TWI671831B - Semiconductor component manufacturing method - Google Patents

Abstract

A method for manufacturing a semiconductor element, comprising: crimping a component having a temporary adhesive layer on a carrier substrate and a crystal grain having a circuit on at least one side in a manner that the temporary adhesive layer is in contact with the crystal grain at a temperature T1, And forming a forming layer at a temperature T2 on the surface of the crystal grain on the side opposite to the side where the temporary adhesive layer is in contact, 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 became 4000 Pa. s or more and 10000Pa. The temperature is below s, and the temperature T2 is that the melt viscosity of the temporary adhesive layer measured at a measurement frequency of 10 Hz becomes 4000 Pa. temperature above s.

Description

Manufacturing method of semiconductor element

The present invention relates to a method for manufacturing a semiconductor element and a method for manufacturing a laminated body.

Semiconductor devices are sometimes used by forming a molding layer on a die having a circuit on the surface and packaging it. As one of the methods for manufacturing such a packaged semiconductor device, a method is known in which a temporary adhesive layer is formed on a carrier substrate and crystal grains are arranged on the formed temporary adhesive layer, and then the temporary A molding layer is formed on the adhesive layer, and the carrier substrate is peeled off (for example, Patent Documents 1 to 4).

[Prior Art Literature]

[Patent Literature]

[Patent Document 1] US Patent No. 7202107

[Patent Document 2] US Patent No. 9082806

[Patent Document 3] Japanese Patent Laid-Open No. 2013-168417

[Patent Document 4] Japanese Patent Laid-Open No. 2001-308116

However, it has been known that if the crystal grains are arranged on the surface of the temporary adhesive layer as described in the aforementioned patent document, and a molding layer is formed on the surface of the temporary adhesive layer, then When the crystal grains are crimped to the temporary adhesive layer, crystal grain displacement becomes a problem, or there is a problem in the peelability between the temporary adhesive layer and the molding layer.

The present invention has been made to solve the above problems, and an object thereof is to provide a method for producing a semiconductor element and a method for producing a laminated body, which effectively suppress crystal grain displacement and have excellent peelability of a temporary adhesive layer and a molding layer.

Based on the above-mentioned situation, the present inventors conducted research, and as a result, it was found that the reason for the problem of crystal grain displacement or peelability was that the temporary adhesive layer was caused by heating during the compression bonding of the crystal grains or the formation of the molding layer. Melting. In addition, it has been found that the problem can be solved by increasing the melt viscosity of the temporary adhesive layer at the time of pressure bonding of the crystal grains or at the time of forming the formed layer. Specifically, the problem is solved by the following means <1>, preferably <2> to <7>.

<1> A method for manufacturing a semiconductor element, wherein a component having a temporary adhesive layer on a carrier substrate and a crystal grain having a circuit on at least one side are connected at a temperature T1 such that the temporary adhesive layer is in contact with the crystal grain. Press down and form a forming layer at a temperature T2 on the surface of the crystal grain on the side opposite to the side where the temporary adhesive layer is in contact, and then peel the carrier substrate at a temperature below 40 ° C; here The temperature T1 is that the melt viscosity of the temporary adhesive layer measured at a measurement frequency of 10 Hz becomes 4000 Pa. s or more and 10000Pa. The temperature is below s, and the temperature T2 is that the melt viscosity of the temporary adhesive layer measured at a measurement frequency of 10 Hz becomes 4000 Pa. temperature above s.

<2> The method for manufacturing a semiconductor device according to <1>, wherein After forming the mold layer, heat treatment at 100 ° C or higher is performed.

<3> The method for manufacturing a semiconductor device according to <1> or <2>, wherein the carrier substrate is peeled at a temperature of 40 ° C. or lower, and then the temporary adhesive layer is removed at 40 ° C. or lower. .

<4> The method for manufacturing a semiconductor device according to any one of <1> to <3>, wherein the temporary adhesive layer includes a thermoplastic elastomer having a styrene structure, a cycloolefin polymer, and acrylic acid. At least one of resins.

<5> The method for manufacturing a semiconductor element according to any one of <1> to <4>, wherein the molding layer includes an epoxy resin.

<6> The method for manufacturing a semiconductor element according to any one of <1> to <5>, wherein the position before the crimping at the temperature T1 of the crystal grains and the pressure at the temperature T1 of the crystal grains The moving distance of the following position is less than 100 μm.

<7> The method for manufacturing a semiconductor device according to any one of <1> to <6>, wherein the temporary adhesive layer contains at least one of a fluorine atom and a silicon atom.

According to the present invention, it is possible to provide a method for producing a semiconductor element and a method for producing a laminated body, which are effective in suppressing crystal grain displacement and have excellent peelability of a temporary adhesive layer and a molding layer.

10‧‧‧ carrier substrate

20‧‧‧ temporary adhesive layer

30‧‧‧ Grain

40‧‧‧forming layer

FIGS. 1 (A1) to 1 (A5) are schematic views showing an embodiment of a method for manufacturing a semiconductor element according to the present invention.

Hereinafter, the content of this invention is demonstrated in detail. In addition, in this specification, "~" is used in the meaning which includes the numerical value described before and after it as a lower limit and an upper limit.

In the description of the group (atomic group) in the present specification, the descriptions of the substituted and unsubstituted expressions include a group (atomic group) having no substituent, and also include a group (atomic group) having a substituent. For example, the "alkyl group" includes not only an alkyl group (unsubstituted alkyl group) having no substituent, but also an alkyl group (substituted alkyl group) having a substituent.

In this specification, "(meth) acrylate" means acrylate and methacrylate, "(meth) acrylic" means acrylic and methacrylic, and "(meth) acryl" refers to "acryl" "And" methacrylfluorenyl. "

In this specification, a weight average molecular weight and a number average molecular weight are defined as the polystyrene conversion value measured by the gel permeation chromatography (GPC). In this specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) can be, for example, HLC-8220 (manufactured by Tosoh Co., Ltd.) and TSKgel Super AWM-H (Tosoh) (Manufactured), 6.0 mm (inner diameter) × 15.0 cm) was used as a column, and a 10 mmol / L lithium bromide N-methyl pyrrolidinone (NMP) solution was used as a washing solution.

Unless otherwise stated, the thickness and the like in the present invention are those that mean the average thickness.

The method for manufacturing a semiconductor device according to the present invention is characterized in that: A component having a temporary adhesive layer on a substrate and a die having a circuit on at least one side are crimped at a temperature T1 in a manner that the temporary adhesive layer is in contact with the die, and the die is temporarily bonded to the die. A surface on the opposite side of the side where the agent layers are in contact is formed at a temperature T2, and then the carrier substrate is peeled off at a temperature of 40 ° C or lower.

Here, the temperature T1 is that the melt viscosity of the temporary adhesive layer measured at a measurement frequency of 10 Hz becomes 4000 Pa. s or more and 10000Pa. The temperature is below s, and the temperature T2 is that the melt viscosity of the temporary adhesive layer measured at a measurement frequency of 10 Hz becomes 4000 Pa. temperature above s. This laminated body can be provided with a larger area of redistribution (RDL: Redistribution layer) than the wafer size, so it can be better used for fan-out wafer level featuring no substrate and low backing. In a package (Fan-out Wafer Level Package, FOWLP).

With such a configuration, a method for manufacturing a semiconductor element or a laminate having excellent peelability can be provided. In other words, conventionally, a molding layer has been formed on the surface of a temporary adhesive layer to manufacture a laminated body such as a semiconductor element. However, it has been known that the peelability of the temporary adhesive layer and the molded layer may be deteriorated in the previous manufacturing method. The present inventors have studied the reason, and as a result, they have found the following problem: a forming layer is formed after a temporary adhesive layer is provided, but the temporary adhesive layer is melted due to heating during the formation of the forming layer, and the forming layer is constituted The resin and the resin constituting the temporary adhesive layer are mixed in the surface layer. Therefore, in the present invention, the melt viscosity of the temporary adhesive layer when the molding layer is formed is set to 4000 Pa. s or more to avoid this point.

Furthermore, it has been known that crystal grains having a circuit are provided between the temporary adhesive layer and the molding layer. However, when the crystal grains are aligned and pressed on the surface of the temporary adhesive layer, the In some cases, the temporary adhesive layer is melted and the crystal grains are displaced due to heating when the crystal grains are pressed against the temporary adhesive layer. In the present invention, a component having a temporary adhesive layer on a carrier substrate and a crystal having a circuit on at least one side are crimped at a temperature T1 in a manner that the temporary adhesive layer and the crystal are in contact with each other. Inhibit grain shift.

By suppressing the displacement of the crystal grains, the pitch between the crystal grains is less likely to vary, and a semiconductor element can be manufactured with high accuracy.

In addition, a large pressure is also applied when the forming layer is formed, but the pressure is uniformly applied to the temporary adhesive layer of the crystal grains and the portion having no crystal grains. Therefore, it is estimated that there is almost no crystal grain shift during the formation of the molding layer. The impact.

Hereinafter, the manufacturing method of the semiconductor element of the present invention will be described as an example, but the same applies to the manufacturing method of the laminated body of the present invention.

A method for manufacturing a semiconductor element according to 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 a carrier substrate 10.

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

The temporary adhesive layer 20 can be formed using the temporary adhesive composition mentioned 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 doctor blade coating method, a screen printing method, and a dip coating method. Buffa and so on. Alternatively, a method may be used in which the temporary adhesive composition is extruded from the slit-shaped opening under pressure to apply the temporary adhesive composition to the carrier substrate 10. In addition, in (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 formed into a film in advance, and the film may be formed on the carrier substrate 10 by lamination.

In addition, the temporary adhesive layer may be only one layer, or may be two or more layers. For example, the laminated body in the present invention may have a structure including a carrier substrate / a first temporary adhesive layer / a second temporary adhesive layer / a die-forming layer.

The application amount of the temporary adhesive composition is, for example, preferably an application amount in which the average film thickness of the temporary adhesive layer after drying is 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, and more preferably 200 μm or less.

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

In the above-mentioned embodiment, the member having a temporary adhesive layer on the carrier substrate may have another layer within a range not departing from the gist of the present invention. Examples of the other layer include a layer called a release layer, a release layer, and a release layer. As a release layer, For example, reference can be made to the descriptions of paragraphs 0025 to 0055 in Japanese Patent Laid-Open No. 2014-212292, which are incorporated into this specification. In addition, as the separation layer, the descriptions in paragraphs 0069 to 0124 of the manual WO2013-065417 can be referred to, and these contents are incorporated into this specification.

However, in the present invention, it is preferable to have a temporary adhesive layer on the surface of the carrier substrate.

Next, as shown in FIG. 1 (A2), the crystal grains 30 are arranged on the temporary adhesive layer 20 by pressure bonding.

The die 30 has a circuit on at least one surface, and preferably has a circuit on only one surface. Examples of the crystal grain include wafer wafers including silicon, sapphire, silicon carbide (SiC), gallium arsenide (GaAs), gallium phosphide (GaP), and gallium nitride (GaN).

In the present invention, as for the pressure bonding of the crystal grains 30, it is preferable that the melt viscosity of the temporary adhesive layer measured at a measurement frequency of 10 Hz becomes 4000 Pa. s or more and 10000Pa. Compression bonding is performed at a temperature T1 of s or less. The temperature T1 is preferably such that the melt viscosity of the temporary adhesive layer becomes 4300Pa. s ~ 9800Pa. The temperature of s is more preferably that the melt viscosity of the temporary adhesive layer becomes 4500Pa. s ~ 9700Pa. s temperature.

The temperature T1 is not particularly limited, and may be set to 100 ° C to 300 ° C (the lower limit is preferably 130 ° C or higher, more preferably 160 ° C or higher, the upper limit is preferably 260 ° C or lower, more preferably 240 ° C or lower, and even more It is preferably in the range of 180 ° C or lower).

The compression bonding is preferably performed under the condition that the pressure applied to the crystal grains 30 is 0.001 MPa to 10 MPa, and more preferably 0.01 MPa to 5 MPa. The crimping time is preferably 0.1 to 15 seconds, and more preferably 0.5 to 10 seconds.

Next, as shown in FIG. 1 (A3), a molding layer is formed at a temperature T2 on the surface of the crystal grain 30 on the side opposite to the side where the temporary adhesive layer 20 is in contact. As shown in FIG. 1, the molding layer is disposed on the crystal grains and temporarily adheres to the surface of the agent layer. The molding layer is preferably covered in a manner of sealing the crystal grains, but the case where it is not completely covered is of course also included in the scope of the present invention. In addition, the molding layer does not have to be a complete layer, and for example, a state in which it 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.

Regarding the temperature T2 when the forming layer was formed, the melt viscosity of the temporary adhesive layer measured at a measurement frequency of 10 Hz was 4000 Pa. Perform at temperatures above s. If the temperature T2 is temporary, the melt viscosity of the adhesive layer becomes 4000Pa. For temperatures above s, the upper limit of the melt viscosity is not particularly specified, and it is preferable that the melt viscosity of the temporary adhesive layer becomes 4300Pa. s ~ 15000Pa. The temperature of s is more preferably that the melt viscosity of the temporary adhesive layer becomes 4500Pa. s ~ 12000Pa. s temperature.

The temperature T2 is not particularly specified, but is preferably 20 ° C to 300 ° C (preferably 100 ° C to 260 ° C, more preferably 130 ° C to 260 ° C, and even more preferably 160 ° C to 240 ° C).

In addition, in the present invention, the melt viscosity of the temporary adhesive layer at temperature T1 is preferably higher than the melt viscosity of the temporary adhesive layer at temperature T2, and the melt viscosity of the temporary adhesive layer at temperature T1 is preferably lower than the temperature. The melting viscosity of the temporary adhesive layer under T2 is 30Pa higher. s or more.

By setting it as such a range, it is more difficult to cause a crystal grain shift, and it is preferable. It is even more preferred that the melt viscosity of the temporary adhesive layer at temperature T1 is preferably 30 Pa higher than the melt viscosity of the temporary adhesive layer at temperature T2. s ~ 600Pa. s.

A die is also called a wafer and has a circuit on at least one side. The die is usually provided with a circuit on the surface of the substrate. Examples of the substrate include a silicon substrate. The crystal grain is, for example, a quadrangle having a surface area of a substrate of crystal grains of about 1 mm ² to 500 mm ² . The main idea of the quadrangle here is to include those that are generally quadrangular in addition to the quadrilateral in the mathematical sense. The quadrangular shape is generally rectangular. It is usually obtained by cutting and separating a substrate formed on a semiconductor wafer such as a silicon wafer.

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

Examples of the curable resin include novolac-type phenol resins such as phenol novolac resin, cresol novolac resin, bisphenol A novolac resin, phenol resins such as soluble phenol resin (resole) -type phenol resin, and phenol novolac Type epoxy resin, cresol novolac 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 epoxy resin, stilbene epoxy resin, trisphenol methane epoxy resin, alkyl modified trisphenol methane epoxy resin, triazine core-containing epoxy resin, dicyclopentane Diene modified phenol type epoxy resin, naphthol type epoxy resin, naphthalene type epoxy resin, phenol aralkyl type epoxy resin having phenylene and / or biphenyl group, / Or epoxy resins such as aralkyl epoxy resins such as naphthol aralkyl epoxy resins with biphenyl skeleton, resins with triazine rings such as urea resins and melamine resins, unsaturated polyesters Resin, bis-cis butylene diimide resin, polyurethane resin Grease, diallyl phthalate resin, silicone resin, with benzene The oxazine ring-containing resin, cyanate resin and the like may be used alone or in combination. The term "epoxy resin" used herein refers to the entire monomer, oligomer, and polymer having two or more epoxy groups in one molecule. Among these, epoxy resin is preferable. This improves electrical characteristics. Furthermore, even if a large amount of inorganic filler is added, moldable fluidity can be maintained.

In particular, as a preferred embodiment, a resin using epoxy resin as a main component of the molding layer 40 and a resin using a styrene-based elastomer as a main component of the temporary adhesive layer 20 are exemplified. By using such a combination, high peelability of the laminated body can be achieved, which is preferable. The resin of the main component herein refers to a component having the largest content among the resin components 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 it is preferably 3% to 30% by mass of the entire molding layer, and particularly preferably 5% to 20% by mass. When the content is at least the lower limit value, a decrease in fluidity can be suppressed, and the sealing of the crystal grains 30 can be made better. Moreover, by making it into the said upper limit or less, the fall of solder heat resistance can be suppressed effectively. The resin may be used alone or in combination of two or more.

Examples of the hardener include aliphatic polyamines such as diethylene triamine (DETA), triethylene tetramine (TETA), and meta-xylylene diamine (MXDA), and diamine groups. In addition to aromatic polyamines such as diamino diphenyl methane (DDM), m-phenylene diamine (MPDA), and diamino diphenyl sulfone (DDS), examples include: Dicyandiamide DICY), amine-based hardeners such as polyamine compounds such as organic acid dihydrazine, phenol-based hardeners such as novolac phenol resins, phenol polymers (hardeners with phenolic hydroxyl groups), and hexahydrophthalic anhydride (hexahydrophthalic anhydride (HHPA)), methyl tetrahydrophthalic anhydride (MTHPA) and other cyclic fatty acid anhydrides (liquid acid anhydride), trimellitic anhydride (TMA), pyromellitic acid dihydrate Anhydride hardeners such as aromatic anhydrides (pyromellitic dianhydride (PMDA), benzophenone tetracarboxylic dianhydride (BTDA), etc.), polyamide resins, and polysulfide resins.

When using the said epoxy resin as a resin, hardening | curing agent is not specifically limited, It is preferable to use the hardening | curing agent which has a phenolic hydroxyl group. A hardener having a phenolic hydroxyl group is easier to control the reaction of the resin than other hardeners, and therefore, it is possible to ensure good fluidity when manufacturing a semiconductor device. Moreover, since the hardening | curing agent which has a phenolic hydroxyl group is easy to control reactivity, high filling of an inorganic filler can also be achieved. Therefore, excellent reliability of the semiconductor element can be ensured. The curing agent having a phenolic hydroxyl group here is a monomer, an oligomer, and 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 include modification of novolac-type phenol resins such as phenol novolac resin, cresol novolac resin, triphenol methane-type phenol resin, terpene-modified phenol resin, and dicyclopentadiene-modified phenol resin. Phenol resins, aralkyl-type phenol resins, such as phenol aralkyl resins having a phenylene and / or biphenyl group, naphthol aralkyl resins having a phenylene and / or biphenyl group, These may be used alone or in combination.

The content of the hardener is not particularly limited, but is preferably 2% by mass to 10% by mass of the entire molding layer, and particularly preferably 4% by mass to 7% by mass. The hardener may be used alone or in combination of two or more.

In addition, when the resin is an epoxy resin, as the curing agent, a curing agent having a phenolic hydroxyl group can be preferably used. In this case, the epoxy group of the epoxy resin and the curing having a phenolic hydroxyl group are used. The equivalent ratio of the phenolic hydroxyl group (epoxy group / 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 curability and moisture resistance reliability are particularly excellent.

It is preferable to contain an inorganic filler in a molding layer. Examples of the inorganic filler include silicates such as talc, calcined clay, uncalcined clay, mica, and glass; titanium oxide, aluminum oxide, and fused silica (spherical fused silica, crushed fused silica). Silicon dioxide), oxides such as crystalline silicon dioxide, and other silicon dioxide powders; carbonates such as calcium carbonate, magnesium carbonate, and hydrotalcite; hydroxides such as aluminum hydroxide, magnesium hydroxide, and calcium hydroxide; barium sulfate, calcium sulfate, Sulfates or sulfites such as calcium sulfite, borates such as zinc borate, barium metaborate, aluminum borate, calcium borate, and sodium borate; nitrides such as aluminum nitride, boron nitride, and silicon nitride. The inorganic fillers can be used alone or in combination. Among these, fused silicon dioxide, crystalline silicon dioxide, and the like are also preferred, and spherical fused silica is particularly preferred. Thereby, heat resistance, moisture resistance, strength, etc. can be improved. The shape of the inorganic filler is not particularly limited, it is preferably spherical, and preferably has a wide particle size distribution. Thereby, especially the fluidity | liquidity of a molding resin composition can be improved. Furthermore, the surface of the inorganic filler may be surface-treated with a coupling agent.

The content of the inorganic filler contained in the molding layer is not particularly limited, but it is preferably 20% to 95% by mass of the entire molding resin composition, and particularly preferably 30% to 90% by mass. If the content is greater than or equal to the lower limit value, a decrease in moisture resistance is suppressed, and if it is less than or equal to the upper limit value, good fluidity can be maintained. Only one type of inorganic filler may be used, or two or more types may be used.

In addition, as long as the object of the present invention is not impaired, diazabicyclic olefins such as 1,8-diazabicyclo [5,4,0] undecene-7 and derivatives thereof may be added to the molding layer. Amine compounds such as tributylamine and benzyldimethylamine, imidazole compounds such as 2-methylimidazole, organic phosphines such as triphenylphosphine and methyldiphenylphosphine, tetraphenylphosphonium. Tetraphenylborate, tetraphenylphosphonium. Tetrabenzoic acid borate, tetraphenylphosphonium. Tetranaphthoic acid borate, tetraphenylphosphonium. Tetranaphthylmethyloxyborate, tetraphenylphosphonium. Tetranaphthyloxyborate and other tetra-substituted hydrazones. Hardening accelerators such as tetra-substituted borate, silane coupling agents such as epoxy silane, mercapto silane, amine silane, alkyl silane, ureido silane, vinyl silane, or titanate coupling agent, aluminum coupling agent, aluminum / Coupling agents such as zirconium coupling agents, colorants such as carbon black and iron oxide (bengala), natural waxes such as carnauba wax, synthetic waxes such as polyethylene wax, higher fatty acids such as stearic acid or zinc stearate, and metal salts thereof , Release agents such as paraffin, low stress components such as silicone oil and silicone rubber, flame retardants such as brominated epoxy resins or antimony trioxide, aluminum hydroxide, magnesium hydroxide, zinc borate, zinc molybdate, phosphazene, etc. Additives such as bismuth hydrate and inorganic ion exchangers. These components may be used alone or in combination of two or more.

As a commercially available product of the molding layer, Sumikon EME-G750 series manufactured by Sumitomo Bakelite, Sumikon (sumikon) EME-G760 series, Sumikon EME-G770 series, Sumikon EME-G790 series, CEL series manufactured by Hitachi Chemical, R4000 series manufactured by Nagase chemteX, Han GR series manufactured by Henkel, KE series manufactured by Kyocera Chemical, etc.

The thickness of the molding layer 40 is preferably 100 μm or more at the thinnest portion, and more preferably 1000 μm or more. The upper limit of the thickness is preferably 3,000 μm or less at the thinnest portion, and more preferably 5,000 μm or less.

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

In addition, in the present invention, when the molding layer 40 is formed, a state in which a molten resin is used may be adopted. In this case, the viscosity of the molded resin composition when covering the crystal grains 30 is preferably 3.0 Pa. s ~ 20.0Pa. s around.

In the case of using a molten resin, the molded resin composition is, for example, a raw material that is sufficiently and uniformly mixed using a mixer, etc., and further melt-kneaded by a kneading machine such as a hot roll, a kneader, or an extruder, and pulverized after cooling. obtain.

The viscosity at the time of sealing with a molded resin composition is not particularly limited, but is preferably 3.0 Pa. s or more, more preferably 5.0Pa. s or more. On the other hand, the viscosity is preferably 30.0Pa. Below s, more preferably 20.0Pa. s or less. This can suppress generation of voids. The viscosity can be obtained, for example, with a high-performance flow tester. For molding resin After the product is sealed, the molded resin composition is cured. As a method of hardening a molded resin composition, the method of heating, the method of light irradiation, etc. are mentioned.

The molding layer 40 may be formed by molding using a solid compression-molded resin composition. That is, the solid compression-molded resin composition may be molded in the mold by heating and pressing to form the molding layer 40. Here, as the solid compression-molded resin composition, resin pellets obtained by melt-kneading the molten resin, cooling it, and adding pellets are exemplified.

In addition, it is not necessary to use a "mold" for the molding layer, a method of laminating a film-like molding resin composition, a method of forming a paste-like molding resin composition by screen printing or a dispenser, and applying a liquid-state molding resin. The case where the composition is hardened is also included in the scope of the present invention.

In the method for manufacturing a semiconductor device according to the present invention, a temporary adhesive layer can be formed by a so-called non-reactive system without causing the temporary adhesive layer to harden by reaction.

In the method for manufacturing a semiconductor device of the present invention, a heat treatment at 100 ° C. or higher can be performed after the forming layer is formed. In the manufacturing process of a semiconductor device, a heat treatment of 100 ° C. or higher may be performed. However, the present invention can withstand such a high temperature treatment, and is valuable in this regard. The heat treatment may be performed before the carrier substrate is peeled off, or the carrier substrate or the temporary adhesive layer may be peeled off. Perform after removal. The heat treatment temperature is preferably 100 ° C or higher, more preferably 110 ° C or higher, and even more preferably 140 ° C or higher. The upper limit is preferably 260 ° C or lower, and more preferably 220 ° C or lower. By further heating the molding layer 40, for example, a thermosetting resin (preferably epoxy resin) is used as When the resin composition is molded, the thermosetting resin can be sufficiently cured. Examples of the heat treatment time include 10 minutes to 10 hours.

Next, as shown in (A4) of FIG. 1, the carrier substrate 10 is peeled from the laminated body (the peeling described herein includes the principle of separation and separation). The method for peeling the carrier substrate 10 is not particularly limited, and it is preferred that the carrier substrate 10 be peeled from the laminated body by a 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 compounding amount of a component with high releasability formulated in two or more temporary adhesive layers. For example, in a case where peeling is to be performed between the carrier substrate and the temporary adhesive layer in contact with the carrier substrate, a more highly releasable adhesive layer may be blended in the temporary adhesive layer in contact with the carrier substrate. ingredient. In particular, it is effective if a component with high mold releasability has a biased existence. The position of the laminated body can be appropriately determined according to the application and the like. It is preferable to peel at the interface of a carrier substrate and a temporary adhesive layer.

Regarding peeling, for example, it is preferred that the molding layer be pulled up from the end portion of the carrier substrate in a vertical direction without any treatment to peel. At this time, it is also preferable to use a sharp jig such as a cutter to cut into the gap between the carrier substrate and the temporary adhesive layer before peeling. The speed during the separation is preferably 30 mm / min to 120 mm / min, and more preferably 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, and even more preferably 20 ° C to 30 ° C.

In addition to the above, the peeling of the carrier substrate may be temporarily Then, the agent layer is dissolved and the carrier substrate is peeled from the laminated body. As the peeling liquid in this case, a solvent (organic solvent) can be used.

When one or two or more temporary adhesive layers remain on the laminated body of the peeled carrier substrate, the temporary adhesive layer is usually removed. Removal of the temporary adhesive layer is preferably performed at 40 ° C or lower.

The means for removing the temporary adhesive layer is not particularly limited, and it can be mechanically removed at a temperature of 40 ° C. or lower in the laminated body of the peeled carrier substrate. The term "mechanical property" herein refers to the principle of peeling without performing a chemical treatment or the like, and also includes peeling by hand. The temperature at the time of removing the temporary adhesive layer is preferably 40 ° C or lower, more preferably 10 ° C to 40 ° C, and even more preferably 20 ° C to 30 ° C. In order to improve the releasability, a part of the adhesive layer may be modified by irradiating with radiation or heating.

The temporary adhesive layer may be peeled 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 for removing the temporary adhesive layer 20, if it is in a film state, a physical removal method by spraying with a brush, ultrasonic waves, ice particles, or aerosol; and dissolving it in an aqueous solution may be mentioned. Or a method of dissolving and removing organic solvents; chemical removal methods such as a method of decomposing and vaporizing by irradiation with actinic rays, radiation, and heat; depending on the carrier substrate, a previously known cleaning method may be used.

For example, in the case where an element substrate is used as a carrier substrate, a previously known method for cleaning a silicon wafer can be used, for example, it can be used for chemical removal Examples of the aqueous solution or organic solvent include strong acids, strong bases, strong oxidants, or mixtures thereof. Specific examples include acids such as sulfuric acid, hydrochloric acid, hydrofluoric acid, nitric acid, and organic acids; tetramethylammonium, ammonia, Bases such as organic bases; oxidants such as hydrogen peroxide; or mixtures of ammonia and hydrogen peroxide, mixtures of hydrochloric acid and hydrogen peroxide water, mixtures of sulfuric acid and hydrogen peroxide water, mixtures of hydrofluoric acid and hydrogen peroxide water, A mixture of hydrofluoric acid and ammonium fluoride.

From the viewpoint of adhesiveness when using a regenerated carrier substrate, it is preferable 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 can be selected from inorganic acids such as hydrogen iodide, perchloric acid, hydrogen bromide, hydrogen chloride, nitric acid, and sulfuric acid, or organic acids such as alkylsulfonic acids and arylsulfonic acids. From the viewpoint of the cleanability of the temporary adhesive layer on the carrier substrate, an inorganic acid is preferred, and sulfuric acid is most preferred.

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

Next, in the manufacturing method of the semiconductor element of this invention, the temporary adhesive composition for temporarily adhering the formation of a material composition is demonstrated.

<Temporary adhesive composition>

The temporary adhesive layer used in the present invention can usually be formed using a temporary adhesive composition.

The temporary adhesive composition preferably contains a resin, and more preferably contains a resin and a solvent. Agent. The temporary adhesive composition is more preferably a compound containing at least one of a fluorine atom and a silicon 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 use a moderate anchor effect to form a temporary adhesive layer having excellent adhesion. In addition, when the carrier substrate is peeled from the laminated body, the carrier substrate can be peeled from the laminated body without applying stress to the laminated body, and damage or peeling of the laminated body can be prevented.

In addition, in this specification, an "elastomer" means a polymer compound which shows elastic deformation. That is, it is defined as a polymer compound having the following properties: when an external force is applied, it instantly deforms in response to the external force, and returns to its original shape in a short time when the external force is removed.

Examples of the resin contained in the temporary adhesive include a thermoplastic elastomer having a styrene structure, a thermoplastic silicone polymer, a cycloolefin polymer, an acrylic resin, polycarbonate, polyether fluorene, thermoplastic polyamine, The thermoplastic polyimide preferably contains at least one of a thermoplastic elastomer having a styrene structure, a thermoplastic siloxane polymer, a cycloolefin-based polymer, an acrylic resin, and a thermoplastic polyimide. At least one of a thermoplastic elastomer having a styrene structure, a cycloolefin-based 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-based polymer. Particularly preferred is a thermoplastic elastomer containing a styrene structure.

<<< Thermoplastic elastomer with 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 repeating units derived from styrene in all the repeating units in a proportion of 50% by mass or more and 95% by mass or less. The example further includes a case where the elastomer Y includes a repeating unit derived from styrene in a proportion 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, it has excellent releasability, and the flatness of the polished surface of the processed substrate (hereinafter also referred to as flat abrasiveness) is good, which can effectively suppress the warpage of the processed substrate after polishing 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, the inclusion of the elastomer X makes it possible to produce a temporary adhesive layer having excellent peelability. In addition, since the elastomer Y is a relatively soft material, it is easy to form a temporary adhesive layer having elasticity. In addition, even if the laminated body after the polishing is heated and then cooled, the internal stress generated during cooling can be relieved by temporarily adhering the adhesive layer, so that the occurrence of warpage can be effectively suppressed. For example, in the process of cooling the laminated body to room temperature after forming the molding 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 when the elastomer Y is blended in the elastomer X, there is a region in which the elastomer X is phase-separated, etc., and thereby the excellent peeling using the elastomer X can be sufficiently achieved. From sex.

The thermoplastic elastomer having a styrene structure is not particularly limited, and may be appropriately selected depending on the purpose. Examples include: styrene-butadiene-styrene block copolymer (SBS), styrene-isoprene-styrene block copolymer (SIS), styrene-ethylene-butene-styrene block copolymer Segment copolymer (SEBS), styrene-butadiene-butene-styrene copolymer (SBBS) and hydride, styrene-ethylene-propylene-styrene block copolymer (SEPS), styrene -Ethylene-ethylene-propylene-styrene block copolymers and the like.

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

In the present invention, examples of the thermoplastic elastomer having a styrene structure include a block copolymer, a random copolymer, and a graft copolymer. A block copolymer is preferable, and benzene is preferably used at one or both ends. The block copolymer of ethylene is particularly preferably a block copolymer having styrene at both ends. When the both ends of the thermoplastic elastomer having a styrene structure is a styrene block copolymer (repeating unit derived from styrene), the thermal stability tends to be further improved. The reason is that a repeating unit derived from styrene having high heat resistance exists at the terminal. In particular, with repeating units derived from styrene The block portion is preferably a reactive polystyrene-based hard block, which tends to be more excellent in heat resistance and chemical resistance. In addition, 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 thought that this phase-separated shape contributes to suppress generation | occurrence | production of the unevenness | corrugation on the surface of the processing substrate of an element wafer. Moreover, such a thermoplastic elastomer is more preferable 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. When the thermoplastic elastomer having a styrene structure is a hydride, thermal stability or storage stability is improved. Furthermore, the peelability and the cleaning-removability of the temporary adhesive after peeling are improved. The hydride refers to a polymer having a hydrogenated structure of an elastomer.

The 5% thermal mass reduction temperature of a thermoplastic elastomer having a styrene structure increased from 25 ° C to 20 ° C / min is preferably 250 ° C or higher, more preferably 300 ° C or higher, even more preferably 350 ° C or higher, and particularly preferably 400 Above ℃. The upper limit value is not particularly limited, but is preferably 1000 ° C or lower, more preferably 800 ° C or lower. According to this aspect, it is easy to form a temporary adhesive layer excellent in heat resistance. Furthermore, by providing a temporary adhesive layer excellent in heat resistance, heat resistance can be provided to the laminated body after the forming layer is formed, and the laminated body itself can be heat-treated, and thereafter can be peeled off.

The thermoplastic elastomer having a styrene structure preferably has the following properties: 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 In a short time, it recovered to below 130%.

Unsaturated double bond as a thermoplastic elastomer with a styrene structure From the viewpoint of peelability after the processing step, the amount is preferably less than 15 mmol / g, more preferably 7 mmol / g or less, still more preferably less than 5 mmol / g, and even more preferably less than 0.5 mmol / g. There is no particular limitation on the lower limit, and it may be, for example, 0.001 mmol / g or more.

The amount of unsaturated double bonds described herein does not include unsaturated double bonds derived from the benzene ring derived from styrene. The amount of unsaturated double bonds can be calculated by nuclear magnetic resonance (Nuclear Magnetic Resonance, NMR) measurement.

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

Examples of commercially available thermoplastic elastomers having a styrene structure include Tufprene A, Tufprene 125, Tufprene 126S, and Soluprene ( 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, Tuftec ( Tuftec) M1943, Tuftec M1911, Tuftec H1041, Tuftec MP10, Tuftec M1913, Tuftec H1051, Tuftec H1053, Tufteo P2000, Tuftec H1043 (the above are the trade names, manufactured by Asahi Kasei Corporation); Elastomer AR-850C, 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 AR-SC-45, Elastomer AR-720, Elasticity 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 are trade names, manufactured by Aronkasei); Kraton D1111, Kraton D1113, Kraton D1114, Kraton D1117, Kraton D1119 Kraton D1124, Kraton D1126, Kraton D1161, Kraton D1162, Kraton D1163, Kraton D1164, Kraton D1165, Kraton D1183, Kraton D1193, Kraton DX406, Kraton D4141, Kraton D4150, Kraton D4153, Kraton D4158, Kraton D4270, Kraton D4271, Kraton D4433 Kraton D1170, Kraton D1171, Kraton D1173, Cariflex IR0307, Cariflex IR0310, Cariflex IR0401, Kraton D0242, Kraton D1101, Kraton D1102, Kraton D1116, Kraton D1118, Kraton D1133, Kraton D1152, Kraton (Kraton) D1153, Kraton D1155, Kraton D1184, Kraton D1186, Kraton D1189, Kraton D1191, Kraton D1192, Kraton ( Kraton DX405, Kraton DX408, Kraton DX410, Kraton DX414, Kraton DX415, Kraton A1535, Kraton A1536, Kraton ) FG1901, Kraton FG1924, Kraton G1640, Kraton G1641, Kraton G1642, Kraton G1643, Kraton G1645, Kraton G1633, Kraton G1650, Kraton G16 51, Kraton G1652, Kraton G1654, Kraton G1657, Kraton G1660, Kraton G1726, Kraton G1701, Kraton G1702 , Kraton G1730, Kraton G1750, Kraton G1765, Kraton G4609, Kraton G4610 (the above are the trade names, manufactured by Kraton); TR2000, TR2001, TR2003, TR2250, TR2500, TR2601, TR2630, TR2787, TR2827, TR1086, TR1600, SIS5002, SIS5200, SIS5250, SIS5405, SIS5505, Dynaron 6100P, Dynaron 4600P, Dynaron 6200P, Dynaron 4630P, Dynar Dynaron 8601P, Dynaron 8630P, Dynaron 8600P, Dynaron 8903P, Dynaron 6201B, Dynaron 1321P, Dynaron Dynaron) 1320P, Dynaron 2324P, Dynaron 9901P (the above are the trade names, manufactured by JSR (stock)); Denka STR series (the above are the trade names, electrochemical industry (stock )); Quintac 3520, Quintac 3433N, Quintac 3421, Quintac 3620, Quintac 3450, Quintac 3460 (manufactured by ZEON, Japan); TPE-SB series (the above are the trade names, manufactured by Sumitomo Chemical Co., Ltd.); Rabalon series (the above are the trade names, manufactured by Mitsubishi Chemical Corporation); Sai Septon 1001, Septon 8004, Septon 4033, Septon 2104, Septon 8007, Septon 2007, Septon (Septon) 20 04, Septon 2063, Septon HG252, Septon 8076, Septon 2002, Septon 1020, Septon 8104, Septon 2005, Septon 2006, Septon 4055, Septon 4044, Septon 4077, Septon 4099, Sepp Septon 8006, Septon V9461, Septon V9475, Septon V9827, Hybrar 7311, Hybrar 7125, Hybron ( Hybrar) 5127, Hybrar 5125 (above the trade name, manufactured by Kuraray); Sumiflex (above the trade name, manufactured by Sumitomo Bakelite (shares)); Leos Leostomer, Actymer (the above are trade names, manufactured by Riken Ethylene Industry), etc.

Next, a preferable range peculiar to "Elastomer X" will be described.

Elastomer X is an elastomer containing repeating units derived from styrene in a proportion of 50% by mass to 95% by mass of all repeating units. The content of repeating units derived from styrene is preferably more than 50% by mass and 95% by mass or less, more preferably 50% by mass to 90% by mass, even more preferably 50% by mass to 80% by mass, particularly preferably 55% by mass to 75% by mass, and even more preferably 56% by mass to 70% by mass.

The hardness of the elastomer X is preferably 83 or more, more preferably 85 or more, and even more preferably 90 or more. The upper limit value is not particularly limited, and is, for example, 99 or less. The hardness is a value obtained by measuring with a type A hardness tester in accordance with the method of JIS (Japanese Industrial Standard) K6253.

Next, the preferable range peculiar to "elastomer Y" is described.

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

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

The difference between the hardness of the elastomer X and the hardness of the elastomer Y is preferably 5 to 40, more preferably 10 to 35, still more preferably 15 to 33, and particularly preferably 17 to 29. By setting it as such a range, the effect of this invention is exhibited more effectively.

In the present invention, elastomers other than the elastomer X and the elastomer Y may be blended. As other elastomers, polyester-based elastomers, polyolefin-based elastomers, polyurethane-based elastomers, polyamide-based elastomers, polyacrylic-based elastomers, silicone-based elastomers, and polyfluorenes can be used. Imine elastomer and the like.

The total amount of the elastomer X, the elastomer Y, and other elastomers in the temporary adhesive composition used in the present invention is preferably 50.00% to 99.99% by mass relative to the mass of the temporary adhesive composition other than the solvent. , More preferably 70.00% to 99.99% by mass, and particularly preferably 88.00% to 99.99% by mass. When content of an elastomer is the said range, adhesiveness and peelability will be more excellent.

In addition, the elastomer X, the elastomer Y, and other elastomers in the temporary adhesive composition used in the present invention may be 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 preferred is 98% by mass or more.

In the case of blending the elastomer Y, the quality of the elastomer X and the elastomer Y is better as the elastomer X: the elastomer Y = 5: 95 ~ 95: 5, more preferably 20: 80 ~ 90: 10, especially good for 40: 60 ~ 85: 15. If it is the said range, it will be more effective to suppress a curvature and to obtain peelability.

<<< thermoplastic silicone polymer >>>

The temporary adhesive composition may use a thermoplastic siloxane polymer as a resin component.

The thermoplastic siloxane polymer contains R ²¹ R ²² R ²³ SiO _1/2 units (R ²¹ , R ²² , and R ²³ are unsubstituted or substituted monovalent hydrocarbon groups having 1 to 10 carbon atoms or hydroxyl groups, respectively) And an SiO _4/2 unit and an organopolysiloxane having a molar ratio of 0.6 to 1.7 of the R ²¹ R ²² R ²³ SiO _1/2 unit / SiO _4/2 unit and the following general formula (1) It is preferable that the organic polysiloxane is partially dehydrated and condensed, and the ratio of the dehydrated and condensed organic polysiloxane to the organic polysiloxane represented by the following general formula (1) is 99. : 1 to 50: 50, and the weight average molecular weight is 200,000 to 1,500,000.

(Wherein R ¹¹ and R ¹² each represent an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, and n is 5000 to 10,000)

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

In the general formula (1), the organic substituents R ¹¹ and R ¹² are unsubstituted or substituted monovalent hydrocarbon groups having 1 to 10 carbon atoms, specifically: methyl, ethyl, and n-propyl , Isopropyl, n-butyl, third butyl, n-pentyl, cyclopentyl, n-hexyl and other alkyl groups; cycloalkyl such as cyclohexyl; hydrocarbon groups such as aryl such as phenyl and tolyl; these hydrogens A group in which part or all of the atoms are substituted with a halogen atom; methyl and phenyl are preferred.

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

As a commercial item, SILRES 604 (Asahi Kasei Wacker Silicone) is exemplified.

<<< Cycloolefin polymer >>>

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

[Chemical 2]

In the formula, m represents an integer of 0 to 4. R ¹ to R ⁶ each represent a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, X ¹ to X ³ and Y ¹ to Y ³ each represent a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, a halogen atom, or a halogen atom substituted C1-C10 hydrocarbon group,-(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 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), Z represents a hydrocarbon group or a halogen-substituted hydrocarbon group, W Represents SiR ¹⁸ _p D _3-p (R ¹⁸ represents a hydrocarbon group having 1 to 10 carbon atoms, D represents a halogen atom and represents -OCOR ¹⁸ or -OR ¹⁸ , and p represents an integer of 0 to 3). n represents an integer from 0 to 10.

The norbornene-based polymer is disclosed in Japanese Patent Laid-Open No. 10-7732, Japanese Patent Laid-Open No. 2002-504184, US2004 / 229157A1, or WO2004 / 070463A1. A norbornene-based polymer can be obtained by addition polymerization of a norbornene-based polycyclic unsaturated compound with each other. In addition, if necessary, the norbornene-based polycyclic unsaturated compound may be used with ethylene and propylene. The olefin, butene, conjugated diene such as butadiene, isoprene, and non-conjugated diene such as ethylene norbornene are subjected to addition polymerization. This norbornene-based polymer is sold by Mitsui Chemicals Co., Ltd. under the trade name of Apel, and has different glass transition temperatures (Tg) such as APL8008T (Tg70 ° C), APL6013T (Tg125 ° C), or APL6015T ( Tg145 ° C) and other grades. Poly plastics (stocks) sell TOPAS8007, TOPAS5013, TOPAS6013, TOPAS6015 and other pellets.

Furthermore, Appear 3000 is sold by Ferrania.

The hydrides of the norbornene-based polymer can be, for example, Japanese Patent Laid-Open No. 1-240517, Japanese Patent Laid-Open No. 7-176736, Japanese Patent Laid-Open No. 60-26024, and Japanese Patent Laid-Open No. 62-19801. As disclosed in Japanese Unexamined Patent Publication, Japanese Patent Laid-Open No. 2003-1159767, Japanese Patent Laid-Open No. 2004-309979, and the like, polyhydric unsaturated compounds are subjected to hydrogenation after addition polymerization or ring-opening shift polymerization, followed by hydrogenation. Manufacturing.

In the general formula (III), R ⁵ and R ^{6 are} preferably a hydrogen atom or a methyl group, X ³ and Y ^{3 are} preferably a hydrogen atom, and other groups may be appropriately selected. This norbornene-based polymer is sold by JSR (stock) under the trade names of Arton G or Arton F, and is sold by Zeon of Japan as Zeonor ZF14, ZF16, Zeonex 250, Zeonex 280, and Zeonex 480R are commercially available under the trade names, and these may also be used.

The polystyrene-equivalent weight average molecular weight of the cycloolefin-based polymer obtained by gel permeation chromatography (GPC) is preferably 10,000 to 1,000,000, and more preferably It is 50,000 to 500,000, and more preferably 100,000 to 300,000.

In addition, as the cycloolefin-based polymer used in the present invention, a cycloolefin-based polymer described in paragraphs 0039 to 0052 of Japanese Patent Laid-Open No. 2013-241568 can also be exemplified, and these 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, n-propyl (meth) acrylate, Isopropyl (meth) acrylate, amyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, isononyl (meth) acrylate, n- (meth) acrylate Butyl, isobutyl (meth) acrylate, hexyl (meth) acrylate, n-nonyl (meth) acrylate, iso-amyl (meth) acrylate, n-decyl (meth) acrylate, (meth) ) Isodecyl acrylate, dodecyl (meth) acrylate, isobornyl (meth) acrylate, cyclohexyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate Ester, and 2-methylbutyl (meth) acrylate.

In addition, other monomers may be copolymerized within a range not exceeding the gist of the present invention. In the case of copolymerizing other monomers, it is preferably 10 mol% or less of all monomers.

In addition, in the present invention, an acrylic resin having an organic polysiloxane in a side chain is also preferable. Examples of the resin having an organic polysiloxane in the side chain include those represented by the following formula (3).

Equation (3)

In the formula (3), when there are a plurality of R ¹ , they may be the same or different, and represent CH ₃ , C ₂ H ₅ , CH ₃ (CH ₂ ) ₂ or CH ₃ (CH ₂ ) ₃ . When there are a plurality of R ² , they may be the same or different, and represent H, CH ₃ , C ₂ H ₅ , CH ₃ (CH ₂ ) ₂ or CH ₃ (CH ₂ ) ₃ . When R ³ is plural, they may be the same or different, and represent H or CH ₃ . When R ⁴ is plural, 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 R 4. An alkyl group having 1 to 6 carbon atoms substituted with at least one functional group in the group consisting of hydroxy, carboxyl, amine, alkoxy, vinyl, silanol, and isocyanate groups.

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 a silicone-grafted acrylic resin manufactured by Shin-Etsu Chemical Industry 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 Synthesis ), Rezeta GS-1000 series (GS-1015, GS-1302, etc.) and so on.

In addition to the above, examples include acryl MF 001 manufactured by Mitsubishi Rayon Corporation.

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

The temporary adhesive composition used in the present invention may contain only one resin or two or more resins. When two or more types are included, the total amount is preferably within the range.

<< Solvent >>

The temporary adhesive composition used in the present invention preferably contains a solvent. When the temporary adhesive layer is formed by applying the temporary adhesive composition used in the present invention, it is preferable to prepare a solvent. A known solvent can be used without limitation, and an organic solvent is preferred.

As the organic solvent, ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, Ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, alkyl alkoxyacetate (for example: methyl alkoxyacetate, ethyl alkoxyacetate, Alkyloxybutyl acetate (e.g. methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.), 3-alkane Alkyloxypropanoates (e.g. methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc. (e.g. methyl 3-methoxypropionate, 3-methoxy Ethyl propionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)), 2-alkyloxy propionate alkyl esters (for example: 2-alkyloxy Methyl propionate, ethyl 2-alkyloxypropionate, propyl 2-alkyloxypropionate, etc. (e.g. methyl 2-methoxypropionate, ethyl 2-methoxypropionate, 2 -Propyl methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), methyl 2-alkyloxy-2-methylpropionate and 2-alkane Ethyloxy-2-methylpropionate (e.g. 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methylpyruvate , Ethyl pyruvate, propyl pyruvate, methyl acetate, ethyl acetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, 1-methoxy-2-propane Esters such as methyl acetate; diethylene glycol dimethyl ether Tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethyl ether Ethers such as glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate; methyl ethyl ketone, cyclohexanone, 2-heptane Ketones such as ketones, 3-heptanone, N-methyl-2-pyrrolidone, γ-butyrolactone; toluene, xylene, anisole, mesitylene, ethylbenzene, propylbenzene, cumene , N-butylbenzene, second butylbenzene, isobutylbenzene, third butylbenzene, pentylbenzene, isoamylbenzene, (2,2-dimethylpropyl) benzene, 1-phenylhexyl Alkane, 1-phenylheptane, 1-phenyloctane, 1-phenylnonane, 1-phenyldecane, cyclopropylbenzene, cyclohexylbenzene, 2-ethyltoluene, 1,2-diethylbenzene, o-isopropyltoluene, indan, 1,2,3,4-tetrahydronaphthalene, 3-ethyltoluene, m-isopropyltoluene, 1,3-diiso Propylbenzene, 4-ethyltoluene, 1,4-diethylbenzene, p-isopropyltoluene, 1,4-diisopropylbenzene, 4-tert-butyltoluene, 1,4-di- Tert-butylbenzene, 1,3-diethylbenzene, 1,2,3-trimethylbenzene, 1,2,4-trimethylbenzene, 4-tert-butyl-o-xylene, 1, 2,4-triethylbenzene, 1,3,5-triethylbenzene, 1,3,5-triisopropylbenzene, 5-third butyl-m-xylene, 3,5-di- Aromatic hydrocarbons such as tributyl toluene, 1,2,3,5-tetramethylbenzene, 1,2,4,5-tetramethylbenzene, pentamethylbenzene; limonene, p-menthane, nonane, Hydrocarbons such as decane, dodecane, and decalin.

Of these, mesitylene, third butylbenzene, 1,2,4-trimethylbenzene, p-menthane, γ-butyrolactone, anisole, and methyl 3-ethoxypropionate are preferred. , Ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone , 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, these solvents are also preferably in the form of a mixture of two or more. In this case, it is particularly preferable that the mixed solution contains a material selected from the group consisting of mesitylene, third butylbenzene, 1,2,4-trimethylbenzene, p-menthane, γ-butyrolactone, and benzyl 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 .

Temporary adhesive in the composition of 1013.25 hPa The boiling point is preferably 110 ° C to 250 ° C, and more preferably 140 ° C to 190 ° C. By using such a solvent, a temporary adhesive having more excellent in-plane uniformity can be obtained. When two or more solvents are used, the boiling point of the solvent having the highest boiling point is set as the boiling point.

In the case where the temporary adhesive composition has a solvent, the content of the solvent in the temporary adhesive composition is preferably from the viewpoint of coating properties such that the total solid content concentration of the temporary adhesive composition is 5 to 80% by mass The amount of% is more preferably 10% by mass to 50% by mass, and particularly preferably 15% by mass to 40% by mass.

The solvent may be only one kind, or two or more kinds. When there are two or more solvents, it is preferable that the total thereof is within the above range.

The content of the solvent in the temporary adhesive layer 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 fluorine atom and silicon atom >>

The temporary adhesive composition used in the present invention is preferably a compound containing at least one of a fluorine atom and a silicon atom. By blending such components, it becomes easier to separate the carrier substrate and the processing substrate. Furthermore, regarding compounds containing at least one of a fluorine atom and a silicon atom, since silicon atoms or fluorine atoms tend to be biased near the surface layer of the temporary adhesive layer, even if the amount of these compounds is relative to that of the temporary adhesive composition, There are few resins and the like, and a temporary adhesive layer having excellent releasability from a processing substrate or a carrier substrate can also be formed.

<<< Compounds with fluorine atom >>>

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

Examples of the compound having a fluorine atom include liquid compounds. The so-called liquid compound is a compound having fluidity at 25 ° C., for example, means that the viscosity at 25 ° C. is 1 mPa. s ~ 100,000mPa. s compound.

The viscosity at 25 ° C of the compound having a fluorine atom is, for example, more preferably 10 mPa. s ~ 20,000mPa. s, particularly preferably 100mPa. s ~ 15,000mPa. s. When the viscosity of the compound having a fluorine atom is within the above range, the compound having a fluorine atom tends to be biased on the surface of the temporary adhesive.

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

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 polymer include a radical polymer, a cationic polymer, and an anionic polymer, 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 the compound having a fluorine atom can easily achieve a biased existence on the surface of the temporary adhesive layer and have excellent peelability.

In the present invention, an oligomer is defined as a compound having a weight average molecular weight of 500 or more and less than 2000. The polymer is defined as a compound having a weight average molecular weight of 2,000 or more.

The weight average molecular weight of the compound having a fluorine atom is preferably 500 to 100,000, more preferably 1,000 to 50,000, and even more preferably 2,000 to 20,000.

In the present invention, the compound having a fluorine atom is preferably a compound which is not modified when a substrate to be temporarily adhered is processed. For example, a compound which can exist in a liquid form even after being heated at 250 ° C. or more or a substrate is treated with various chemical liquids is preferred. As a specific example, the viscosity at 25 ° C after being heated to 250 ° C from a state of 25 ° C under a temperature rise condition of 10 ° C / min is preferably 1 mPa. s ~ 100,000mPa. s, more preferably 10mPa. s ~ 20,000mPa. s, particularly preferably 100mPa. s ~ 15,000mPa. s.

The liquid compound having a fluorine atom having such characteristics is preferably a non-thermosetting compound having no reactive group. The reactive group mentioned here means the whole group which reacts by heating at 250 degreeC, and a polymeric group, a hydrolysable group, etc. are mentioned. Specific examples include (meth) acrylic groups, epoxy groups, and isocyanate groups.

As the non-thermosetting compound, a polymer containing one or two or more fluorine-containing monofunctional monomers can be preferably used. More specifically, a fluororesin selected from at least one polymer selected from the group consisting of tetrafluoroethylene, hexafluoropropylene, tetrafluoroethylene oxide, hexafluoropropylene oxide, and perfluoroalkylethylene can be listed. Homopolymer of one or two or more kinds of fluorinated monofunctional monomers or copolymerization of one or more of fluorinated ethers, chlorotrifluoroethylene, vinylidene fluoride, (meth) acrylates containing perfluoroalkyl groups Copolymer of ethylene, one or two or more kinds of fluorine-containing monofunctional monomers, and a copolymer of one or two or more kinds of fluorine-containing monofunctional monomers with chlorotrifluoroethylene.

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

From the standpoint of releasability, in addition to the (meth) acrylic acid ester containing a perfluoroalkyl group, the (meth) acrylic acid copolymer containing a perfluoroalkyl group may optionally have a copolymerization component selected. Examples of the radically polymerizable compound capable of forming a copolymerizable component include acrylates, methacrylates, N, N-2 substituted acrylamides, and N, N-2 substituted acrylamides. , Styrenes, acrylonitriles, methacrylonitrile, and other radical polymerizable compounds.

More specifically, for example, acrylates (such as methyl acrylate, ethyl acrylate, propyl acrylate, and butyl acrylate) such as alkyl acrylate (preferably those having 1 to 20 carbon atoms in the alkyl group) can be cited. , Pentyl acrylate, ethylhexyl acrylate, octyl acrylate, third octyl acrylate, chloroethyl acrylate, -2,2-dimethylhydroxypropyl acrylate, 5-hydroxypentyl acrylate, trimethylol Propane monoacrylate, pentaerythritol monoacrylate, glycidyl acrylate, benzyl acrylate, methoxybenzyl acrylate, furfuryl acrylate, tetrahydrofurfuryl acrylate, etc.); aryl acrylates (such as acrylic acid Phenyl esters, etc.); methacrylic esters such as alkyl methacrylates (preferably those having 1 to 20 carbon atoms in the alkyl group) (e.g. methyl methacrylate, ethyl methacrylate, methyl Propyl acrylate, isopropyl methacrylate, amyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, chlorobenzyl methacrylate, octyl methacrylate , 4-hydroxybutyl methacrylate, methyl 5-hydroxypentyl acrylate, -2,2-dimethyl-3-hydroxypropyl methacrylate, trimethylolpropane monomethacrylate, pentaerythritol monomethacrylate, glycidyl methacrylate , Furfuryl methacrylate, tetrahydrofurfuryl methacrylate, etc.); aryl methacrylates (such as phenyl methacrylate, Cresol-based acrylate, naphthyl methacrylate, etc.); styrenes such as styrene, alkylstyrene (e.g. methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, Diethylstyrene, isopropylstyrene, butylstyrene, hexylstyrene, cyclohexylstyrene, decylphenethyl, benzylstyrene, chloromethylstyrene, trifluoromethylstyrene, Ethoxymethylstyrene, ethoxymethylstyrene, etc.), alkoxystyrene (such as methoxystyrene, 4-methoxy-3-methylstyrene, dimethoxybenzene Ethylene, etc.), halogenated styrene (e.g. chlorostyrene, dichlorostyrene, trichlorostyrene, tetrachlorostyrene, pentachlorostyrene, bromostyrene, dibromostyrene, iodostyrene, fluorostyrene, Trifluorostyrene, 2-bromo-4-trifluoromethylstyrene, 4-fluoro-3-trifluoromethylstyrene, etc.); acrylonitrile; radical polymerizable compounds containing carboxylic acid (acrylic acid, methyl Acrylic acid, itaconic acid, butenoic acid, methacrylic acid, maleic acid, p-carboxystyrene, and metal salts and ammonium compounds of these acid groups ). From the standpoint of releasability, a (meth) acrylate having a hydrocarbon group having 1 to 24 carbon atoms is particularly preferred, and examples include methyl (meth) acrylate, butyl ester, 2-ethylhexyl ester, and lauryl (Meth) acrylates of higher alcohols such as 2-ethylhexyl, lauryl, and stearyl are preferred, and particularly preferred are acrylates.

In the present invention, the 10% thermal mass reduction temperature of the compound having a fluorine atom increased from 25 ° C at 20 ° C / min is preferably 250 ° C or more, and more preferably 280 ° C or more. The upper limit value is not particularly limited, but is preferably 1000 ° C or lower, more preferably 800 ° C or lower. According to this aspect, it is easy to form a temporary bonding laminated body having excellent heat resistance. In addition, the 10% thermal mass reduction temperature refers to a measurement using a thermogravimetric measurement device under a nitrogen flow under the temperature rising condition, and it can be seen that the weight before measurement is reduced. 10% temperature.

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.

Examples of the alkyl group include a linear alkyl group, a branched alkyl group, and a cyclic alkyl group.

The carbon number of the linear alkyl group is preferably from 2 to 30, more preferably from 4 to 30, even more preferably from 6 to 30, particularly preferably from 12 to 20.

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

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

Specific examples of the linear alkyl group or the branched alkyl group include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, and dodecyl. , Tetradecyl, octadecyl, isopropyl, isobutyl, second butyl, third butyl, 1-ethylpentyl, 2-ethylhexyl.

Specific examples of the cyclic alkyl group include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl, adamantyl, norbornyl, norbornyl, and pinenyl. , Decahydronaphthyl, tricyclodecyl, tetracyclodecyl, fluorenyldifluorenyl, dicyclohexyl, pinenyl.

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

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

The carbon number of the alkoxy group is preferably 1 to 30, more preferably 1 to 20, and even more preferably 1 to 10. The alkoxy group is preferably a linear alkoxy group or a branched alkoxy group.

The aromatic group may be monocyclic or polycyclic. The carbon number of the aromatic group is preferably 6 to 20, more preferably 6 to 14, and most preferably 6 to 10. The aromatic group preferably does not contain a hetero atom (for example, a nitrogen atom, an oxygen atom, a sulfur atom, etc.) in the element constituting the ring. Specific examples of the aromatic ring include a benzene ring, a naphthalene ring, a pentalene ring, an indene ring, a fluorene ring, a heptene ring, a benzodiindene ring, a fluorene ring, a pentacene ring, a fluorene ring, Phenanthrene ring, anthracene ring, fused tetraphenyl ring, Ring, triphenylene ring, fluorene ring, biphenyl ring, pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, indoxazine Ring, indole ring, benzofuran ring, benzothiophene ring, isobenzofuran ring, quinazine ring, quinoline ring, phthalazine ring, naphthyridine ring, quinoxaline ring, quinazoline ring, isoquine A phthaloline ring, a carbazole ring, a pyridine ring, an acridine ring, a phenanthroline ring, a thiathracene ring, a benzopiperan ring, a xanthracene ring, a phenothiazine 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 kind of lipophilic group, or may contain two or more kinds. The lipophilic group may contain a fluorine atom. That is, the compound having a fluorine atom may be a compound having only a lipophilic group containing a fluorine atom. In addition, it may be a compound containing a group having a fluorine element (also referred to as a fluorine-containing group) in addition to the lipophilic group. Compounds containing a lipophilic group and a fluorine-containing group are preferred.

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 or may not contain a fluorine atom, and it is preferable that the lipophilic group does not contain a fluorine atom.

The compound having a fluorine atom has more than one lipophilic group in one molecule, preferably has 2 to 100, and particularly preferably has 6 to 80.

As the fluorine-containing group, a known fluorine group can be used. Examples include fluorine-containing alkyl groups and fluorine-containing alkylene groups. Furthermore, those which function as a lipophilic group among the fluorine-containing groups are included in the lipophilic group.

The carbon number of the fluorine-containing alkyl group is preferably 1 to 30, more preferably 1 to 20, and even more preferably 1 to 15. The fluorine-containing alkyl group may be any of linear, branched, and cyclic. Moreover, it may have an ether bond. The fluorine-containing alkyl group may be a perfluoroalkyl group in which all of the hydrogen atoms are replaced with fluorine atoms.

The number of carbon atoms of the fluorine-containing alkylene group is preferably 1 to 30, more preferably 2 to 20, and even more preferably 2 to 15. The fluorine-containing alkylene group may be any of linear, branched, and cyclic. Moreover, it may have an ether bond. The fluorine-containing alkylene group may be a perfluoroalkylene group in which all the hydrogen atoms are replaced with fluorine atoms.

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

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

As the compound having a fluorine atom, a commercially available product can also be used. Examples of the non-thermosetting compound include Teflon (registered trademark) (DuPont), Tefzel (DuPont), and Fluon. (Asahi Glass), Heira (SolvaySolexis) Company), Heiler (SolvaySolexis), Lumiflon (Asahi Glass), Aflas (Asahi Glass), Sefot ( Cefralsoft (Central Glass), Cefralcoat (Central Glass) and other fluororesins; Viton (DuPont), Kalrez ) (DuPont), SIFEL (Shin-Etsu Chemical Co., Ltd.) and other branded fluorine rubber; Krytox (DuPont), Fomblin (Fomblin) ( Daitoku Tech), Demnum (Daikin Industries), Surflon (e.g. Surflon S243, etc.), AGC Seimi Chemical (manufactured by Chemical)) and other fluoro oils represented by perfluoropolyether oil; or Daifree FB962 and other Daifree FB series (Daikin Industrial Company), Megafac ) Series (Dicson (DIC)) and other brand-name fluorine-containing release agents.

In addition, as a commercially available compound having a fluorine atom having an oleophilic group, there may be mentioned, for example, F-251, F-281, F-477, and F-Megafac series manufactured by DIC Corporation. 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 silane coupling agent may be used as the compound having a fluorine atom. The fluorine-containing silane coupling agent is preferably a silane coupling agent, particularly preferably A fluorine-containing alkoxysilane. Examples of commercially available products include Optool DAC-HP and Optool DSX manufactured by Daikin Industrial Co., Ltd.

<<< compound containing silicon atom >>>

The compound containing a silicon atom is preferably a so-called thermosetting compound (for example, a compound that starts to harden at a temperature of at least 100 ° C).

In addition, the silicon atom-containing compound used in the present invention is preferably a compound having high heat resistance, and a 10% thermal mass reduction temperature which is increased from 25 ° C at 20 ° C / min is preferably 250 ° C or more, more preferably 280 ° C or more . The upper limit value is not particularly limited, but is preferably 1000 ° C or lower, more preferably 800 ° C or lower. According to this aspect, it is easy to form a temporary adhesive layer excellent in heat resistance. The term “thermal mass reduction temperature” refers to a value obtained by performing measurement under a temperature rise condition using a thermogravimetric analyzer (TGA) under a nitrogen flow.

The compound containing a silicon atom may be a monomer, an oligomer, or a polymer, and is preferably an oligomer or a polymer. The weight average molecular weight of the silicon atom-containing compound is preferably 1,000 or more, more preferably 3,000 or more, and may be 5,000 or more, and may be 10,000 or more. The upper limit of the weight average molecular weight is preferably 500,000 or less, and more preferably 100,000 or less.

The compound containing a silicon atom used in the present invention preferably has a siloxane bond, and more preferably contains a repeating unit having a siloxane bond represented by the following formula.

[Chemical 4]

In the formula, R is each independently a hydrogen atom or a substituent. The silicon atom-containing compound contains a repeating unit having a siloxane bond, thereby obtaining a temporary adhesive composition having more excellent heat resistance.

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, and an aryl group, and still more preferably a hydrogen atom and an alkyl group having 1 to 3 carbon atoms.

The compound containing a silicon atom contained in the temporary adhesive composition is preferably such that 20% by mass or more of the compound is a repeating unit having a siloxane bond.

The silicon atom-containing compound used in the present invention may include the following repeating units in addition to the repeating units having a siloxane bond.

In the formula, R ^{1 is} each independently a hydrogen atom or a substituent, and X is an alkylene or an 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, and 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 or a phenylene group having 1 to 3 carbon atoms.

The silicon atom-containing compound contained in the temporary adhesive composition is preferably such that the repeating unit is 80% by mass or less.

As a preferable first embodiment of the silicon atom-containing compound used in the present invention, a state having a crosslinkable group can be exemplified. The crosslinkable group refers to a group that forms a crosslinked structure by heating (for example, 150 ° C. or higher), and specifically includes a phenolic hydroxyl group, an epoxy group, an oxetanyl group, a methylol group, and an alkyl Oxymethylol is a preferred example. In the first embodiment, it is more preferable that the temporary adhesive composition contains a crosslinking agent that crosslinks the crosslinkable group.

The silicon atom-containing compound used in the first embodiment is preferably a polymer containing a repeating unit represented by the general formula (21).

General formula (21)

In the general formula (21), R ¹ to R ⁴ are each independently 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 even more preferably a methyl group.

m is preferably an integer of 3 to 80, more preferably an integer of 8 to 60, and even more preferably an integer of 10 to 40.

B is preferably an integer of 5 to 100. A is preferably an integer from 0 to 5. In addition, A / B is preferably 0-20, and particularly preferably 0.5-5.

As a crosslinkable group which X has, a phenolic hydroxyl group, an epoxy group, and an oxetanyl group are preferable, and a phenolic hydroxyl group and an epoxy group are more preferable.

X is more preferably a divalent organic group represented by the following general formula (2) or (4).

Formula (2)

In the general formula (2), Z is a divalent linking group, and preferably contains [Chem. 8]

Any one or a combination of two or more divalent organic groups.

n is 0 or 1, preferably 1.

R ⁵ and R ⁶ are each independently an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms.

k is independently any one of 0, 1, 2, and is preferably 0 or 1, and more preferably 0.

Formula (4)

In the general formula (4), V is a divalent linking group, and a preferable range of V is the same as Z in the general formula (2).

p is 0 or 1, preferably 1.

R ⁷ and R ⁸ are each independently an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms.

h is independently any one of 0, 1, 2, and is preferably 0 or 1, and more preferably 0.

The cross-linking agent is preferably selected from the group consisting of formalin or formalin-alcohol. And modified amine-based condensates, melamine resins, urea resins, phenol compounds having an average of two or more methylol or alkoxymethyl groups in one molecule, and an average of two or more The epoxy-based epoxy compound is more preferably selected from a phenol compound having an average of two or more methylol or alkoxymethyl groups in one molecule and an average of two or more epoxy groups in one molecule Epoxy compound.

When the crosslinkable group possessed by the silicon atom-containing compound is an epoxy group, it can be preferably used for a phenol compound having an average of two or more hydroxyphenyl groups in one molecule. A 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 cresol novolac resin or α, α, α ', α'-Tetra (4-hydroxyphenyl) -p-xylene. Examples of commercially available products include EP-6030G manufactured by Asahi Organic Materials Industry, Tris-P-PA manufactured by Honshu Chemical Industry, and TEP-TPA manufactured by Asahi Organic Materials Industry.

When the crosslinkable group of the compound containing a silicon atom is a phenolic hydroxyl group, it can be preferably used for an epoxy compound having an average of two or more epoxy groups in one molecule. An 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. As commercially available products, EOCN-1020, EOCN-102S can be exemplified. , EOCN-103S, XD-1000, NC-2000-L, EPPN-201, GAN, NC6000 (the above are manufactured by Nippon Kayaku). Moreover, the crosslinking agent of the structure shown below can also be used preferably.

[Chemical 10]

Blending of a crosslinking agent to 100 parts by mass of a compound containing a silicon atom The amount is preferably from 0.1 to 50 parts by mass, more preferably from 0.1 to 30 parts by mass, and even more preferably from 1 to 20 parts by mass. The crosslinking agent may be one kind, or two or more kinds. In the case of two or more types, the total amount is preferably in the range.

Moreover, it is preferable to mix | blend a catalyst with the temporary adhesive composition of this embodiment. The catalyst is a hardening catalyst, and an acid anhydride can be exemplified, preferably bis (third butylsulfonyl) diazomethane (manufactured by Wako Pure Chemical Industries, BSDM), tetrahydrophthalic anhydride (manufactured by Nippon Physicochemical) , Physical and chemical acid (RIKACID) HH-A). The catalyst can be prepared in a range of 0.001 to 10 parts by mass with respect to 100 parts by mass of the compound containing a silicon atom. The catalyst may be used alone, or two or more catalysts may be used.

As a preferable second embodiment of the silicon atom-containing compound used in the present invention, a state in which the silicon atom-containing compound has a Si-H structure can be exemplified. Here, the Si-H structure refers to a structure in which at least one of four bonding bonds of a silicon atom is bonded to a hydrogen atom. The remaining bonding bonds of the silicon atom may be bonded to a hydrogen atom, or may be bonded to other atoms (such as an oxygen atom or a carbon atom).

In the second embodiment, the temporary adhesive composition preferably contains a catalyst, and in addition to the compound having the Si-H structure and containing a silicon atom, the compound containing a silicon atom and a compound containing a vinyl group (i.e. At least one of a compound containing a silicon atom and a vinyl group), and another compound containing a vinyl group (that is, a compound containing a silicon atom and 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 silicon atom, and a compound containing a silicon atom and a vinyl group. Further, the compound having a Si-H structure and containing a silicon atom, and the compound containing a silicon atom and a vinyl group, respectively, preferably have silicon oxide. Alkanes.

First, a state in which a compound containing a silicon atom has a Si-H structure will be described. When the compound containing a silicon atom has Si-H, the compound containing a silicon atom is preferably represented by the following formula.

In the formula, v is in the range of 0 to 1, u is in the range of 0 to 2, and z is in the range of 0 to 1. 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 formula, p is preferably an integer of 1 to 100, and more preferably an integer of 20 to 80.

As an example of a compound having a Si-H structure and containing a silicon atom, F1-3546 or 6-3570 manufactured by Dow Corning Corp. can be exemplified.

The compound having a Si-H structure and containing a silicon atom may be used alone, or two or more kinds may be used.

Next, the vinyl-containing compound will be described. The vinyl-containing compound used in the present invention may be a monomer, an oligomer, or a polymer. It is preferably an oligomer or a polymer, and the weight-average molecular weight of the vinyl-containing compound is preferably 1,000 or more, more preferably 3,000 or more, 5,000 or more, or 10,000 or more. The upper limit of the weight average molecular weight is preferably 500,000 or less, and more preferably 100,000 or less.

The vinyl-containing compound preferably has a siloxane bond, and more preferably contains at least one of three siloxane bond-containing repeating unit constituents based on the following formula E1.

E1 E (C1) _m (C2) _n (C3) _o E

In the formula E1, E each independently represents an end-capping group, m, n, and o each independently represent a mole ratio of each constituent in a vinyl-containing compound, and m is 0.025 to 1.0. Range, 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) includes a vinyl group.

The formula E1 is preferably represented by the following formula E2.

E2

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; u is in the range of 0 to 2; m, n, and o each independently represents a compound containing a vinyl group; The molar ratio of each constituent component of m is 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, and more preferably an alkyl group having 1 to 4 carbon atoms. The aryl group is preferably an aryl group having 6 to 12 carbon atoms. The vinyl group is preferably substituted by a hydrogen atom of an aliphatic group or an aryl group.

As examples 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-containing compound is preferably 20 to 500 parts by mass, more preferably 40 parts by mass to 100 parts by mass of the compound having a Si-H structure and containing a silicon atom. 300 parts by mass.

The vinyl-containing compound may be used alone or in combination of two or more.

The catalyst used in the second embodiment will be described. In the second embodiment, the catalyst is formulated so as to promote a thermosetting reaction of the compound containing a silicon atom and a compound containing a vinyl group (in particular, a reaction for hardening by heat of 150 ° C. or higher).

The catalyst may be selected from the group consisting of chloroplatinic acid, an aliphatic unsaturated organosilicon compound and chlorination Platinum-containing catalysts obtained by the reaction of platinum acid or platinum dichloride (for example, platinum (0) -1,3-divinyl-1,1,3,3-tetramethyldisilaxane complex ), Acetoacetone platinum, and any other transition metal catalyst that can be used in the hydrosilylation reaction.

The amount of the catalyst to be blended can be appropriately determined according to the type of the catalyst and the like. Regarding the blending amount of the catalyst, when blending, for example, it can be blended at a ratio of 0.01% by mass to 40% by mass with respect to the mass of the temporary adhesive composition. The catalyst may be used alone, or two or more catalysts may be used.

In addition, in the second embodiment, in order to delay the start of the catalyst reaction, an inhibitor that can interact with the catalyst may be included. Examples of the blocking agent include diallyl maleate, ethynyl cyclohexanol, bis (2-methoxy-1-methylethyl) maleate, and N, N, N ', N'-tetramethylethylenediamine. The inhibitor can be formulated at a ratio of 0.01% to 40% by mass of the catalyst. The blocking agent may be used alone or in combination of two or more.

In addition, as the compound having a Si-H structure and containing a silicon atom described in the second embodiment, a low-molecular compound may be used. Examples of the low-molecular compound include the following compounds.

In addition to the above, as the silicon atom-containing compound used in the present invention, an epoxy group-containing polymer compound described in claim 1 of Japanese Patent Laid-Open No. 2012-188650 and the like, and a Japanese patent may be used. The non-aromatic saturated hydrocarbon group-containing organopolysiloxane described in claim 1 and the like of Japanese Patent Application Laid-Open No. 2013-82801 is incorporated into this specification.

The content of the silicon atom-containing compound in the temporary adhesive composition is preferably 50.00% to 99.99% by mass, and more preferably 70.00% to 99.99% by mass relative to the mass of the temporary adhesive composition other than the solvent. Particularly preferred is 88.00% to 99.99% by mass. When the content of the silicon atom-containing compound is within the above range, the adhesiveness and peelability are more excellent.

In addition, the compound containing a silicon atom in the temporary adhesive composition may be only one kind, or a combination of plural kinds. In this case, the total amount of the content is preferably in the range.

The total content of the compound containing at least one of a fluorine atom and a silicon 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. Above, more preferably 0.0001% by mass or more, even more preferably 0.001% by mass or more, particularly preferably 0.005% by mass or more, particularly preferably 0.01% by mass or more. The upper limit is preferably 10% by mass or less, more preferably 5% by mass or less, and even more preferably less than 2.5% by mass.

When the total content of the compound containing at least one of a fluorine atom and a silicon atom is within the above range, the adhesiveness and peelability are more excellent. In particular, in the present invention, even if the amount of the temporary adhesive composition is small, the effect of the present invention can be achieved. The value is high.

The compound containing at least one of a fluorine atom and a silicon atom may be used alone or in combination of two or more. When two or more types are used in combination, the total content is preferably in the above range.

<< Antioxidant >>

The temporary adhesive composition used in the present invention may contain an antioxidant from the viewpoint of preventing the low molecular weight or gelation of the elastomer due to oxidation during heating. As the antioxidant, a phenol-based antioxidant, a sulfur-based antioxidant, a phosphorus-based antioxidant, a quinone-based antioxidant, an amine-based antioxidant, or the like can be used.

Examples of the phenolic antioxidant include p-methoxyphenol, 2,6-di-tert-butyl-4-methylphenol, and "Irganox" manufactured by BASF. 1010 "," Irganox 1330 "," Irganox 3114 "," Irganox 1035 "," Sumilizer "manufactured by Sumitomo Chemical Co., Ltd. ) MDP-S "," Sumilizer GA-80 ", etc.

Examples of the sulfur-based antioxidant include 3,3'-thiodipropionate distearyl, "Sumilizer TPM" manufactured by Sumitomo Chemical Co., Ltd., and "Sumilizer ( Sumilizer) TPS "," Sumilizer TP-D ", etc.

Examples of the phosphorus-based antioxidant include tris (2,4-di-third-butylphenyl) phosphite, bis (2,4-di-third-butylphenyl) pentaerythritol diphosphite, Poly (dipropylene glycol) phenylphosphite, diphenylisodecylphosphite, 2-ethylhexyldiphenylphosphite, triphenylphosphite, BASF "Irgafos 168", "Irgafos 38" and so on.

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

Examples of the amine-based antioxidant include dimethylaniline and phenothiazine.

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

Among the antioxidants, it is preferable to use a phenol-based antioxidant and a sulfur-based antioxidant or a phosphorus-based antioxidant in combination, and it is particularly preferable to use a phenol-based antioxidant and a sulfur-based antioxidant in combination. In particular, when a thermoplastic elastomer having a styrene structure is used as the elastomer, it is preferable to use a phenol-based antioxidant and a sulfur-based antioxidant in combination. By setting it as such a combination, the effect which can suppress the deterioration of the elastomer by an oxidation reaction efficiently can be expected. In the case of using a phenol-based antioxidant and a sulfur-based antioxidant together, the quality of the phenol-based antioxidant and the sulfur-based antioxidant is better: phenol-based antioxidant: sulfur-based antioxidant = 95: 5 ~ 5: 95, more preferably 25: 75 ~ 75: 25.

As a combination of antioxidants, Irganox 1010 and Sumilizer TP-D, Irganox 1330 and Sumilizer TP-D and Su Sumilizer GA-80 and Sumilizer TP-D, more preferably Irganox 1010 and Sumilizer TP-D, Irganox 1330 and Sumilizer TP-D, particularly preferred is Irganox 1010 and Sumilizer TP-D.

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

In the case where the temporary adhesive composition has an antioxidant, the content of the antioxidant is preferably 0.001% to 20.0% by mass, and more preferably 0.005% to 10.0% by mass relative to the total solid content of the temporary adhesive composition. .

The antioxidant may be only one kind, or two or more kinds. When there are two or more antioxidants, it is preferable that the total thereof is within the above range.

<< Radical Polymerizable Compound >>

The temporary adhesive composition used in the present invention also preferably contains a radical polymerizable compound. By using a temporary adhesive composition containing a radically polymerizable compound, it is easy to suppress the flow deformation of the temporary adhesive layer during heating. Therefore, for example, in a case where the laminated body after the substrate is polished is subjected to a heat treatment, the temporary deformation of the adhesive layer during heating can be suppressed, and the occurrence of warpage can be effectively suppressed. In addition, since a temporary adhesive layer having hardness can be formed, even if a local pressure is applied during polishing of the substrate, the temporary adhesive layer is not easily deformed, and is excellent in flat abrasiveness.

In the present invention, the radically polymerizable compound is a compound having a radically polymerizable group, and a known radically polymerizable compound that can be polymerized by a radical can be used. Such compounds are widely known in the industrial field, and these compounds can be used without particular limitation in the present invention. These may be, for example, any of chemical forms such as a monomer, a prepolymer, an oligomer, a mixture of these, and a polymer of these. As a radical polymerizable compound, refer to Japanese Patent Laid-Open No. 2015-087611 The descriptions of paragraphs 0099 to 0180 are incorporated into this specification.

In addition, as the radical polymerizable compound, for example, Japanese Patent Publication No. 48-41708, Japanese Patent Publication No. 51-37193, Japanese Patent Publication No. 2-32293, and Japanese Patent Publication No. 2 Acrylic urethanes disclosed in -16765 or Japanese Patent Publication No. 58-49860, Japanese Patent Publication No. 56-17654, Japanese Patent Publication No. 62-39417, and Japanese Patent Publication No. 62 The urethane compounds having an ethylene oxide-based skeleton described in Japanese Patent No. -39418. Furthermore, JP-A-63-277653, JP-A-63-260909, and JP-A-105238 can be used to have an amine structure or a thioether structure in the molecule. Addition polymerizable monomers are used as radical polymerizable compounds.

Examples of commercially available products of the radical polymerizable compound include urethane oligomers UAS-10 and UAB-140 (manufactured by Sanyo Kokusaku Pulp); NK ester M-40G, and 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 (Manufactured by Nippon Oil Co., Ltd.), etc.

In the present invention, from the viewpoint of heat resistance, the radical 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 (P-3) part of the structure. * In the formula is a link key.

Specific examples of the radical polymerizable compound having the partial structure include trimethylolpropane tri (meth) acrylate, isocyanurate ethylene oxide modified di (meth) acrylate, Isocyanurate ethylene oxide modified tri (meth) acrylate, triallyl isocyanurate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dimethylolpropane Tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tetramethylolmethane tetra (meth) acrylate, etc. are particularly preferred in the present invention. These radically polymerizable compounds are used.

In the temporary adhesive composition used in the present invention, from the viewpoints of good adhesion, flat abrasiveness, peelability, and warpage suppression, it is free to add to the quality of the temporary adhesive composition other than the solvent. The content of the base polymerizable compound is preferably 1% by mass to 50% by mass, more preferably 1% by mass to 30% by mass, and even more preferably 5% by mass to 30% by mass. The radical polymerizable compound may be used singly or in combination of two or more kinds.

In addition, in the temporary adhesive composition used in the present invention, the mass ratio of the elastomer and the radical polymerizable compound when a radical polymerizable compound is added is preferred. Elastomer: radical polymerizable compound = 98: 2 ~ 10: 90, more preferably 95: 5 ~ 30: 70, particularly preferably 90: 10 ~ 50: 50. When the mass ratio of the elastomer to the radically polymerizable compound is within the above range, a temporary adhesive layer having excellent adhesion, flat abrasiveness, peelability, and warpage suppression can be formed.

<< Other ingredients >>

To the extent that the effects of the present invention are not impaired, the temporary adhesive composition used in the present invention may optionally be formulated with various additives such as a surfactant, a plasticizer, a hardener, Other catalysts, fillers, adhesion promoters, ultraviolet absorbers, anti-agglomerating agents, elastomers, or other polymer compounds. When these additives are blended, the blending amounts thereof are each preferably 3% by mass or less, and more preferably 1% by mass or less of the total solid content of the temporary adhesive composition. The lower limit values at the time of blending are each preferably 0.0001% by mass or more. The total blended amount of these additives is preferably 10% by mass or less, and more preferably 3% by mass or less of the total solid content of the temporary adhesive composition. The lower limit of the total blended amount when these components are blended is preferably 0.0001% by mass or more.

The temporary adhesive composition used in the present invention is preferably free of impurities such as metals. The content of impurities contained in these materials is preferably 1 mass ppm or less, more preferably 1 mass ppb or less, still more preferably 100 mass ppt or less, particularly preferably 10 mass ppt or less, and particularly preferably substantially Not included (below the detection limit of the measuring device).

Examples of a method for removing impurities such as metals from the temporary adhesive composition include filtration using a filter. The filter pore diameter is preferably a fine pore diameter of 10 nm Hereinafter, it is 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 may be previously cleaned with an organic solvent. In the filter filtration step, various filters can be used in series or in parallel. When multiple filters are used, filters with different pore sizes and / or materials can be used in combination. In addition, various materials may be filtered multiple times, and the step of multiple filtering may also be a cyclic filtering step.

In addition, as a method for reducing impurities such as metals contained in the temporary adhesive composition, methods such as: selecting a raw material with a small metal content as a raw material constituting the temporary adhesive composition; and selecting a raw material constituting the temporary adhesive composition Filtering is performed; distillation is performed under conditions that use polytetrafluoroethylene equal to forming a lining in the device to suppress contamination as much as possible. The preferable conditions in the filter filtration of the raw material which comprises a temporary adhesive composition are the same as the said conditions.

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

<Preparation of temporary adhesive composition>

The temporary adhesive composition used in the present invention can be prepared by mixing the respective components. Mixing of each component is performed normally in the range of 0 degreeC-100 degreeC. Moreover, after mixing each component, it is preferable to filter with a filter, for example. Filtration can be performed in multiple stages or iteratively. Alternatively, the filtered liquid may be refiltered.

The filter can be used without particular limitation as long as it has been used for filtering purposes and the like. Examples include the use of fluororesins such as polytetrafluoroethylene (PTFE), polyamide resins such as nylon-6, nylon-6,6, polyolefin resins such as polyethylene and polypropylene (including polypropylene) Density, ultra-high molecular weight polyolefin resin) and other raw material filters. Among these raw materials, polypropylene (containing high-density polypropylene) and nylon are preferred.

The pore diameter of the filter is preferably about 0.003 μm to 5.0 μm, for example. By setting it as this range, clogging of a filter can be suppressed, and the fine foreign matter, such as an impurity and an aggregate, contained in a composition can be removed reliably.

When using filters, different filters can be combined. At this time, the filtration using the first filter may be performed only once, or may be performed twice or more. When two or more filtrations are performed by combining different filters, it is preferable that the pore diameters of the second and subsequent pores are the same as or smaller than those of the first filtration. In addition, it is also possible to combine the first filters with different pore diameters within the range. The pore size here can refer to the nominal value of the filter manufacturer. As commercially available filters, for example, Pall Corporation (Japan), Advantec Toyo Corporation, Japan Entegris Corporation (formerly Japan Micore ( Mykrolis Co., Ltd.) or Kitz Microfilter Co., Ltd.

The semiconductor element obtained in the present invention enables the moving distance between the position before the crimping at the temperature T1 of the die and the position after the crimping at the temperature T1 of the die to be small. At 100 μm, the moving distance can be made smaller than 50 μm, and the moving distance can be made smaller than 30 μm. The lower limit value is preferably 0 μm, but a level of 3 μm or more is a practically sufficient level.

[Example]

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

<Preparation of temporary adhesive composition>

The following compositions were mixed and filtered using a polytetrafluoroethylene filter having a pore size of 5 μm to prepare a temporary adhesive composition, respectively.

<< The composition of the temporary adhesive composition >>

． Resin listed in Table 1

． Irganox 1010 (manufactured by BASF): 1 part by mass

． Sumilizer TP-D (manufactured by Sumitomo Chemical Co., Ltd.): 1 part by mass

． Megafac F-557 (manufactured by DIC): 0.3 parts by mass

． Solvent (third butylbenzene (manufactured by Toyo Kogyo Co., Ltd.)): parts by mass shown in Table 1

The composition of the temporary adhesive composition used in each Example is shown below.

The compounds described in Table 1 are as follows.

<Measurement of melt viscosity>

The melt viscosity of the temporary adhesive layer is measured by the following method.

The temporary adhesive composition was cast on a 20 mm diameter PFA dish and After drying for 3 days, heating at 190 ° C for 5 minutes, and recovering from a petri dish, an evaluation sample having a diameter of 20 mm and a thickness of 300 µm was obtained. ARES-RDA (manufactured by TA Instruments) was used to measure the samples for evaluation at a temperature rise rate of 10 ° C / min and a measurement frequency: 10 Hz, T1, and T2.

<Example 1 to Example 9, Example 12 to Example 15 and Comparative Example 1 to Comparative Example 3>

As the carrier substrate, a silicon wafer with a diameter of 12 inches (2.54 cm in 1 inch) was used. On the surface, a wafer bonding device (Synapse V, Tokyo Electron) was used. ) Forming a temporary adhesive layer. Specifically, the temporary adhesive composition was coated on a carrier substrate, and heated at 160 ° C. for 3 minutes using a hot plate, and further heated at 190 ° C. for 3 minutes, thereby forming 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 was formed, a 10 mm × 10 mm silicon wafer (thickness: 775 μm) was cut as a crystal grain using a flip chip bonder (TFC-3000, Shibaura Mechatronics Co., Ltd.) was crimped for 2 seconds at the temperature (T1) shown in Table 3 so that the pressure applied to the crystal grains became 0.1 MPa.

About the obtained laminated body, the crystal grain shift was evaluated as follows.

<Evaluation 1: Crystal grain shift>

For the moving distance of the vertices of the crystal grains in the laminated body (| the design value of the coordinates of the vertices-the coordinates of the vertices after installation |), a wafer automatic appearance inspection device (shen Condor 203 (manufactured by Camtek) 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 criteria. In addition, the coordinates of the vertices of the design value are the same as the coordinates of the vertices before crimping, and the coordinates of the vertices after mounting refer to the coordinates of the vertices after 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 laminated body on which the crystal grains are provided, a compression molding machine (WCM-300, manufactured by APIC YAMADA) was used under the temperature (T2) conditions described in Table 3. For 80 seconds at a pressure of 80 × 10 ⁵ Pa for an epoxy resin molding material for semiconductor sealing (Sumikon EME-G770H, manufactured by Sumitomo Bakelite Co., Ltd.) as a molding resin composition. Compression molding. Then, it heated at 175 degreeC for 6 hours.

In addition, in Example 10, CEL-9200 HF10 (manufactured by Hitachi Chemical Co., Ltd.) was used as the molding resin composition, and in Example 11, KE-300TS-1 (Kyocera Chemical (Stock)) was used as the molding resin. A composition was molded in the same manner as in Example 1 except that the composition was molded.

About the obtained laminated body, the curvature was evaluated as follows.

<Evaluation 2: Warpage>

A film thickness sensor (manufactured by Keyence Corporation, ST-T80) was fixed to the X-Y stage, and the warpage in the laminate was measured. In the measurement, the X direction (substrate surface direction) and the Y direction (direction orthogonal to the X direction in the substrate surface direction) were specified, and the measurement was performed every 0.1 mm in the X direction and the measurement was performed every 1 mm in the Y direction.

Warpage was defined as the difference between the maximum value and the minimum value at all 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: 1000μm or more

<Evaluation 3: Peelability>

The molding layer of the obtained laminated body was set to the lower side, and the lower silicon wafer and the dicing frame were fixed to the center of the dicing tape using a dicing tape mounting machine. Thereafter, the wafer bonding device (manufactured by Tokyo Electron, Synapse Z) was used to position the upper silicon wafer in a direction perpendicular to the lower molding layer at 25 ° C. It was pulled up at a speed of 50 mm / min to peel off the upper silicon wafer. Next, the temporary adhesive layer laminated on the molding resin surface was pulled up at a speed of 50 mm / min in a vertical direction at 25 ° C., and the peel force at this time was evaluated by the following criteria. The measurement of the peeling force was performed using a dynamometer (ZTS-100N manufactured by Imada).

A: Peelable at less than 30N

B: Peelable at 30N or more and less than 50N

C: Peelable at 50N or more

D: Unable to peel

Claims (7)

A method for manufacturing a semiconductor element, comprising: crimping a component having a temporary adhesive layer on a carrier substrate and a crystal grain having a circuit on at least one side in a manner that the temporary adhesive layer is in contact with the crystal grain at a temperature T1, And forming a forming layer at a temperature T2 on the surface of the crystal grain on the side opposite to the side where the temporary adhesive layer is in contact, 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 becomes a temperature of 4000 Pa · s or more and 10,000 Pa · s or less, and the temperature T2 is the temperature of 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 manufacturing a semiconductor device according to item 1 of the scope of patent application, wherein a heat treatment at 100 ° C. or higher is performed after the forming layer is formed. The method for manufacturing a semiconductor device according to claim 1 or claim 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 manufacturing a semiconductor device according to claim 1 or claim 2, wherein the temporary adhesive layer includes at least one selected from a thermoplastic elastomer having a styrene structure, a cycloolefin-based polymer, and an acrylic resin. One. The method for manufacturing a semiconductor device according to claim 1 or claim 2, wherein the molding layer includes an epoxy resin. The method for manufacturing a semiconductor device according to item 1 or 2 of the scope of patent application, wherein the position before the crimping at the temperature T1 of the crystal grains and the position after the crimping at the temperature T1 of the crystal grains The moving distance is less than 100 μm. The method for manufacturing a semiconductor device according to claim 1 or claim 2, wherein the temporary adhesive layer contains at least one of a fluorine atom and a silicon atom.