylene group in which all of the hydrogen atoms are substituted with a fluorine atom.

The content of the fluorine atom-containing compound is preferably from 1% by mass to 90% by mass, more preferably from 2% by mass to 80% by mass, even more preferably from 5% by mass to 70% by mass. When the fluorine content is in the above range, the peeling property is excellent. The content of the fluorine atom is defined by "{(the mass of the fluorine atom in one molecule, the mass of the fluorine atom) / the mass of all the atoms in one molecule} ́100".

A commercially available product can also be used as the compound having a fluorine atom. As a non-thermosetting compound, commercially available ones include Teflon (registered trademark) (DuPont), Tefzel (DuPont), and Fluon. (Asahi Glass Co., Ltd.), Heira (SolvaySolexis), Hailer (SolvaySolexis), Lumiflon (Asahi Glass) Company), Aflas (Asahi Glass), Cefralsoft (Central Glass), Cefralcoat (Central Glass), etc. Resin; fluoro rubber such as Viton (DuPont), Kalrez (DuPont), SIFEL (Shin-Etsu Chemical Industry Co., Ltd.); Kura Krytox (DuPont), Fomblin (Daitoku Tech), Demnum (Daikin Industries), Shafu Surflon (such as Surflon S243, etc., AGC Seimi Chemical Co., Ltd.), etc., various fluorocarbons represented by perfluoropolyether oil; or Dai-Fai FB962 Fluoride release agent such as Dairy FB series (Daikin Industrial Co., Ltd.) and Megafac series (DIC). In addition, as a compound having a fluorine atom-containing compound having a oleophilic group, for example, F-251, F-281, F-477, F- of the Megafac series manufactured by DiCai (DIC) Co., Ltd. may be mentioned. 553, F-554, F-555, F-556, F-557, F-558, F-559, F-560, F-561, F-563, F-565, F-567, F-568, F-571, R-40, R-41, R-43, R-94; or 710F, 710FM, 710FS, 710FL, 730FL, 730LM of the Ftergent series manufactured by NEOS.

In the present invention, a fluorine-containing decane coupling agent may be used as the compound having a fluorine atom. The fluorine-containing decane coupling agent is preferably a decane coupling agent, particularly preferably a fluorine-containing alkoxy decane. As a commercial item, Optool DAC-HP and Optool DSX by Daikin Industrial Co., Ltd. are mentioned.

<<<A compound containing a ruthenium atom>>> The compound containing a ruthenium atom is preferably a so-called thermosetting compound (for example, a compound which starts to harden at least at 100 ° C or higher). Further, the ruthenium atom-containing compound used in the present invention is preferably a compound having high heat resistance, and the 10% heat mass reduction temperature which is raised from 20 ° C at 20 ° C / min is preferably 250 ° C or higher, more preferably 280 ° C or higher. . Further, the upper limit is not particularly limited, and is, for example, preferably 1000 ° C or lower, more preferably 800 ° C or lower. According to this aspect, it is easy to form a temporary adhesive layer excellent in heat resistance. In addition, the mass reduction temperature means a value measured by a thermogravimetric analyzer (TGA) under a nitrogen gas flow under the above-described temperature rising conditions.

The compound containing a halogen atom may be a monomer, an oligomer, or a polymer, preferably an oligomer or a polymer. The weight average molecular weight of the compound containing a halogen atom is preferably 1,000 or more, more preferably 3,000 or more, and may be 5,000 or more, and further may be 10,000 or more. The upper limit of the weight average molecular weight is preferably 500,000 or less, more preferably 100,000 or less. The ruthenium atom-containing compound used in the present invention preferably has a decane bond, and more preferably contains a repeating unit having a decane bond represented by the following formula. [Chemical 4] In the formula, R is each independently a hydrogen atom or a substituent. The compound containing a ruthenium atom obtains a temporary adhesive composition which is more excellent in heat resistance by containing a repeating unit having a decane bond. Here, R is preferably a hydrogen atom and a monovalent hydrocarbon group having 1 to 8 carbon atoms, more preferably a hydrogen atom, an alkyl group or an aryl group, and still more preferably a hydrogen atom and an alkyl group having 1 to 3 carbon atoms. Further, the ruthenium atom-containing compound contained in the temporary adhesive composition is preferably 20% by mass or more of the repeating unit having a decane bond. The ruthenium atom-containing compound used in the present invention may further contain the following repeating unit in addition to the repeating unit having a decane bond. [Chemical 5] In the formula, R ^{1 is} each independently a hydrogen atom or a substituent, and X is an alkylene group or an extended aryl group. R ^{1 is} preferably a hydrogen atom and a monovalent hydrocarbon group having 1 to 8 carbon atoms, more preferably a hydrogen atom, an alkyl group or an aryl group, and still more preferably a hydrogen atom and an alkyl group having 1 to 3 carbon atoms. X is preferably an alkylene group having a carbon number of 1 to 3 or a phenyl group. Further, the ruthenium atom-containing compound contained in the temporary adhesive composition is preferably 80% by mass or less of the repeating unit.

As a preferable first embodiment of the ruthenium atom-containing compound used in the present invention, a crosslinkable group can be exemplified. The crosslinkable group refers to a group which forms a crosslinked structure by heating (for example, 150 ° C or higher), and specific examples thereof include a phenolic hydroxyl group, an epoxy group, an oxetanyl group, and a methylol group. And alkoxymethylol groups are preferred examples. In the first embodiment, it is preferable that the temporary adhesive composition contains a crosslinking agent that crosslinks the crosslinkable group.

The ruthenium atom-containing compound used in the first embodiment is preferably a polymer containing a repeating unit represented by the formula (21). General formula (21) [Chemical 6] In the above formula (21), R ¹ to R ⁴ each independently represent a monovalent hydrocarbon group having 1 to 8 carbon atoms, m is an integer of 1 to 100, B is a positive integer, and A is 0 or a positive integer. X is a divalent organic group containing a crosslinkable group.

R ¹ to R ⁴ are each independently preferably an alkyl group having 1 to 8 carbon atoms, more preferably a methyl group or an ethyl group, and still more preferably a methyl group. m is preferably an integer of from 3 to 80, more preferably an integer of from 8 to 60, still more preferably an integer of from 10 to 40. B is preferably an integer of 5 to 100. A is preferably an integer of 0 to 5. Further, A/B is preferably from 0 to 20, particularly preferably from 0.5 to 5. The crosslinkable group of X is preferably a phenolic hydroxyl group, an epoxy group or an oxetanyl group, and more preferably a phenolic hydroxyl group or an epoxy group. Further, X is more preferably a divalent organic group represented by the following formula (2) or formula (4).

General formula (2) [Chemical 7] In the above formula (2), Z is a divalent linking group, and preferably contains [Chemical 8] Any one or two or more combinations of divalent organic groups. n is 0 or 1, preferably 1. R ⁵ and R ⁶ each independently represent an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms. k is independently any of 0, 1, 2, preferably 0 or 1, more preferably 0.

General formula (4) [Chemical 9] In the above formula (4), V is a divalent linking group, and a preferred range of V is the same as Z in the formula (2). p is 0 or 1, preferably 1. R ⁷ and R ⁸ each independently represent an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms. h is independently any of 0, 1, 2, preferably 0 or 1, more preferably 0.

The crosslinking agent is preferably an amine condensate modified from formalin or formalin-alcohol, a melamine resin, a urea resin, and an average of two or more methylol groups in one molecule. Or a phenol compound of an alkoxymethylol group, and an epoxy compound having an average of two or more epoxy groups in one molecule, more preferably selected from an average of two or more methylol groups or alkane in one molecule. A phenolic compound of an oxyhydroxymethyl group and an epoxy compound having an average of two or more epoxy groups in one molecule.

When the crosslinkable group of the compound containing a ruthenium atom is an epoxy group, a phenol compound having an average of two or more hydroxyphenyl groups in one molecule can be preferably used. The phenol compound having an average of two or more hydroxyphenyl groups in one molecule is preferably a compound having 3 to 5 hydroxyphenyl groups in one molecule, and may be exemplified by a cresol novolak resin or α, α, α', α'-Tetrakis(4-hydroxyphenyl)-p-xylene. Examples of commercially available products include EP-6030G manufactured by Asahi Organic Materials Co., Ltd., Tris-P-PA manufactured by Honshu Chemical Co., Ltd., and TEP-TPA manufactured by Asahi Organic Industries.

When the crosslinkable group of the compound containing a ruthenium atom is a phenolic hydroxyl group, an epoxy compound having an average of two or more epoxy groups in one molecule can be preferably used. The epoxy compound having an average of two or more epoxy groups in one molecule is preferably a compound having 2 to 5 epoxy groups in one molecule, and as a commercial product, EOCN-1020, EOCN-102S can be exemplified. , EOCN-103S, XD-1000, NC-2000-L, EPPN-201, GAN, NC6000 (above is manufactured by Nippon Kayaku). Further, a crosslinking agent having the structure shown below can also be preferably used. [化10]

The amount of the crosslinking agent is preferably from 0.1 part by mass to 50 parts by mass, more preferably from 0.1 part by mass to 30 parts by mass, even more preferably from 1 part by mass to 20 parts by mass, per 100 parts by mass of the compound containing a ruthenium atom. . The crosslinking agent may be one type or two or more types. In the case of two or more types, it is preferred that the total amount is in the above range.

Further, it is preferred to prepare a catalyst in the temporary adhesive composition of the present embodiment. The catalyst is a hardening catalyst, and an acid anhydride or the like can be exemplified, and it is preferably bis(t-butylsulfonyl)diazomethane (manufactured by Wako Pure Chemical Industries, BSDM), tetrahydrophthalic anhydride (new Japanese physical and chemical manufacturing). , physicochemical acid (RIKACID) HH-A). The catalyst may be formulated in a range of 0.001 part by mass to 10 parts by mass based on 100 parts by mass of the compound containing a ruthenium atom. The catalyst may be used alone or in combination of two or more.

As a preferred second embodiment of the ruthenium atom-containing compound used in the present invention, a compound containing a ruthenium atom has a Si-H structure. Here, the Si—H structure means a structure in which at least one of the four bond bonds of a ruthenium atom is bonded to a hydrogen atom. The remaining bond of the ruthenium atom may be bonded to a hydrogen atom or may be bonded to another atom such as an oxygen atom or a carbon atom. In the second embodiment, the temporary adhesive composition preferably contains a catalyst, and a compound containing a ruthenium atom and a vinyl group in addition to the compound having the Si-H structure and containing a ruthenium atom (ie, At least one of a compound containing a ruthenium atom and a vinyl group, and another compound containing a vinyl group (that is, a compound containing no ruthenium atom and containing a vinyl group). In the second embodiment, the temporary adhesive composition preferably contains at least a compound having a Si-H structure and containing a ruthenium atom, and a compound containing a ruthenium atom and a vinyl group. Further, a compound having a Si—H structure and containing a ruthenium atom, and a compound containing a ruthenium atom and a vinyl group each preferably have a decane bond.

First, a description will be given of a state in which a compound containing a ruthenium atom has a Si-H structure. In the case where the compound containing a ruthenium atom has Si-H, it is preferred that the compound containing a ruthenium atom is represented by the following formula. [11] In the above formula, v is in the range of 0 to 1, u is in the range of 0 to 2, z is in the range of 0 to 1, and R ¹ , R ² , R ³ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ each independently represents an organic group, and when the total of (u+v+z) is 0, at least one of R ⁸ , R ⁹ and R ¹⁰ is a hydrogen atom. p is a positive integer. In the above formula, p is preferably an integer of from 1 to 100, more preferably an integer of from 20 to 80. As an example of the compound having a Si-H structure and containing a ruthenium atom, F1-3546 or 6-3570 manufactured by Dow Corning Corp. can be exemplified. The compound having a Si-H structure and containing a ruthenium atom may be used alone or in combination of two or more.

Next, a compound containing a vinyl group will be described. The vinyl group-containing compound used in the present invention may be a monomer, an oligomer, or a polymer, preferably an oligomer or a polymer, and the weight average molecular weight of the compound containing a vinyl group is preferably 1,000 or more, more preferably 3,000 or more, and may be 5,000 or more, and further may be 10,000 or more. The upper limit of the weight average molecular weight is preferably 500,000 or less, more preferably 100,000 or less. The vinyl group-containing compound preferably has a decane bond, and more preferably contains at least one of C1, C2 and C3, which are three repeating unit constituents containing a decane bond, according to the following formula E1. E1 E(C1) _m (C2) _n (C3) _o E In the formula E1, E independently represents an end-capping group, and m, n and o each independently represent a compound containing a vinyl group. The molar ratio of each of the constituent components is m in the range of 0.025 to 1.0, n is in the range of 0.0 to 0.95, and o is in the range of 0.0 to 0.60. At least one of E and (C1) contains a vinyl group.

The formula E1 is preferably represented by the following formula E2. E2 [12] In the formula E2, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ¹⁵ and R ¹⁶ each independently represent an organic group, and at least one of R ² , R ³ , R ⁴ , R ¹⁵ and R ¹⁶ Contains vinyl. R ⁶ represents a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms, v is in the range of 0 to 1, and u is in the range of 0 to 2, and m, n and o each independently represent a compound containing a vinyl group. The molar ratio of each constituent component is m in the range of 0.025 to 1.0, n is in the range of 0.0 to 0.95, and o is in the range of 0.0 to 0.60. At least one of R ² , R ³ , R ⁴ , R ¹⁵ and R ¹⁶ is preferably an aliphatic group or an aryl group containing a vinyl group. The carbon number of the aliphatic group is preferably an alkyl group having 1 to 8 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms. Further, the aryl group is preferably an aryl group having 6 to 12 carbon atoms. The vinyl group is preferably present in place of a hydrogen atom of an aliphatic group or an aryl group. As an example of such a compound, SFD-119, SFD-120, and 6-3444 manufactured by Dow Corning Corp. can be exemplified. In the second embodiment, the compounding amount of the vinyl group-containing compound is preferably 20 parts by mass to 500 parts by mass, more preferably 40 parts by mass, per 100 parts by mass of the compound having a Si—H structure and containing a ruthenium atom. 300 parts by mass. The vinyl group-containing compound may be used singly or in combination of two or more.

The catalyst used in the second embodiment will be described. In the second embodiment, the catalyst is prepared by a thermosetting reaction (especially a reaction of curing by heat of 150 ° C or more) of a compound containing a ruthenium atom and a compound containing a vinyl group. The catalyst may be selected from platinum chloride acid, a platinum-containing catalyst obtained by reacting an aliphatic unsaturated organic phosphonium compound with platinum chloride acid or platinum chloride (for example, platinum (0)-1,3-di A group of vinyl-1,1,3,3-tetramethyldioxane complexes, acetoacetate platinum, and any other transition metal catalyst that can be used in the hydrogenation of hydrazine. The amount of the catalyst to be formulated can be appropriately determined depending on the type of the catalyst or the like. The amount of the catalyst to be blended may be adjusted in a ratio of 0.01% by mass to 40% by mass based on the mass of the temporary adhesive composition, for example, in the case of blending. The catalyst may be used alone or in combination of two or more.

Further, in the second embodiment, in order to delay the start of the catalyst reaction, an inhibitor capable of interacting with the catalyst may be included. The inhibitor may be exemplified by diallyl maleate, ethynylcyclohexanol, bis(2-methoxy-1-methylethyl) maleate, and N,N,N', N'-tetramethylethylenediamine. The inhibitor may be formulated in a ratio of 0.01% by mass to 40% by mass of the catalyst. The inhibitor may be used singly or in combination of two or more.

Further, as the compound having a Si-H structure and containing a ruthenium atom described in the second embodiment, a low molecular compound can also be used. The following compounds are exemplified as the low molecular compound. [Chemistry 13] In addition, as the compound containing a ruthenium atom used in the present invention, an epoxy group-containing polymer compound described in the claim 1 of JP-A-2012-188650, and a Japanese patent can be used. The non-aromatic saturated hydrocarbon group-containing organopolyoxane described in the above-mentioned claim 1 of the Japanese Patent Publication No. 2013-82801, the contents of which are incorporated herein by reference.

The content of the ruthenium atom-containing compound in the temporary adhesive composition is preferably from 50.00% by mass to 99.9% by mass, and more preferably from 70.00% by mass to 99.99% by mass, based on the mass of the temporary adhesive composition other than the solvent. It is particularly preferably from 88.00% by mass to 99.99% by mass. When the content of the compound containing a ruthenium atom is in the above range, the adhesion and the releasability are more excellent. Further, the compound containing a ruthenium atom in the temporary adhesive composition may be used alone or in combination of plural kinds. In this case, it is preferred that the total amount of the content is the above range.

The total content of the compound containing at least one of a fluorine atom and a ruthenium atom in the temporary adhesive composition used in the present invention is preferably 0.009% by mass based on the total amount of the resin contained in the temporary adhesive composition. The above is more preferably 0.0001% by mass or more, still more preferably 0.001% by mass or more, particularly preferably 0.005% by mass or more, and particularly preferably 0.01% by mass or more. Further, the upper limit is preferably 10% by mass or less, more preferably 5% by mass or less, and still more preferably 2.5% by mass or less. When the total content of the compound containing at least one of a fluorine atom and a ruthenium atom is in the above range, the adhesion and the releasability are more excellent. In particular, in the present invention, the effect of the present invention can be attained even if the amount of the temporary adhesive composition is small, and the value is high in this point. The compound containing at least one of a fluorine atom and a ruthenium atom may be used alone or in combination of two or more. When two or more types are used together, it is preferable that the total content is the said range.

<<Antioxidant>> The temporary adhesive composition used in the present invention may contain an antioxidant from the viewpoint of preventing degradation of the elastomer or gelation due to oxidation during heating. As the antioxidant, a phenol-based antioxidant, a sulfur-based antioxidant, a phosphorus-based antioxidant, a lanthanoid 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, and "BARN" (Irganox). "1010", "Irganox 1330", "Irganox 3114", "Irganox 1035", Sumitomo Chemical (Sumilizer) ) MDP-S", "Sumilizer GA-80", etc. Examples of the sulfur-based antioxidant include 3,3'-dithiolactyl thiodipropionate, "Sumilizer TPM" manufactured by Sumitomo Chemical Co., Ltd., and "Sumi Laize ( Sumilizer) TPS", "Sumilizer TP-D", etc. Examples of the phosphorus-based antioxidant include tris(2,4-di-t-butylphenyl)phosphite, bis(2,4-di-t-butylphenyl)pentaerythritol diphosphite, Poly(dipropylene glycol) phenyl phosphite, diphenyl isodecyl phosphite, 2-ethylhexyl diphenyl phosphite, triphenyl phosphite, BASF (BASF) Irgafos 168, Irgafos 38, etc. Examples of the lanthanoid antioxidant include p-benzoquinone and 2-tert-butyl-1,4-benzoquinone. Examples of the amine-based antioxidant include dimethylaniline or phenothiazine. The antioxidant is preferably Irganox 1010, Irganox 1330, 3,3'-dithiolactyl thiodipropionate, Sumilizer TP-D, More preferably, it is Irganox 1010, Irganox 1330, and especially Irganox 1010. Further, among the antioxidants, a phenolic antioxidant, a sulfur-based antioxidant or a phosphorus-based antioxidant is preferred, and a phenolic antioxidant and a sulfur-based antioxidant are particularly preferred. In particular, when a thermoplastic elastomer having a styrene structure is used as the elastomer, it is preferred to use a phenol-based antioxidant and a sulfur-based antioxidant. By such a combination, an effect of efficiently suppressing deterioration of the elastomer due to the oxidation reaction can be expected. In the case of phenolic antioxidants and sulfur-based antioxidants, the quality of phenolic antioxidants and sulfur-based antioxidants is preferably phenolic antioxidants: sulfur-based antioxidants = 95:5 to 5:95, more preferably It is 25:75 to 75:25. As a combination of antioxidants, Irganox 1010 and Sumilizer TP-D, Irganox 1330 and Sumilizer TP-D and Sue are preferred. Sumilizer GA-80 and Sumilizer TP-D, more preferably Irganox 1010 and Sumilizer TP-D, Irganox 1330 and Sumilizer TP-D, especially good for Irganox 1010 and Sumilizer TP-D.

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

When the temporary adhesive composition has an antioxidant, the content of the antioxidant is preferably 0.001% by mass to 20.0% by mass, and more preferably 0.005% by mass to 10.0% by mass based on the total solid content of the temporary adhesive composition. . The antioxidant may be used alone or in combination of two or more. When the amount of the antioxidant is two or more, it is preferred that the total is in the above range.

<<Radical Polymerizable Compound>> The temporary adhesive composition used in the present invention preferably further contains a radical polymerizable compound. By using a temporary adhesive composition containing a radical polymerizable compound, flow deformation of the temporary adhesive layer at the time of heating can be easily suppressed. Therefore, for example, when the laminated body after polishing the substrate is subjected to heat treatment, the flow deformation of the temporary adhesive layer during heating can be suppressed, and the occurrence of warpage can be effectively suppressed. Further, since the temporary adhesive layer having hardness can be formed, even if pressure is locally applied when the substrate is polished, the temporary adhesive layer is less likely to be deformed, and the flat polishing property is excellent.

In the present invention, the radically polymerizable compound is a compound having a radical polymerizable group, and a known radically polymerizable compound which can be polymerized by a radical can be used. Such a compound is widely known in the industrial field, and it can be used without particular limitation in the present invention. These may be, for example, any of a chemical form such as a monomer, a prepolymer, an oligomer, or a mixture thereof, and a polymer of the above. As the radically polymerizable compound, the description of paragraphs 0099 to 0180 of JP-A-2015-087611 can be referred to, and the contents are incorporated in the present specification.

In addition, as a radically polymerizable compound, it is also preferable to use Japanese Patent Publication No. Sho 48-41708, Japanese Patent Laid-Open No. Sho 51-37193, Japanese Patent Laid-Open No. 2-32293, and Japanese Patent Special Fair 2 Japanese Patent Publication No. Sho-58-49860, Japanese Patent Publication No. SHO-58-17654, Japanese Patent Publication No. Sho 62-39417, and Japanese Patent Publication No. Sho 62-62 A urethane compound having an ethylene oxide skeleton as described in JP-A-39418. Further, an amino group structure or a thioether structure in the molecule described in Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. The addition polymerizable monomer is a radical polymerizable compound.

The commercially available product of the radically polymerizable compound may, for example, be a urethane oligomer UAS-10 or UAB-140 (manufactured by Sanyo Kokusaku Pulp Co., Ltd.); NK ester M-40G, NK ester. 4G, NK ester A-9300, NK ester M-9300, NK ester A-TMMT, NK ester A-DPH, NK ester A-BPE-4, UA-7200 (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.); DPHA- 40H (manufactured by Nippon Kayaku Co., Ltd.); UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoeisha Chemical Co., Ltd.); Blemmer PME400 (Nippon Oil (stock) manufacturing) and so on.

In the present invention, the radically polymerizable compound preferably has at least one of the partial structures represented by the following (P-1) to (P-4), and more preferably has the following structure. Partial structure represented by (P-3). The * in the formula is a link key.

[Chemistry 14]

Specific examples of the radically polymerizable compound having the partial structure include trimethylolpropane tri(meth)acrylate and isocyanuric acid ethylene oxide modified di(meth)acrylate. Isocyanuric acid ethylene oxide modified tris(meth)acrylate, triallyl isocyanurate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dimethylolpropane Tetrakis (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tetramethylol methane tetra (meth) acrylate, etc., in the present invention, particularly excellent These radical polymerizable compounds are used in situ.

In the temporary adhesive composition used in the present invention, free radicals are added to the mass of the temporary adhesive composition other than the solvent from the viewpoint of good adhesion, flat polishing property, peelability, and warpage. The content of the polymerizable compound is preferably from 1% by mass to 50% by mass, more preferably from 1% by mass to 30% by mass, even more preferably from 5% by mass to 30% by mass. The radically polymerizable compound may be used alone or in combination of two or more. Further, in the temporary adhesive composition used in the present invention, the mass ratio of the elastomer to the radically polymerizable compound when the radical polymerizable compound is added is preferably an elastomer: radical polymerizable compound = 98:2 - 10:90, more preferably 95:5~30:70, especially good 90:10~50:50. When the mass ratio of the elastomer and the radically polymerizable compound is in the above range, a temporary adhesive layer excellent in adhesion, flatness, releasability, and warpage can be formed.

<<Other Ingredient>> The temporary adhesive composition used in the present invention may be optionally formulated with various additives such as a surfactant having no fluorine atom and a halogen atom, and plastic, insofar as the effects of the present invention are not impaired. A chemical agent, a hardener, a catalyst other than the above, a filler, a adhesion promoter, an ultraviolet absorber, an anti-agglomeration agent, an elastomer or other polymer compound. When these additives are blended, the blending amount thereof is preferably 3% by mass or less, and more preferably 1% by mass or less, based on the total solid content of the temporary adhesive composition. The lower limit of the blending time is preferably 0.0001% by mass or more. In addition, the total amount of the additives is preferably 10% by mass or less, and more preferably 3% by mass or less based on the total solid content of the temporary adhesive composition. The lower limit of the total amount of the ingredients to be blended is preferably 0.0001% by mass or more.

The temporary adhesive composition used in the present invention preferably contains no impurities such as metal. The content of the impurities contained in the materials is preferably 1 ppm by mass or less, more preferably 1 mass ppb or less, still more preferably 100 masses or less, more preferably 10 masses or less, and particularly preferably substantially Not included (below the detection limit of the measuring device). As a method of removing impurities such as metal from the temporary adhesive composition, for example, filtration using a filter is mentioned. The filter pore diameter is preferably a pore diameter of 10 nm or less, more preferably 5 nm or less, and still more preferably 3 nm or less. The material of the filter is preferably a filter made of polytetrafluoroethylene, polyethylene or nylon. The filter can be cleaned beforehand using an organic solvent. In the filter filtration step, a plurality of filters can be used in series or in parallel. In the case of using a variety of filters, filters with different apertures and/or materials can be used in combination. In addition, various materials may be filtered multiple times, and the step of multiple filtration may also be a cyclic filtration step. In addition, as a method of reducing impurities such as a metal contained in the temporary adhesive composition, a method of selecting a raw material having a small metal content as a raw material constituting the temporary adhesive composition and a raw material constituting the temporary adhesive composition may be mentioned. Filter filtration is carried out; distillation is carried out under conditions in which polytetrafluoroethylene is equal to the inner liner formed in the apparatus to inhibit contamination as much as possible. The preferred conditions for filter filtration of the raw materials constituting the temporary adhesive composition are the same as those described above. In addition to filter filtration, the adsorbent material may be used for impurity removal, and a filter may be used in combination to filter and adsorb the material. As the adsorbent, a known adsorbent can be used. For example, an inorganic adsorbent such as tannin, zeolite or activated carbon, or an organic adsorbent can be used.

<Preparation of Temporary Adhesive Composition> The temporary adhesive composition used in the present invention can be prepared by mixing the above components. The mixing of the components is usually carried out in the range of 0 °C to 100 °C. Moreover, after mixing each component, it is preferable to filter by a filter, for example. Filtration can be carried out in multiple stages, or it can be repeated multiple times. Alternatively, the filtered liquid can be refiltered. The filter is not particularly limited as long as it is a filter used for filtration applications or the like. For example, a fluororesin such as polytetrafluoroethylene (PTFE), a polyamide resin such as nylon-6 or nylon-6,6, or a polyolefin resin such as polyethylene or polypropylene (polypropylene) may be used. A filter for raw materials such as density, ultra-high molecular weight polyolefin resin). Among these raw materials, polypropylene (containing high density polypropylene) and nylon are preferred. The pore diameter of the filter is, for example, suitably from about 0.003 μm to about 5.0 μm. By setting it as this range, it is possible to suppress the clogging of the filter, and it is possible to surely remove fine foreign matter such as impurities or aggregates contained in the composition. When using a filter, different filters can be combined. At this time, the filtration using the first filter may be performed only once, or may be performed twice or more. In the case where two or more filtrations are performed by combining different filters, it is preferred that the pore diameter after the second time is the same as the pore diameter of the first filtration or smaller than the pore diameter of the first filtration. In addition, a first filter of different pore sizes may also be combined within the range. The aperture here can be referred to the nominal value of the filter manufacturer. As a commercially available filter, for example, from PALL Co., Ltd., Advantec Toyo Co., Ltd., and Japan's Entegris Co., Ltd. (formerly Japan's Miikeri ( Choose from various filters offered by Mykrolis) or Kitz Microfilter Co., Ltd.

The semiconductor element obtained in the present invention can make the moving distance of the position before the pressure bonding at the temperature T1 of the crystal grain and the position after the pressure contact at the temperature T1 of the crystal grain less than 100 μm, and the moving distance can be made smaller than 50 μm, in particular, the moving distance can be less than 30 μm. Regarding the lower limit value, it is preferably 0 μm, but 3 μm or more is also a practical level. [Examples]

Hereinafter, the present invention will be specifically described by way of examples, and the present invention is not limited to the following examples, without departing from the spirit of the invention. In addition, unless otherwise indicated, "part" and "%" are the quality standards.

<Preparation of Temporary Adhesive Composition> The following compositions were mixed and filtered using a filter made of polytetrafluoroethylene having a pore diameter of 5 μm to prepare a temporary adhesive composition, respectively. <<Component of temporary adhesive composition>> - The resin described in Table 1 Irganox 1010 (manufactured by BASF): 1 part by mass · Sumilizer TP-D ( Sumitomo Chemical Co., Ltd.): 1 part by mass · Megafac F-557 (manufactured by Diane Health (DIC) Co., Ltd.): 0.3 parts by mass · Solvent (Third butylbenzene (Toyo Synthetic Industry Co., Ltd.) Manufacture)): Parts by mass as shown in Table 1

The composition of the temporary adhesive composition used in each of the examples is shown below. [Table 1] The compounds described in Table 1 are as follows.

<Measurement of Melt Viscosity> The melt viscosity of the temporary adhesive layer was measured by the following method. The temporary adhesive composition was cast in a PFA dish of 20 mm in diameter and dried for 3 days, then heated at 190 ° C for 5 minutes, and recovered from the dish to obtain a diameter of 20 mm and a thickness of 300 μm. Sample for evaluation. The sample for evaluation was measured at a temperature increase rate of 10 ° C/min and a measurement frequency of 10 Hz, T1 and T2 using ARES-RDA (manufactured by TA Instruments).

<Example 1 to Example 9, Example 12 to Example 15, and Comparative Example 1 to Comparative Example 3> As a carrier substrate, a crucible wafer having a diameter of 12 Å (1 吋 is 2.54 cm) was used, and on the surface thereof, A temporary adhesive layer was formed by a wafer bonding apparatus (Synapse V, manufactured by Tokyo Electron Co., Ltd.). Specifically, the temporary adhesive composition was applied onto a carrier substrate, and heated at 160 ° C for 3 minutes using a hot plate, and further heated at 190 ° C for 3 minutes to form a temporary adhesive layer on the carrier substrate. The film thickness of the temporary adhesive at this time was 40 μm. On the surface of the carrier substrate on which the temporary adhesive layer is formed, a flip chip bonder (TFC) is used for a germanium wafer (thickness 775 μm) which is cut into 10 mm × 10 mm as a crystal grain. -3000, manufactured by Shibaura MECHATRONICS Co., Ltd., at a temperature (T1) shown in Table 3, was pressed for 2 seconds so that the pressure applied to the crystal grains was 0.1 MPa.

Regarding the obtained laminate, the grain displacement was evaluated as follows. <Evaluation 1: Grain Shift> For the moving distance of the apex of the crystal grains in the laminated body (the design value of the coordinates of the vertex - the coordinate of the vertex after mounting |), the wafer automatic visual inspection device (God) is used. Condor 203, manufactured by Camtek Co., Ltd., measured the four vertices of all the crystal grains, and evaluated the sum of the moving distances of the vertices of each crystal grain by the following reference. Furthermore, the coordinates of the vertices of the design values coincide with the coordinates of the vertices before the crimping, and the coordinates of the vertices after the mounting refer to the coordinates of the vertices after the crimping. A: less than 30 μm B: 30 μm or more and less than 50 μm C: 50 μm or more and less than 100 μm D: 100 μm or more

On the surface of the laminate in which the crystal grains are provided, a compression molding machine (WCM-300, manufactured by APIC YAMADA Co., Ltd.) is used, and the temperature (T2) conditions shown in Table 3 are used. 90 seconds for a semiconductor sealing epoxy resin molding material (sumikon EME-G770H, Sumitomo Bakelite) manufactured as a molding resin composition at a pressure of 80 ^{́10 5} Pa Compression molding. Thereafter, it was further heated at 175 ° C for 6 hours. Further, in Example 10, CEL-9200 HF10 (manufactured by Hitachi Chemical Co., Ltd.) was used as a molding resin composition, and in Example 11, KE-300TS-1 (Kyocera Chemical Co., Ltd.) was used as a molding resin. The molding was carried out in the same manner as in Example 1 except for the composition. [table 3]

Regarding the obtained laminate, the warpage was evaluated as described below. <Evaluation 2: Warpage> The warpage in the laminate was measured by fixing a film thickness sensor (manufactured by KEYENCE Co., Ltd., ST-T80) to an X-Y stage. In the measurement, the X direction (substrate surface direction) and the Y direction (the direction orthogonal to the X direction in the substrate surface direction) are defined, and the measurement is performed every 0.1 mm in the X direction, and every 1 mm in the Y direction. The warpage was defined as the difference between the maximum value and the minimum value of all the measurement points, and was evaluated by the following criteria. A: less than 250 μm B: 250 μm or more and less than 500 μm C: 500 μm or more and less than 750 μm D: 1000 μm or more

<Evaluation 3: Peelability> The formed layer of the obtained laminate was set to the lower side, and the lower crucible wafer was fixed to the center of the dicing tape together with the dicing frame using a dicing tape mounting machine. Thereafter, the upper side germanium wafer was oriented in a vertical direction with respect to the lower molding layer at 25 ° C by a wafer bonding apparatus (manufactured by Tokyo Electron Co., Ltd., Synapse Z). The speed of 50 mm/min was pulled up to peel off the upper wafer. Next, the temporary adhesive layer laminated on the surface of the molded resin was pulled up at a speed of 50 mm/min in the vertical direction at 25 ° C, and the peeling force at this time was evaluated by the following criteria. Further, the peeling force was measured using a dynamometer (manufactured by Imada, ZTS-100N). A: peeling at less than 30 N B: peeling at 30 N or more and less than 50 N C: peeling at 50 N or more D: peeling is impossible

[Table 4]

10‧‧‧ Carrier substrate
20‧‧‧ Temporary adhesive layer
30‧‧‧ grain
40‧‧‧Forming layer

(A1) to (A5) of FIG. 1 are schematic views showing an embodiment of a method of manufacturing a semiconductor device of the present invention.

10‧‧‧ Carrier substrate

20‧‧‧ Temporary adhesive layer

30‧‧‧ grain

40‧‧‧Forming layer

Claims (7)

A method of manufacturing a semiconductor device, wherein a member having a temporary adhesive layer on a carrier substrate and a die having a circuit on at least one surface are crimped at a temperature T1 so that the temporary adhesive layer is in contact with the die. And forming a molding layer at a temperature T2 on a surface on the opposite side of the side of the crystal grain that is in contact with the temporary adhesive layer, and then peeling the carrier substrate at a temperature of 40 ° C or lower; here, the temperature T1 is The melt viscosity of the temporary adhesive layer measured at a measurement frequency of 10 Hz is a temperature of 4000 Pa·s or more and 10000 Pa·s or less, and the temperature T2 is the temporary adhesive layer measured at a measurement frequency of 10 Hz. The melt viscosity is a temperature of 4000 Pa·s or more. The method for producing a semiconductor device according to claim 1, wherein the forming layer is formed by heat treatment at 100 ° C or higher. The method for producing a semiconductor device according to claim 1 or 2, wherein after the carrier substrate is peeled off at a temperature of 40 ° C or lower, the temporary adhesive layer is further removed at 40 ° C or lower. . The method for producing a semiconductor device according to the above aspect, wherein the temporary adhesive layer comprises at least one selected from the group consisting of a thermoplastic elastomer having a styrene structure, a cycloolefin polymer, and an acrylic resin. One. The method of producing a semiconductor device according to the above aspect, wherein the molding layer comprises an epoxy resin. The method for producing a semiconductor device according to the first or second aspect of the invention, wherein the position before the crimping at the temperature T1 of the crystal grain and the position after the crimping at the temperature T1 of the crystal grain The moving distance is less than 100 μm. The method for producing a semiconductor device according to the first or second aspect of the invention, wherein the temporary adhesive layer contains at least one of a fluorine atom and a germanium atom.