KR20170085578A - Laminated body for temporary adhesion, laminated body, and kit - Google Patents

Abstract

Provided are a laminate for adhesion, a laminate, and a kit capable of linking peelability, flat polishing performance, and flexural restraint. An adhesive layer laminate having an adhesive layer comprising a curable composition and a release layer comprising a block copolymer and a compound having a fluorine atom.

Description

LAMINATED BODY FOR TEMPORARY ADHESION, LAMINATED BODY, AND KIT}

The present invention relates to a laminate for adhesion, a laminate, and a kit. More particularly, the present invention relates to a laminate for adhesion, a laminate, and a kit, which can be suitably used for manufacturing semiconductor devices and the like.

BACKGROUND ART [0002] In a manufacturing process of a semiconductor device such as an IC (integrated circuit) or an LSI (large-scale integrated circuit), a plurality of IC chips are formed on a device wafer and are diced into individual pieces.

In accordance with the demand for further miniaturization and high performance of electronic devices, further miniaturization and high integration of IC chips mounted in electronic devices are required.

Conventionally, a wire bonding method has been widely known as an electrical connection method from an integrated circuit in an IC chip to an external terminal of an IC chip. In order to miniaturize the IC chip, a device wafer has recently been provided with a through hole (A method of forming a so-called silicon through electrode (TSV)) is known in which a metal plug as an external terminal is connected to an integrated circuit so as to pass through the through hole. However, the method of forming the silicon penetrating electrode alone can not sufficiently cope with the recent demand for higher integration of the IC chip.

In view of the above, there is known a technique for improving the degree of integration per unit area of a device wafer by making the integrated circuit in the IC chip multilayered. However, since the thickness of the IC chip is increased in the multilayered structure of the integrated circuit, it is necessary to reduce the thickness of the member constituting the IC chip. As for such thinning of the member, for example, the thinning of the device wafer has been studied, leading to the miniaturization of the IC chip, and the manufacturing process of the through-hole of the device wafer in manufacturing the silicon through- In terms of being able, it is becoming promising. In addition, in semiconductor devices such as power devices and image sensors, thinning has been attempted from the viewpoints of improvement of the degree of integration and freedom of device structure.

As device wafers, those having a thickness of about 700 to 900 mu m are widely known. In recent years, attempts have been made to thin device wafer thicknesses to 200 mu m or less for the purpose of miniaturization of IC chips and the like.

For example, a technique has been known in which a device wafer and a carrier substrate before thinning are temporarily fixed (adhered) by an adhesive, and the back surface of the device wafer is ground to be thinned, followed by removing the carrier substrate from the device wafer.

Patent Document 1 discloses that a device wafer before thinning is adhered to a carrier substrate using a layer containing a styrene polymer and a silicone-based surface modifier.

Patent Document 2 discloses an adhesive for wafer processing which has a circuit surface on its surface and to which a wafer to be processed on its back surface is to be adhered to a support. The adhesive includes a thermoplastic siloxane bond-free (A), and a second adhesive layer which is laminated only on the central portion excluding the outer peripheral portion of the first adhesive layer and composed of the thermoplastic siloxane polymer layer (B), and further, in contact with the support, a thermosetting And a third adhesive layer comprising a siloxane polymer layer (C), wherein the polymer layer (A) containing no thermoplastic siloxane bond-containing polymer layer (A) and the thermosetting modified siloxane polymer And a composite adhesive layer in which the outer peripheral portions of the cinnabar polymer layer (C) are in direct contact with each other.

Patent Document 1: US Patent Publication No. 2013/0192754 Patent Document 2: JP-A-2013-243350

In the case where the device wafer and the carrier substrate adhere to each other, there is a demand for a property that the adhesion between the device wafer and the carrier substrate is good and the adhesion state between the device wafer and the carrier substrate is easily released.

According to a study made by the present inventors, in the method disclosed in Patent Document 1, it was found that when the laminate after the device wafer and the carrier substrate are adhered to each other is heat-treated, heat transfer of the adhesive layer causes deflection of the device wafer. Particularly, when the device wafer before thinning is adhered to the carrier substrate, and the back surface of the device wafer is ground to be thinned and then subjected to heat treatment, the device wafer after thinning is prone to bending. Further, the adhesive layer is liable to be deformed at the time of polishing the device wafer, and as a result, fine irregularities may be generated on the polished surface of the device wafer. In addition, the peelability of the device wafer and the carrier substrate was insufficient.

Further, in the method disclosed in Patent Document 2, the peeling property between the device wafer and the carrier substrate is insufficient. Further, since the adhesive has a three-layer structure, it has been necessary to carry out complicated processes in order to manufacture a laminate by adhering a device wafer and a carrier substrate.

SUMMARY OF THE INVENTION The present invention has been made in view of the above background, and an object of the present invention is to provide a laminate for adhesion, a laminate, and a kit, which can adhere peelability, flat polishing performance, and bending inhibition.

Means for Solving the Problems The present inventors have intensively studied in order to solve the above problems, and as a result, they have found that by using a laminating adhesive layer having an adhesive layer containing a curable composition and a release layer containing a block copolymer and a compound having a fluorine atom, The present inventors have found that the above object can be achieved by adhering the wafer and the carrier substrate together, thereby completing the present invention. The present invention provides the following.

≪ 1 > A pressure-sensitive adhesive laminate having an adhesive layer made of a curable composition, a block copolymer, and a release layer comprising a compound having a fluorine atom.

<2> The adhesive layered laminate according to <1>, wherein the fluorine atom-containing compound is a (meth) acrylic polymer.

&Lt; 3 > The adhesive laminate according to < 1 > or < 2 >, wherein the block copolymer comprises a repeating unit derived from styrene.

&Lt; 4 > The adhesive laminate according to any one of < 1 > to < 3 >, wherein the block copolymer is an elastomer.

&Lt; 5 > The adhesive layered laminate according to any one of < 1 > to < 4 >, wherein the block copolymer is a hydrogenated product.

<6> The adhesive layered laminate according to any one of <1> to <5>, wherein the block copolymer is a block copolymer having one or both ends of styrene block.

<7> The adhesive layered laminate according to any one of <1> to <6>, wherein the fluorine atom-containing compound has a hydrophilic group.

<8> The adhesive layered laminate according to any one of <1> to <7>, wherein the curable composition comprises a radically polymerizable compound.

<9> The adhesive layered laminate according to <8>, wherein the radical polymerizable compound is a compound having two or more radically polymerizable groups.

&Lt; 10 > The adhesive layered laminate according to any one of < 1 > to < 9 >, wherein the curable composition comprises a binder.

<11> The adhesive layered laminate according to any one of <1> to <10>, wherein the curable composition is a thermosetting composition.

<12> A laminate having a substrate on one side or both sides of the laminate for adhesion according to any one of <1> to <11>.

<13> The laminate according to <12>, wherein the base material is provided on both sides of the laminate for adhesion, one side of the base material is a carrier base material, and the other is a device wafer.

<14> The laminate according to <13>, wherein one side of the laminate for adhesion is in contact with the surface of the device wafer, and the other side of the laminate for adhesion is in contact with the surface of the carrier substrate.

<15> The laminate according to claim 14, wherein the release layer of the adhesive laminate is in contact with the surface of the device wafer.

<16> A kit for forming a laminate for adhesion comprising a composition for forming an adhesive layer comprising a curable composition, and a composition for forming a release layer comprising a block copolymer and a compound having a fluorine atom.

<17> The kit according to <16>, wherein the adhesive laminate is a laminate for adhesive lamination described in any one of <1> to <11>.

INDUSTRIAL APPLICABILITY According to the present invention, it becomes possible to provide a laminate for adhesion, a laminate, and a kit that can achieve peelability, flat polishing performance, and flexural restraint.

1 is a schematic view of an embodiment showing a method of manufacturing a semiconductor device.

Hereinafter, embodiments of the present invention will be described in detail.

In the notation of the group (atomic group) in the present specification, the notation in which substitution and non-substitution are not described includes those having a substituent and having a substituent. For example, the "alkyl group" includes not only an alkyl group having no substituent (an unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).

The term &quot; active ray &quot; or &quot; radiation &quot; in this specification includes, for example, visible light, ultraviolet light, far ultraviolet light, electron beam, X-ray and the like.

In the present specification, the term &quot; light &quot; means an actinic ray or radiation.

As used herein, the term &quot; exposure &quot; refers to exposure not only to exposure to far ultraviolet rays, X-rays, extreme ultraviolet rays (EUV) represented by mercury lamps, ultraviolet rays and excimer lasers, but also to particle beams such as electron beams and ion beams It also means drawing by.

As used herein, "(meth) acrylate" refers to acrylate and methacrylate, "(meth) acrylic" refers to acrylic and methacrylic, "(meth) acryloyl" Quot; and &quot; methacryloyl &quot;.

In the present specification, the weight average molecular weight and the number average molecular weight are defined as polystyrene reduced values by Gel Permeation Chromatography (GPC) measurement.

In the present specification, the term "hydrophilic group" means a functional group not containing a hydrophilic group. The term &quot; hydrophilic group &quot; means a functional group exhibiting affinity with water.

In the present specification, the viscosity can be measured using a B-type viscometer, and the viscosity is measured by using a viscosity measurement using a B-type viscometer (Viscol Advan, manufactured by FUNNYLAG Co., Ltd.).

In the embodiments described below, the members described in the drawings already referred to are denoted by the same reference numerals or signs in the drawings, thereby simplifying or omitting the description.

&Lt; Adhesive laminate &

The adhesive laminate of the present invention has an adhesive layer containing a curable composition and a release layer comprising a block copolymer and a compound having a fluorine atom.

The releasable layer of the adhesive laminate of the present invention contains a fluorine atom-containing compound, whereby excellent releasability can be obtained. Particularly, when the release layer contains a block copolymer, the fluorine atom-containing compound is unevenly distributed on the surface of the release layer, so that the release property can be enhanced. Further, even when the release layer is further provided with a block copolymer, even if the release layer is adhered to the device wafer or the like after the adhesion between the device wafer and the carrier substrate is released, the release layer can be easily released from the surface of the device wafer, The layer can be easily removed, and the cleaning and removing property is also excellent.

In addition, since the adhesive layer of the adhesive laminate of the present invention is formed of the curable composition, it is possible to suppress the deformation of the flow during heating after curing. This makes it possible to suppress the flow deformation of the adhesive layer at the time of heating, for example, when the laminate after the device wafer is polished is subjected to heat treatment, and the occurrence of warpage in the device wafer after polishing can be effectively . Further, since the adhesive layer having a high hardness can be formed after curing, even if the pressure is locally applied at the time of polishing the device wafer, the adhesive layer is hardly deformed and the flat polishing property of the device wafer is excellent.

When the adhesive layer contains a radically polymerizable compound, warpage may occur due to shrinkage upon curing of the radically polymerizable compound. However, when the release layer contains a block copolymer, By the action, the stress generated by the curing shrinkage of the adhesive layer can be relaxed, and warping can be suppressed.

Hereinafter, the adhesive layer laminate of the present invention will be described in detail.

<< Disclaimer >>

The release layer of the adhesive laminate of the present invention has a release layer containing a block copolymer and a compound having a fluorine atom. The release layer may be provided only on one side of the adhesive layer, or on both sides of the adhesive layer. Preferably, the adhesive layer has only one side of the adhesive layer.

The film thickness of the release layer is preferably 0.01 to 50 mu m. The lower limit is more preferably 0.1 탆 or more, and more preferably 1.0 탆 or more. The upper limit is more preferably 40 μm or less, and further preferably 20 μm or less. When the film thickness of the release layer is within the above range, the peeling property and cleaning property of the surface of the device wafer are excellent, and the effect of suppressing the fluidity at the time of heating can be expected.

The release layer can be formed using a composition comprising a block copolymer and a compound having a fluorine atom (a composition for forming a release layer). Hereinafter, the composition for forming a release layer will be described.

<<< Composition for releasing layer >>>

<<<< Block Copolymer >>>>

The composition for forming a release layer contains a block copolymer. The block copolymer is preferably contained in an amount of 50 to 99.99 mass% with respect to the total solid content of the composition for forming a release layer. The lower limit is more preferably 60% by mass or more, and still more preferably 70% by mass or more. The upper limit is more preferably 99.95 mass% or less. When the content of the block copolymer is within the above range, excellent peelability is likely to be obtained. Further, the cleaning and removing property is also excellent.

Examples of the block copolymer include, but are not limited to, polystyrene type copolymers, polyester type copolymers, polyolefin type copolymers, polyurethane type copolymers, polyamide type copolymers, polyacryl type copolymers, Polyimide-based copolymers, and the like. In particular, a polystyrene-based copolymer, a polyester-based copolymer and a polyamide-based copolymer are preferable, and a polystyrene-based copolymer is more preferable from the viewpoint of heat resistance and releasability. Among them, the block copolymer is preferably a block copolymer of styrene and another monomer, and a styrene block copolymer in which one terminal or both terminals are styrene block is particularly preferable. In the present invention, the styrene block means a unit comprising a repeating unit derived from styrene.

The block copolymer is preferably a hydrogenated product. When the block copolymer is a hydrogenated material, thermal stability and storage stability are improved. Further, the peelability and the removability of the release layer after peeling are improved. The hydrogenated product means a polymer in which a block copolymer is hydrogenated.

In the present invention, the block copolymer is preferably an elastomer. By using an elastomer as the block copolymer, it is possible to obtain a laminate for adhesion which follows the fine irregularities of the base material and has an excellent anchor effect by an appropriate anchor effect. Further, the releasability and the cleaning removability can be improved.

The elastomer may be used alone or in combination of two or more.

In the present specification, the elastomer refers to a polymer compound exhibiting elastic deformation at room temperature (20 ° C). That is, when an external force is applied, it is defined as a polymer compound that has a property of being instantly deformed according to its external force and recovering its original shape in a short time when an external force is removed.

In the present invention, the weight average molecular weight of the elastomer is preferably 2,000 to 200,000 or less, more preferably 10,000 to 200,000, and still more preferably 50,000 to 100,000. Within this range, even when the carrier substrate is peeled from the device wafer and the residue of the elastomer remaining on the device wafer and / or the carrier substrate is removed, the solubility in the solvent is excellent, There is an advantage such as not leaving.

In the present invention, the elastomer preferably has a 5% heat mass reduction temperature of 25 ° C or higher at 20 ° C / min of 250 ° C or higher, more preferably 300 ° C or higher, still more preferably 350 ° C or higher, And most preferably at least 400 ° C. The upper limit value is not particularly limited, but is preferably 1000 占 폚 or lower, for example, and more preferably 800 占 폚 or lower. According to this embodiment, a tacky adhesive layer having excellent heat resistance is easily formed.

In the present invention, the elastomer can be deformed to 200% at a room temperature (20 DEG C) with a small external force when the original size is 100%, and when the external force is removed, the elastomer returns to 130% It is preferable to have the property of coming.

<<<<< Polystyrene block copolymer >>>>>

The polystyrene-based elastomer is not particularly limited and may be appropriately selected depending on the purpose. For example, styrene-butadiene-styrene block copolymer (SBS), styrene-isoprene-styrene block copolymer (SIS), styrene-ethylene-butylene-styrene block copolymer ), Styrene-butadiene-butylene-styrene copolymer (SBBS) and hydrogenated products thereof, styrene-ethylene-propylene-styrene block copolymer (SEPS), styrene- Styrene block copolymer and the like.

The content of the styrene-derived repeating unit in the polystyrene-based block copolymer is preferably from 10 to 90% by mass. From the viewpoint of releasability, the lower limit value is preferably at least 15 mass%, more preferably at least 20 mass%, more preferably at least 40 mass%, even more preferably at least 50 mass%, and still more preferably at least 55 mass% . The upper limit is preferably 85% by mass or less, more preferably 70% by mass or less.

The polystyrenic block copolymer is more preferably a block copolymer in which one terminal or both terminals are styrene blocks, and it is particularly preferable that both terminals are styrene blocks. When both ends of the polystyrene-based elastomer are made of styrene block (a unit composed of repeating units derived from styrene), the heat resistance tends to be further improved. This is because the repeating unit derived from styrene having high heat resistance is present at the terminal. Particularly, since the block portion of the repeating unit derived from styrene is a reactive polystyrene-based hard block, it is preferable because heat resistance and chemical resistance tend to be better. When these are used as a block copolymer, it is considered that phase separation is performed between the hard block and the soft block at 200 캜 or higher. It is considered that the shape of the phase separation contributes to suppression of the generation of irregularities on the surface of the device wafer.

In the present specification, the "repeating unit derived from styrene" is a structural unit derived from styrene contained in the polymer when the styrene or styrene derivative is polymerized, and may have a substituent. Examples of the styrene derivative include? -Methylstyrene, 3-methylstyrene, 4-propylstyrene and 4-cyclohexylstyrene. Examples of the substituent include an alkyl group of 1 to 5 carbon atoms, an alkoxy group of 1 to 5 carbon atoms, an alkoxyalkyl group of 1 to 5 carbon atoms, an acetoxy group, and a carboxyl group.

Examples of commercially available polystyrene block copolymers include toughprene A, toughprene 125, toughprene 126S, solfrene T, asaprene T-411, asaprene T-432, asaprene T-437, 438, Asafrene T-439, Tuftec H1272, Tuftec P1500, Tuftec H1052, Tuftec H1062, Tuftec M1943, Tuftec M1911, Tuftec H1041, Tuftec MP10, Tuftec M1913, Tuftec H1051, Elastomer AR-850C, elastomer AR-840C, elastomer AR-860C, elastomer AR-860C, elastomer AR-875C, elastomer AR-810C, elastomer AR- Elastomer AR-SC-0, elastomer AR-SC-5, elastomer AR-710, elastomer AR-SC-65, elastomer AR-SC-30, elastomer AR- Elastomer AR-760, elastomer AR-741, elastomer AR-731, elastomer AR-750, elastomer AR-760, Elastomer AR-FL-85N, elastomer AR-FL-60N, elastomer AR-1050, elastomer AR-1060, elastomer AR-760, elastomer AR- 1040 (Aaron Gassée), Creighton D1111, Creighton D1113, Creighton D1114, Creighton D1117, Creighton D1119, Creighton D1124, Creighton D1126, Creayton D1161, Creayton D1162, Creayton D1163, Creighton 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, Kr Creighton D1171, Creighton D1173, Creighton D1153, Creayt D1152, Creighton D1153, Creighton D1124, Creighton D1101, Creighton D1102, Creayton D1116, Creayton D1118, Creayton D1133, Creayton D1152, , Creighton D1155, Kraton D1184, Kraton D1186, Kraton D1189, Kraton D1191, Kraton D1192, Kraton DX405, Kraton DX408, Kraton DX410, Kraton DX414, Kraton DX415, Kraton A1535, Kraton A1536, Kraton Fragments of FG1901, Kraton FG1924, Kraton G1640, Kraton G1641, Kraton G1642, Kraton G1643, Kraton G1645, Kraton G1633, Kraton G1650, Kraton G1651, Kraton G1652, Kraton G1654, Kraton G1657, TR2000, TR2001, TR2003, TR2250, TR2500, TR2500, TR2500, TR2500, TR2500, TR2500, TR2500, TR2500, DYNARON 8600P, DYNARON 8600P, DYNARON 8630P, DYNARON 8630P, DYNARON 8630P, DYNARON 8630P, DYNARON 8630P, DYNARON 8600P, DYNARON 8600P, DYNARON 8600P, DYNARON 8600P, DYNARON 8600P, DYNARON 8600P, DYNARON 8600P, DYNARON 8600P, DYNARON 8600P, Dynalon 8903P, Dynalon 6 (Manufactured by JSR Corporation), Denka STR series (manufactured by Denki Kagaku Kogyo), Quintex 3520, Quintex 3433N, Quintax 3421, Quintax 3620, Quintax 3450 and Quintax 3450 (Manufactured by Nippon Zeon), TPE-SB series (manufactured by Sumitomo Chemical), Lavalon series (Mitsubishi Kagaku), Septon 1001, Septon 4033, Septon 2104, Septon 2007, Septon 2004, Septon 2063, Septon HG 252, 8073, Septon 2002, Septon 1020, Septon 8104, Septon 2005, Septon 2006, Septon 4055, Septon 4044, Septon 4077, Septon 4099, Septon 8006, Septon 8004, Septon 8007, Septon 8104, Septon V9461, Septon V9475, Septon V9827, (Manufactured by Sumitomo Bakelite Co., Ltd.), rheostomer (available from Riken Vinyl High Strength Co., Ltd.), and the like can be given.

<<<<< Polyester Block Copolymer >>>>>

The polyester block copolymer is not particularly limited and may be appropriately selected depending on the purpose. For example, those obtained by polycondensation of a dicarboxylic acid or a derivative thereof with a diol compound or a derivative thereof.

Examples of the dicarboxylic acid include aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid and naphthalenedicarboxylic acid, aromatic dicarboxylic acids in which the hydrogen atoms of the aromatic nuclei are substituted with methyl, ethyl, phenyl and the like, adipic acid, Aliphatic dicarboxylic acids having 2 to 20 carbon atoms such as dicarboxylic acid, and alicyclic dicarboxylic acids such as cyclohexane dicarboxylic acid. These may be used alone or in combination of two or more.

Examples of the diol compounds include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,10-decanediol, , Alicyclic diols such as 4-cyclohexane diol, alicyclic diols, and divalent phenols represented by the following structural formula.

[Chemical Formula 1]

^Wherein Y ^DO represents any one of an alkylene group having 1 to 10 carbon atoms, a cycloalkylene group having 4 to 8 carbon atoms, -O-, -S-, and -SO ₂ -, or a direct bond between benzene rings Bond (single bond). R ^DO1 and R ^DO2 each independently represent a halogen atom or an alkyl group having 1 to 12 carbon atoms. p ^do1 and p ^do2 each independently represent an integer of 0 to 4, and n ^do1 represents 0 or 1;

Specific examples of the divalent phenol include bisphenol A, bis- (4-hydroxyphenyl) methane, bis- (4-hydroxy-3-methylphenyl) propane and resorcin. These may be used alone or in combination of two or more.

The polyester-based block copolymer is obtained by copolymerizing an aromatic polyester (e.g., polystyrene terephthalate) portion as a hard segment component and an aliphatic polyester (e.g., polytetramethylene glycol) portion as a soft segment component One multi-block copolymer may be used. As the multi-block copolymer, various grades may be cited depending on the kind, ratio, and molecular weight of the hard segment and the soft segment. Specific examples thereof include Hytrel (DuPont-Doreis), Pelprene (Toyoboseki), Primaloy (Mitsubishi Kagaku), Nouvelle (Deijin Gosei), Espel 1612 and 1620 (made by Hitachi Kasei Corporation) .

<<<<< Polyolefin Block Copolymer >>>>>

The polyolefin block copolymer is not particularly limited and may be appropriately selected depending on the purpose. Examples thereof include block copolymers of? -Olefins having 2 to 20 carbon atoms such as ethylene, propylene, 1-butene, 1-hexene and 4-methyl-pentene. The non-conjugated dienes having 2 to 20 carbon atoms such as dicyclopentadiene, 1,4-hexadiene, cyclooctadiene, methylene norbornene, ethylidene norbornene, butadiene, and isoprene, Block copolymers of olefins, and the like. Further, carboxy modified nitrile rubber obtained by copolymerizing methacrylic acid with a butadiene-acrylonitrile copolymer may be mentioned. Specific examples include ethylene /? - olefin copolymer rubber, ethylene /? - olefin / non-conjugated diene copolymer rubber, propylene /? - olefin copolymer rubber, and butene /? - olefin copolymer rubber.

<<<<< Polyurethane block copolymer >>>>>

The polyurethane-based block copolymer is not particularly limited and may be appropriately selected depending on the purpose. For example, a block copolymer containing a hard segment composed of low molecular weight glycol and diisocyanate and a soft segment composed of polymer (long chain) diol and diisocyanate have.

Examples of the polymer (long chain) diol include polypropylene glycol, polytetramethylene oxide, poly (1,4-butylene adipate), poly (ethylene 1,4-butylene adipate), polycaprolactone, poly (1,6-hexylene carbonate), and poly (1,6-hexylene-neopentylene adipate). The number average molecular weight of the polymer (long chain) diol is preferably from 500 to 10,000.

As a low molecular weight glycol, short chain diols such as ethylene glycol, propylene glycol, 1,4-butanediol, and bisphenol A can be used. The number-average molecular weight of the short-chain diol is preferably 48 to 500.

<<<<< Polyamide Based Block Copolymer >>>>>

The polyamide block copolymer is not particularly limited and may be appropriately selected depending on the purpose. For example, a polyamide such as polyamide-6, 11, 12 or the like may be used for a hard segment and a polyether and / or polyester such as polyoxyethylene, polyoxypropylene, and polytetramethylene glycol may be used as a soft segment And the like. This block copolymer is largely classified into two types, a polyether block amide type and a polyetherester block amide type.

Examples of commercially available products include UBE polyamide elastomer, UBESTA XPA (manufactured by Ube Gosei Co., Ltd.), diamide (manufactured by Daicel Evonik), PEBAX (manufactured by ARKEMA), Grilon ELX (manufactured by EMK Chemie Japan), Novamide (manufactured by Mitsubishi Kagaku) PAA-200, PA-201, TPAE-12, TPAE-32, polyester amide TPAE-617 and TPAE-617C (manufactured by T & K TOKA).

<<<<< Polyacrylic Block Copolymer >>>>>

The polyacrylic block copolymer is not particularly limited and may be appropriately selected depending on the purpose. For example, there may be mentioned acrylic acid esters such as ethyl acrylate, butyl acrylate, methoxyethyl acrylate, ethoxyethyl acrylate and the like as the main components, acrylic esters and glycidyl methacrylate, allyl glycidyl ether And the like. And those obtained by copolymerizing the above monomers with crosslinking point monomers such as acrylonitrile and ethylene. Specific examples include acrylonitrile-butyl acrylate copolymer, acrylonitrile-butyl acrylate-ethyl acrylate copolymer, acrylonitrile-butyl acrylate-glycidyl methacrylate copolymer, and the like. .

As a commercial product, there are Kurariti LA1114, Kurariti LA2140e, Kurariti LA2230, Kurariti LA2250, Kurariti LA3270, Kurariti LA4285 (Kurarayze).

<<<< Compounds Having Fluorine Atoms >>>>

The composition for forming a release layer includes a fluorine atom-containing compound (also referred to as a fluorine compound). The fluorine-containing compound is preferably contained in an amount of 0.01 to 20% by mass relative to the total solid content of the composition for forming a releasing layer. The lower limit is more preferably 0.05 mass% or more. The upper limit is more preferably 10 mass% or less, still more preferably 5 mass% or less, and most preferably 0.5 mass% or less. When the content of the fluorine compound is within the above range, excellent peelability is likely to be obtained.

The content of the fluorine-containing compound is preferably 0.01 to 20 parts by mass, more preferably 0.05 to 10 parts by mass, and most preferably 0.05 to less than 0.5 part by mass based on 100 parts by mass of the block copolymer.

As the fluorine compound, a liquid compound is preferable.

In the present invention, the liquid phase means a compound having fluidity at 25 캜, for example, a compound having a viscosity of 1 to 100,000 mPa 에서 at 25 캜.

The viscosity of the fluorine compound at 25 占 폚 is more preferably 10 to 20,000 mPa 占 퐏, and still more preferably 100 to 15,000 mPa 占 퐏. When the viscosity of the fluorinated compound is within the above range, fluorinated compounds tend to be unevenly distributed on the surface of the release layer.

In the present invention, the fluorinated compound may be any of monomers, oligomers, and polymers. It may also be a mixture of an oligomer and a polymer. Further, it may be a mixture of an oligomer and / or a polymer and a monomer.

The fluorinated compound is preferably an oligomer, a polymer, and a mixture thereof from the viewpoint of heat resistance and the like.

Examples of the oligomer and the polymer include a radical polymer, a cationic polymer, and an anionic polymer, all of which can be preferably used. Among them, a (meth) acrylic polymer is particularly preferable. Use of the fluorine-containing compound of the (meth) acryl-based polymer enables the fluorine-containing compound to be easily unevenly distributed on the surface of the release layer, and the effect of the excellent releasability can be expected.

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 2000 or more.

The weight average molecular weight of the fluorine compound is preferably 500 to 100000, more preferably 1000 to 50000, and still more preferably 2000 to 20,000.

In the present invention, the fluorinated compound is preferably a compound which does not denature at the time of the treatment of the substrate provided for adhesion. For example, a compound which can be present as a liquid phase even after heating at 250 DEG C or higher or after treating the substrate with various chemical solutions is preferable. As a specific example, it is preferable that the viscosity at 25 ° C after heating from 250 ° C to 25 ° C at a temperature elevation condition of 10 ° C / min from 25 ° C and then at 25 ° C is 1 to 100,000 mPa · s, mPa · s is more preferable, and 100 to 15,000 mPa · s is even more preferable.

As the fluorine compound having such characteristics, it is preferable that it is a non-thermosetting compound having no reactive group. The term "reactive group" as used herein refers to the whole group which reacts at a heating temperature of 250 ° C., and includes a polymerizable group and a hydrolyzable group. Specific examples thereof include a metha (acryl) group, an epoxy group, and an isocyanato group.

As the non-thermosetting compound, a polymer comprising one kind or two or more kinds of fluorine-containing monofunctional monomers can be preferably used. More specifically, there may be mentioned tetrafluoroethylene, hexafluoropropene, tetrafluoroethylene oxide, hexafluoropropene oxide, perfluoroalkyl vinyl ether, chlorotrifluoroethylene, vinylidene fluoride, purple (Meth) acrylic acid ester containing at least one fluoroalkyl group, a fluoroalkyl group-containing (meth) acrylic acid ester, and a fluoroalkyl group-containing (meth) acrylate ester, or copolymers of these monomers, , At least one fluorinated resin selected from a copolymer of one or more fluorinated monofunctional monomers and chlorotrifluoroethylene, and the like.

As the non-thermosetting compound, a (meth) acrylic copolymer containing a perfluoroalkyl group which can be synthesized from a perfluoroalkyl group-containing (meth) acrylic acid ester is preferable.

The (meth) acrylic copolymer having a perfluoroalkyl group may optionally be selected from a copolymerizable component in addition to the (meth) acrylic acid ester containing a perfluoroalkyl group, in view of releasability. Examples of the radical polymerizable compound capable of forming a copolymerization component include acrylic acid esters, methacrylic acid esters, N, N-2 substituted acrylamides, N, N-2 substituted methacrylamides, styrene, Acrylonitrile, acrylonitrile, methacrylonitrile, and the like.

More specifically, acrylic acid esters such as alkyl acrylate (preferably having 1 to 20 carbon atoms in the alkyl group) (for example, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, amyl acrylate, Ethylhexyl acrylate, octyl acrylate, t-octyl acrylate, chloroethyl acrylate, 2,2-dimethylhydroxypropyl acrylate, 5-hydroxypentyl acrylate, trimethylolpropane monoacrylate, pentaerythritol mono (E.g., acrylate, glycidyl acrylate, benzyl acrylate, methoxybenzyl acrylate, furfuryl acrylate, and tetrahydrofurfuryl acrylate), aryl acrylates Methacrylic acid esters such as methyl (meth) acrylate, ethyl (meth) acrylate, ethyl , Ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, amyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, chlorobenzyl methacrylate, octyl methacrylate, 4 -Hydroxybutyl methacrylate, 5-hydroxypentyl methacrylate, 2,2-dimethyl-3-hydroxypropyl methacrylate, trimethylolpropane monomethacrylate, pentaerythritol monomethacrylate , Methacrylic acid esters such as glycidyl methacrylate, furfuryl methacrylate, and tetrahydrofurfuryl methacrylate), aryl methacrylates (e.g., phenyl methacrylate, cresyl methacrylate, naphthyl methacrylate, ), Styrenes such as styrene and alkylstyrene (e.g., methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, di Examples of the styrene-butadiene styrene-butadiene styrene copolymer are styrene-butadiene-styrene, isopropyl styrene, butyl styrene, hexyl styrene, cyclohexyl styrene, decyl styrene, benzyl styrene, chloromethyl styrene, trifluoromethyl styrene, (E.g., methoxystyrene, 4-methoxy-3-methylstyrene, dimethoxystyrene and the like), halogensilane (e.g., chlorostyrene, But are not limited to, ethylene, propylene, butylene, dicyclopentadiene, norbornene, norbornene, norbornene, Bromo-4-trifluoromethylstyrene, 4-fluoro-3-trifluoromethylstyrene, etc.), acrylonitrile, methacrylonitrile acrylic acid, and a radically polymerizable compound containing carboxylic acid Methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, p-carboxyl styrene, and metal salts and ammonium salt compounds of these acid groups. (Meth) acrylic acid esters having a hydrocarbon group of 1 to 24 carbon atoms are particularly preferred from the viewpoint of releasability, and examples thereof include methyl, butyl, 2-ethylhexyl, lauryl, stearyl, glycidyl (Meth) acrylates of higher alcohols such as 2-ethylhexyl, lauryl and stearyl, especially higher alcohols such as 2-ethylhexyl, lauryl and stearyl are preferred.

In the present invention, the fluorine compound preferably has a 10% thermal mass reduction temperature at 25 ° C or higher at 20 ° C / min, preferably 250 ° C or higher, more preferably 280 ° C or higher. The upper limit value is not particularly limited, but is preferably 1000 占 폚 or lower, for example, and more preferably 800 占 폚 or lower. According to this embodiment, it is easy to form a laminate for adhesion with excellent heat resistance. The 10% thermal mass reduction temperature is a temperature at which a 10% reduction in mass before measurement is measured by the thermogravimetric analyzer under the above-mentioned temperature elevation condition under a nitrogen gas stream.

In the present invention, the fluorinated compound is preferably a compound containing a hydrophilic group. Examples of the hydrophilic group include an alkyl group and an aromatic group.

The alkyl group includes a straight chain alkyl group, a branched alkyl group and a cyclic alkyl group.

The number of carbon atoms of the straight chain alkyl group is preferably from 2 to 30, more preferably from 4 to 30, still more preferably from 6 to 30, and particularly preferably from 12 to 20.

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

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

Specific examples of the straight chain or branched alkyl group include straight or branched chain alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, An isopropyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a 1-ethylpentyl group and a 2-ethylhexyl group.

Specific examples of the cyclic alkyl group include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl, adamantyl, norbornyl, , A tricyclodecanyl group, a tetracyclodecanyl group, a camphoryl group, a dicyclohexyl group, and a pinenyl group.

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, and a fluorine atom is preferable.

The carbon number of the alkoxy group is preferably from 1 to 30, more preferably from 1 to 20, and even more preferably from 1 to 10. The alkoxy group is preferably straight-chain or branched.

The aromatic group may be monocyclic or polycyclic. The carbon number of the aromatic group is preferably from 6 to 20, more preferably from 6 to 14, and most preferably from 6 to 10.

The aromatic group may be monocyclic or polycyclic. The carbon number of the aromatic group is preferably from 6 to 20, more preferably from 6 to 14, and most preferably from 6 to 10. It is preferable that the aromatic group 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 group include a benzene ring, a naphthalene ring, a pentane ring, an indene ring, an azuren ring, a heptane ring, an indene ring, a perylene ring, a pentacene ring, an acenaphthalene ring, a phenanthrene ring, an anthracene ring, a naphthacene ring, A thiophene ring, a fluorene ring, a biphenyl ring, a pyrrole ring, a furan ring, a thiophen ring, an imidazole ring, an oxazole ring, a thiazole ring, a pyridine ring, a pyrazine ring, a pyrimidine ring, , Indole ring, benzofuran ring, benzothiophen ring, isobenzofuran ring, quinoline ring, quinoline ring, phthalazine ring, naphthyridine ring, quinoxaline ring, quinoxazoline ring, isoquinoline ring, carbazole ring, phenan Triazine ring, acridine ring, phenanthroline ring, thianthrene ring, cromene ring, zanthen ring, phenoxathiine ring, phenothiazine ring, and phenanthrene ring.

The aromatic group may have the substituent described above.

The fluorine-containing compound may be a compound containing only one oil-soluble group, or may contain two or more species. The organic group may contain a fluorine atom. That is, the fluorinated compound may be a compound in which only the oil-containing group contains a fluorine atom. Further, in addition to a hydrophilic group, a compound having a fluorine atom-containing group (also referred to as a fluorine group) may be used. Preferably, it is a compound containing a mineral oil and a fluorine group.

When the fluorine compound is a compound having a hydrophilic group and a fluorine group, the hydrophilic group may or may not contain a fluorine atom, but it is preferable that the hydrophilic group does not contain a fluorine atom.

The fluorine-containing compound preferably has 2 or more, more preferably 6 to 80, groups having at least one lipophilic group in one molecule.

As the fluorine group, a known fluorine group can be used. For example, fluorinated alkyl groups, fluorinated alkylene groups and the like. Among the fluorine groups, those functioning as a lipophilic group are assumed to be included in lipophilic groups.

The carbon number of the fluorinated alkyl group is preferably from 1 to 30, more preferably from 1 to 20, and still more preferably from 1 to 15. The fluorine alkyl group may be linear, branched or cyclic. It may also have an ether bond. The fluorinated alkyl group may also be a perfluoroalkyl group in which all of the hydrogen atoms are substituted with fluorine atoms.

The fluorine-containing alkylene group preferably has 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, and more preferably 2 to 15 carbon atoms. The fluorine-containing alkylene group may be linear, branched or cyclic. It may also have an ether bond. The fluorinated alkylene group may be a perfluoroalkylene group in which all of the hydrogen atoms are substituted with fluorine atoms.

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

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

Commercially available products may also be used as fluorine compounds. (DuPont), Fluor (Asahi Glass Co.), Hyler (Solvay Solexis), Haier (Solvay Solexis), etc., which are commercially available as non-thermosetting compounds, Fluoropolymers such as Lumiproline (Asahi Glass Co., Ltd.), Arplus (Asahi Glass Co., Ltd.), Sephrill Soft (Central Glass Co., Ltd.), Sephreel Coat (Central Glass Co., Ltd.), Viton Fluorine rubber of the trade name SIFEL (Shin-Etsuga Kagaku Kogyo Co., Ltd.), Krytox (DuPont), Pomphlaine (Daitoku Tech), Demnum (Daiking Kogyo) (Fluorocarbon resin), fluorocarbon resin (fluorocarbon resin), fluorocarbon resin (fluorocarbon resin), fluorocarbon resin (fluorocarbon resin), fluorocarbon resin And the like.

F-551, F-555, F-555, F-251, F-281, F-477, F-553, F-566, F-567, F-568, F-571, R-40, R-41, F-556, F-557, F-558, F-559, F- R-43, R-94, and 710F, 710FM, 710FS, 710FL, 730FL, and 730LM of the Neptune fetter series.

In the present invention, a fluorine-containing silane coupling agent may be used as the fluorine compound. The fluorine-containing silane coupling agent is preferably a fluorine-containing alkoxysilane. Commercially available products include an optool DAC-HP and an Optol DSX manufactured by Daikin Industries.

<<<< Antioxidants >>>>

The composition for forming a release layer may contain an antioxidant. As the antioxidant, phenol antioxidants, sulfur antioxidants, phosphorus antioxidants, quinone antioxidants, amine antioxidants and the like can be used.

Examples of the phenol antioxidant include p-methoxyphenol, 2,6-di-tert-butyl-4-methylphenol, BASF products "IRGANOX 1010", "IRGANOX 1330", "IRGANOX 3114", "IRGANOX 1035 Sumilizer MDP-S &quot;, &quot; Sumilizer GA-80 &quot;, and the like.

Examples of the sulfur-based antioxidant include 3,3'-thiodipropionate distearyl, Sumilizer TPM, Sumilizer TPS, Sumilizer TP-D and the like.

Examples of the phosphorus antioxidant include tris (2,4-di-tert-butylphenyl) phosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, poly Dialkyldiphenylphosphite, triphenylphosphite, BASF products &quot; Irgafos 168 &quot;, and &quot; Irgafos 38 &quot;.

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

Examples of the amine-based antioxidant include dimethyl aniline and phenothiazine.

IRGANOX 1010, IRGANOX 1330, 3,3'-thiodipropionate distearyl, Sumilizer TP-D are preferable, IRGANOX 1010 and IRGANOX 1330 are more preferable, and IRGANOX 1010 is particularly preferable.

Among the above-mentioned antioxidants, phenol-based antioxidants and sulfur-based antioxidants or phosphorus-based antioxidants are preferably used in combination, and phenol-based antioxidants and sulfur-based antioxidants are most preferably used in combination. By using such a combination, the effect of effectively suppressing the deterioration of the pseudo adhesion laminate due to the oxidation reaction can be expected. When the phenolic antioxidant and the sulfur antioxidant are used in combination, the mass ratio of the phenol antioxidant to the sulfur antioxidant is preferably 95: 5 to 5:95, : 25 is more preferable.

IRGANOX 1010, Sumilizer TP-D, IRGANOX 1330 and Sumilizer TP-D, Sumilizer GA-80 and Sumilizer TP-D are preferable, IRGANOX 1010 and Sumilizer TP-D, IRGANOX 1330 and Sumilizer TP- D is more preferable, and IRGANOX 1010 and Sumilizer TP-D are particularly preferable.

From the viewpoint of preventing sublimation during heating, the molecular weight of the antioxidant is preferably 400 or more, more preferably 600 or more, and particularly preferably 750 or more. The upper limit value of the molecular weight of the antioxidant is not particularly limited, but may be less than 2000, for example.

When the composition for forming a releasing layer has an antioxidant, the content of the antioxidant is preferably 0.001 to 40.0% by mass based on the total solid content of the composition for forming a releasing layer. The lower limit is more preferably 0.1 mass% or more, and still more preferably 0.5 mass% or more. The upper limit is more preferably 30 mass% or less, and still more preferably 10 mass% or less.

The antioxidant may be of one kind alone or in combination of two or more kinds. When the amount of the antioxidant is two or more, the total amount is preferably in the above range.

<<<< Surfactant >>>>

The composition for forming a release layer may contain a surfactant.

As the surfactant, any of anionic, cationic, nonionic or amphoteric surfactants may be used, but preferred surfactants are nonionic surfactants.

Examples of nonionic surfactants include polyoxyethylene higher alkyl ethers, polyoxyethylene higher alkyl phenyl ethers, higher fatty acid diesters of polyoxyethylene glycol, and silicone surfactants.

The composition for forming a release layer preferably contains a silicone surfactant as a surfactant from the viewpoint of coatability. In general, when a composition having a high viscosity is used, it is difficult to apply the composition in a uniform thickness. However, since it is easy to coat the composition with a uniform thickness by containing a surfactant, it can be more preferably used.

As examples of these silicone surfactants, mention may be made of, for example, JP-A 62-36663, JP-A 61-226746, JP-A 61-226745, JP-A 62-170950, Japanese Patent Application Laid-Open Nos. 63-34540, 7-230165, 8-62834, 9-54432, 9-5988, Japanese Patent Application Laid-Open No. 2001-330953, and surfactants commercially available.

Examples of commercially available silicone surfactants include KP-301, KP-306, KP-109, KP-310, KP-310B, KP-323, KP-326, KP- KP-365, KP-365, KP-358, KP-358, KP-361, KP-361, -368, KP-369, KP-330, KP-650, KP-651, KP-390, KP-391 and KP-392 available from Shin-Etsu Chemical Co.,

When the composition for forming a release layer contains a surfactant, the content of the surfactant is preferably 0.001 to 5.0% by mass based on the total solid content of the composition for forming a release layer. The lower limit is more preferably 0.005 mass% or more, and still more preferably 0.01 mass% or more. The upper limit is more preferably 3.0 mass% or less, and more preferably 1.0 mass% or less.

<<<< Solvent >>>>>

The composition for forming a release layer preferably contains a solvent. As the solvent, any of known solvents can be used without limitation, and organic solvents are preferable.

Examples of the organic solvent include ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, butyl butyrate, butyl lactate, (For example, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.)), 3-oxypropionic acid alkyl esters such as methyl 3-oxypropionate and ethyl 3-oxypropionate (for example, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3- Ethyl ethoxypropionate, etc.)), 2-oxypropionic acid alkyl esters (e.g., methyl 2-oxypropionate, ethyl 2-oxypropionate, Propyl methoxypropionate, ethyl 2-ethoxypropionate), 2-oxy-2- (2-methoxypropionate, Methyl propionate and ethyl 2-oxy-2-methylpropionate (for example, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate and the like), methyl pyruvate, ethyl pyruvate, , Esters such as methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, and 1-methoxy-2-propyl acetate;

Diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol mono Diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether, Ethers such as acetate, propylene glycol monopropyl ether acetate;

Ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone, N-methyl-2-pyrrolidone and? -Butyrolactone;

Aromatic hydrocarbons such as toluene, xylene, anisole, and mesitylene;

And hydrocarbons such as limonene and p-menthane.

These solvents are also preferably mixed with two or more kinds in view of improving the application surface shape and the like. In this case, it is particularly preferable to use methylethylene, p-menthane, y-butyrolactone, anisole, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethylcellosolve acetate, ethyl lactate, But are not limited to, glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, ethylcarbitol acetate, butylcarbitol acetate, propylene glycol methyl ether, Methyl ether acetate, and mixtures thereof.

In the case where the composition for forming a releasing layer has a solvent, the content of the solvent in the releasing layer forming composition is preferably such that the total solid content concentration of the composition for forming a releasing layer is 5 to 80 mass% By mass to 70% by mass, and particularly preferably 10% by mass to 60% by mass.

The solvent may be a single kind or two or more types. When two or more kinds of solvents are used, the total amount is preferably in the above range.

<<<< Other Ingredients >>>>

The composition for forming a release layer may contain various compounds in accordance with the purpose, in addition to the block copolymer and the fluorine compound, insofar as the effect of the present invention is not impaired. For example, a thermal polymerization initiator, a sensitizing dye, and a chain transfer agent can be preferably used. When these additives are compounded, the total amount of these additives is preferably 3% by mass or less based on the total solid content of the composition for forming a release layer.

The composition for forming a release layer in the present invention preferably contains no impurities such as metals. The content of the impurities contained in these materials is preferably 1 mass ppm or less, more preferably 1 mass ppb or less, more preferably 100 mass ppt or less, even more preferably 10 ppt or less, (Which is below the detection limit of the measuring apparatus) is particularly preferable.

Examples of the method for removing impurities such as metals from the composition for forming a release layer include filtration using a filter, for example. The filter hole diameter is preferably 10 nm or less, more preferably 5 nm or less, and further preferably 3 nm or less. As the material of the filter, a filter made of polytetrafluoroethylene, polyethylene or nylon is preferable. The filter may be previously washed with an organic solvent. In the filter filtering step, a plurality of types of filters may be connected in series or in parallel. When a plurality of types of filters are used, filters having different hole diameters and / or different materials may be used in combination. In addition, the various materials may be filtered a plurality of times, and the step of filtering a plurality of times may be a circulating filtration step.

As a method for reducing impurities such as metals contained in the composition for forming a release layer, it is possible to select a raw material having a small metal content as a raw material constituting the composition for forming a release layer, or to select a raw material constituting the composition for forming a release layer Filtration is performed, or a method in which the inside of the device is lined with polytetrafluoroethylene or the like and distillation is carried out under the condition that the contamination is suppressed as much as possible. Is the same as the above-described conditions in the filter filtration performed on the raw material constituting the adhesive.

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

<< Adhesive layer >>

Since the adhesive layer of the adhesive laminate of the present invention is formed of the curable composition, the flow deformation of the adhesive layer during heating can be suppressed. This makes it possible to suppress the flow deformation of the adhesive layer at the time of heating, for example, when the laminate after the device wafer is polished is subjected to heat treatment, and the occurrence of warpage in the device wafer after polishing can be effectively . In addition, since an adhesive layer having a high hardness can be formed, even if pressure is applied locally at the time of polishing the device wafer, the adhesive layer is hardly deformed. As a result, excellent flat polishing performance can be obtained.

Further, in the present invention, the curable composition means a composition in which a polymerization reaction such as a polymerizable compound proceeds by irradiation of energy such as heat or light.

The thickness of the adhesive layer is preferably 0.1 to 1000 mu m. The lower limit is more preferably 0.5 탆 or more, and more preferably 1.0 탆 or more. The upper limit is more preferably 500 μm or less, and further preferably 100 μm or less. If the thickness of the adhesive layer is within the above range, the adhesive layer laminate has a suitable adhesive strength, and the adhesive property to the substrate is good, and the adhesive laminate can be easily peeled off from the surface of the substrate. Furthermore, it is excellent in warpage suppression and flat polishing performance.

The adhesive layer of the adhesive layer preferably has a storage elastic modulus (G ') at 150 ° C before curing (before adhesion) of 1,000 to 5,000,000 Pa, more preferably 10,000 to 2,000,000 Pa, and preferably 100,000 to 1,000,000 Pa Most preferred. The storage elastic modulus (G ') of the adhesive layer at 250 ° C after curing (after adhesion) is preferably 50,000 to 20,000,000 Pa, more preferably 100,000 to 10,000,000 Pa, and even more preferably 400,000 to 1,000,000 Pa Is most preferable. As described above, the storage elastic modulus of the adhesive layer is changed by curing, so that it can follow the unevenness of the surface of the substrate at the time of adhesion, and even after the curing (after adhesion) It is possible to maintain adhesion between the substrates.

The storage elastic modulus G 'referred to herein can be measured using a known dynamic viscoelastic device (for example, Rheosol-G1000 (Ubiquitous)). The sample shape is 1 mm in thickness and 20 mm in diameter, Means a storage elastic modulus (G ') when the temperature is raised from 50 캜 to 300 캜 at a heating rate of 5 캜 / min under a shear condition of a frequency of 10 Hz and a deformation of 0.1 캜.

The adhesive layer can be formed using a composition (a composition for forming an adhesive layer) containing a curable composition. Hereinafter, the adhesive layer forming composition will be described.

<<< Composition for forming an adhesive layer >>>

<<<< Curable Composition >>>>>

In the present invention, the curable composition preferably contains a polymerizable compound. As the polymerizable compound, known compounds that can be crosslinked by radicals, acids and heat can be used. For example, a compound having an ethylenically unsaturated bond, a cyclic ether (epoxy, oxetane) group, a methylol group, or the like can be given. Examples of the group having an ethylenic unsaturated bond include a vinyl group, a (meth) allyl group, and a (meth) acryloyl group.

The curable composition can be suitably used for both the photo-curable composition and the thermosetting composition, but from the viewpoints of adhesion, flexural restraint and flat abrasive property, the thermosetting composition is more preferable. From the viewpoint of curability, the curable composition preferably contains a radically polymerizable compound. As the thermosetting composition, for example, a composition which is cured when it is heated to 60 占 폚 or more.

The content of the polymerizable compound is preferably 10 to 100% by mass relative to the total solid content of the curable composition. The lower limit is more preferably 15 mass% or more, and still more preferably 30 mass% or more. The upper limit is more preferably 95 mass% or less, and further preferably 90 mass% or less.

<<<<< Radical Polymerizable Compound >>>>>

As the radical polymerizing compound, a compound having a radical polymerizing group, a known radical polymerizing compound capable of being polymerized by a radical can be used. Such compounds are widely known in the industrial field, and they can be used without any particular limitation in the present invention. These may be, for example, any of chemical forms such as monomers, prepolymers, oligomers or mixtures thereof and their multimers. Monomers are preferred.

In the present invention, the monomer-type radical polymerizable compound (hereinafter also referred to as polymerizable monomer) is a compound different from the polymer compound. The polymerizable monomer is typically a low molecular compound, preferably a low molecular weight compound having a molecular weight of 2000 or less, more preferably a low molecular weight compound having a molecular weight of 1,500 or less, and still more preferably a low molecular weight compound having a molecular weight of 900 or less. The molecular weight of the polymerizable monomer is usually 100 or more.

The oligomer type radical polymerizable compound (hereinafter also referred to as polymerizable oligomer) is typically a polymer having a relatively low molecular weight, and is preferably a polymer having 10 to 100 polymerizable monomers bonded thereto. The molecular weight is preferably 2000 to 20,000, more preferably 2,000 to 15,000, and most preferably 2,000 to 10,000 in terms of polystyrene conversion by gel permeation chromatography (GPC).

The functional group number of the radical polymerizable compound in the present invention means the number of radical polymerizable groups in one molecule. The radical polymerizable group is a group capable of polymerization by the action of an actinic ray, radiation, or radical. Examples of the radical polymerizable group include groups having an ethylenic unsaturated bond. As the group having an ethylenically unsaturated bond, a styryl group, a (meth) acryloyl group and a (meth) allyl group are preferable, and a (meth) acryloyl group is more preferable. That is, the radical polymerizing compound used in the present invention is preferably a (meth) acrylate compound, more preferably an acrylate compound.

The radically polymerizable compound preferably contains at least one radically polymerizable compound having two or more radically polymerizable groups containing two or more radically polymerizable groups and preferably contains at least one radically polymerizable compound having three or more functional groups . The upper limit of the radically polymerizable group of the radical polymerizable compound is not particularly limited, but may be, for example, 15 or less, and may be 6 or less.

In addition, the radically polymerizable compound in the present invention preferably contains at least one radically polymerizable compound having three or more functional groups in view of improving the heat resistance by forming a three-dimensional crosslinked structure. A mixture of a radically polymerizable compound having two or less functional groups and a radically polymerizable compound having three or more functional groups may be used.

Specific examples of the radical polymerizing compound include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), esters thereof, amides, And is preferably an ester of an unsaturated carboxylic acid and a polyhydric alcohol compound, and an amide of an unsaturated carboxylic acid and a polyvalent amine compound, and a multimer thereof. Further, an addition reaction product of an unsaturated carboxylic acid ester or amide having a nucleophilic substituent such as a hydroxyl group, an amino group or a mercapto group with a monofunctional or multifunctional isocyanate or an epoxide, a monofunctional or polyfunctional A dehydration condensation reaction product with a carboxylic acid, and the like are suitably used. In addition, it is also possible to use an unsaturated carboxylic acid ester or amide having an electrophilic substituent such as an isocyanate group or an epoxy group, an addition reaction product of monofunctional or polyfunctional alcohols, amines, thiols, Unsaturated carboxylic acid esters or amides having a desilyl substituent group and mono- or polyfunctional alcohols, amines, and thioes are also suitable. As another example, in place of the above unsaturated carboxylic acid, it is also possible to use a compound group substituted with an unsaturated phosphonic acid, a vinylbenzene derivative such as styrene, a vinyl ether, an ally ether or the like.

As these specific compounds, the compounds described in paragraphs 0029 to 0037 of JP-A No. 2014-189696 can be suitably used in the present invention.

Also, a urethane-based addition polymerizable monomer prepared by the addition reaction of an isocyanate and a hydroxyl group is also suitable. Specific examples thereof include, for example, 1 in Japanese Patent Publication A polyisocyanate compound having two or more isocyanate groups in a molecule is produced by reacting a vinyl monomer containing two or more polymerizable vinyl groups in a molecule with a vinyl monomer containing a hydroxyl group represented by the following general formula (A) And the like.

CH ₂ = C (R ⁴ ) COOCH ₂ CH (R ⁵ ) OH (A)

(Provided that R ⁴ and R ⁵ each independently represent H or CH ₃ )

In addition, the urethane acrylates described in JP-B-51-37193, JP-A-2-32293, JP-A-2-16765, JP-A-58-49860 Japanese Patent Publication No. 56-17654, Japanese Patent Publication No. 62-39417, and Japanese Patent Publication No. 62-39418, all of which are well known in the art, are also suitable.

As the radical polymerizing compound, the compounds described in paragraphs 0095 to 0108 of Japanese Laid-Open Patent Publication No. 2009-288705 can be suitably used in the present invention.

As the radical polymerizing compound, a compound having at least one addition-polymerizable ethylene group and having a boiling point of 100 占 폚 or more at normal pressure is also preferable. As an example thereof, the compound described in paragraph 0040 of Japanese Laid-Open Patent Publication No. 2014-189696 can be suitably used in the present invention.

As the compound having at least one addition-polymerizable ethylenic unsaturated group having a boiling point of 100 占 폚 or higher at normal pressure, the compounds described in paragraphs 0254 to 0257 of JP-A No. 2008-292970 are also suitable.

Radical polymerizable compounds represented by the following general formulas (MO-1) to (MO-5) may also be suitably used. In the formula, when T is an oxyalkylene group, the terminal on the carbon atom side is bonded to R.

(2)

(3)

In the general formula, n is an integer of 0 to 14, and m is an integer of 1 to 8. A plurality of R and T present in one molecule may be the same or different.

At least one of the plurality of Rs is -OC (= O) CH = CH ₂ or -OC (= O (O) ) C (CH ₃₎ represents a group represented by = CH _2.

As specific examples of the radical polymerizable compound represented by the above formulas (MO-1) to (MO-5), compounds described in paragraphs 0248 to 0251 of JP-A No. 2007-269779 are preferably used also in the present invention .

Further, in JP-A 10-62986, it is also possible to add ethylene oxide or propylene oxide to a polyfunctional alcohol, which is described together with specific examples thereof as general formulas (1) and (2) The compound may also be used as a radical polymerizing compound.

Examples of the radical polymerizable compound include dipentaerythritol triacrylate (KAYARAD D-330, Nippon Kayaku), dipentaerythritol tetraacrylate (KAYARAD D-320, Nippon Kayaku Co., (KAYARAD D-310; Nippon Kayaku), dipentaerythritol hexa (meth) acrylate (KAYARAD DPHA; Nippon Kayaku) as commercial products, and (meth) acryloyl group Ethylene glycol, and propylene glycol residues are preferably bonded to each other. These oligomer types can also be used.

The radically polymerizable compound may be a polyfunctional monomer having an acid group such as a carboxyl group, a sulfonic acid group or a phosphoric acid group. Examples of the polyfunctional monomer having an acid group include an aliphatic polyhydroxy compound and an ester of an unsaturated carboxylic acid, and a polyfunctional monomer having an acid group by reacting an unreacted hydroxyl group of the aliphatic polyhydroxy compound with a nonaromatic carboxylic acid anhydride . Especially preferably, in this ester, the aliphatic polyhydroxy compound is pentaerythritol and / or dipentaerythritol. Commercially available products include, for example, M-510 and M-520 as a polybasic acid-modified acrylic oligomer of Toagosei Corporation.

One kind of polyfunctional monomer having an acid group may be used alone, or two or more kinds thereof may be used in combination.

The acid value of the polyfunctional monomer having an acid group is preferably 0.1 to 40 mg KOH / g, particularly preferably 5 to 30 mg KOH / g. When the acid value of the polyfunctional monomer is within the above range, the preparation and handling properties are excellent.

As the radical polymerizing compound, a polyfunctional monomer having a caprolactone structure may also be used.

The polyfunctional monomer having a caprolactone structure is not particularly limited as long as it has a caprolactone structure in its molecule, and examples thereof include trimethylolethane, ditrimethylolethane, trimethylolpropane, ditrimethylolpropane (Meth) acrylic acid and? -Caprolactone obtained by esterifying polyhydric alcohols such as glycerin, diglycerol, trimethylolmelamine and the like with (meth) acrylic acid and? -Caprolactone, Modified polyfunctional (meth) acrylate. Among them, a polyfunctional monomer having a caprolactone structure represented by the following general formula (B) is preferable.

In general formula (B)

[Chemical Formula 4]

(Wherein all of the six Rs are groups represented by the following formula (C), or one to five of the six Rs are groups represented by the following formula (C) and the remainder is a group represented by the following formula It is an emerging period.)

In the general formula (C)

[Chemical Formula 5]

(Wherein R ¹ represents a hydrogen atom or a methyl group, m represents a number of 1 or 2, and "*" represents a bonding bond.)

In general formula (D)

[Chemical Formula 6]

(Wherein R ¹ represents a hydrogen atom or a methyl group, and "*" represents a bond.)

Such a polyfunctional monomer having a caprolactone structure is commercially available, for example, as a KAYARAD DPCA series from Nippon Kayaku. DPCA-20 (in the above formulas (B) to (D), m = 1, C) number = 2, R ¹ are both a hydrogen atom in the group represented by), DPCA-30 (the same formula, m = 1, the number of groups represented by the general formula (C) = 3, R ¹ is hydrogen atom DPCA-120 (the same formula, m = 1, the number of groups represented by formula (C) = 6 and R ¹ are all hydrogen atoms), DPCA-120 The number of groups represented by the general formula (C) = 6, and R1 are all hydrogen atoms).

In the present invention, the polyfunctional monomer having a caprolactone structure may be used singly or in combination of two or more.

The radical polymerizing compound is preferably at least one selected from the group of compounds represented by the following general formula (i) or (ii).

(7)

In the general formulas (i) and (ii), E independently represents - ((CH ₂ ) y CH ₂ O) - or - ((CH ₂ ) y CH (CH ₃ ) Independently represents an integer of 0 to 10, and each X independently represents a (meth) acryloyl group, a hydrogen atom, or a carboxyl group.

In the general formula (i), the sum of the (meth) acryloyl groups is 3 or 4, m is independently an integer of 0 to 10, and the sum of m is an integer of 0 to 40.

The total number of (meth) acryloyl groups in the general formula (ii) is 5 or 6, and each n independently represents an integer of 0 to 10, and the sum of n is an integer of 0 to 60.

In the general formula (i), m is preferably an integer of 0 to 6, more preferably an integer of 0 to 4.

The sum of m is preferably an integer of 2 to 40, more preferably an integer of 2 to 16, and an integer of 4 to 8 is particularly preferable.

In the general formula (ii), n is preferably an integer of 0 to 6, more preferably an integer of 0 to 4.

The sum of each n is preferably an integer of 3 to 60, more preferably an integer of 3 to 24, and particularly preferably an integer of 6 to 12.

The - ((CH ₂ ) _y CH ₂ O) - or - ((CH ₂ ) _y CH (CH ₃ ) O) - in the general formula (i) or the general formula X is preferable.

Particularly, in the general formula (ii), all of the six X's are preferably acryloyl groups.

The compound represented by the general formula (i) or (ii) can be produced by a process known in the art such as a step of binding an open-chain skeleton to pentaerythritol or dipentaerythritol by ring-opening addition reaction of ethylene oxide or propylene oxide, Can be synthesized from a step of introducing a (meth) acryloyl group by reacting a terminal hydroxyl group of the (meth) acryloyl chloride with, for example, (meth) acryloyl chloride. Each process is a well-known process, and one skilled in the art can easily synthesize the compound represented by the general formula (i) or (ii).

Among the compounds represented by the general formulas (i) and (ii), pentaerythritol derivatives and / or dipentaerythritol derivatives are more preferable.

Specific examples include the compounds represented by the following formulas (a) to (f) (hereinafter also referred to as "exemplified compounds (a) to (f)") (e) and (f) are preferable.

[Chemical Formula 8]

[Chemical Formula 9]

Examples of commercially available radically polymerizable compounds represented by the general formulas (i) and (ii) include SR-494, which is a tetrafunctional acrylate having four ethyleneoxy chains of a saturant, pentyleneoxy chain of Nippon Kayaku Co., DPCA-60, which is a hexafunctional acrylate having 6 carbon atoms, and TPA-330, which is a trifunctional acrylate having three isobutyleneoxy chains.

The radically polymerizable compounds are described in Japanese Patent Publication Nos. 48-41708, 51-37193, 2-32293, and 2-16765, Butene-containing acrylate, ethylene-vinyl acetate copolymer, ethylene-vinyl acetate copolymer, ethylene-vinyl acetate copolymer, Yutein compounds having an oxide-based skeleton are also suitable. Further, as the radical polymerizing compound, addition polymerization having an amino structure or sulfide structure in the molecule, which is described in JP-A-63-277653, JP-A-63-260909 and JP-A-1-105238, Sex monomers may also be used.

N-Ester M-4G, NK Ester A-9300, NK Ester M-9300 (manufactured by Sanyo Chemical Industries, Ltd.), Urethane , NK Ester A-TMMT, NK Ester A-DPH, NK Ester A-BPE-4, UA-7200 (manufactured by Shin Nakamura Kagaku Kogyo K.K.), DPHA-40H (Nippon Kayaku), UA- -306T, UA-306I, AH-600, T-600, AI-600 (now Kyoei) and Blemmer PME400 (Nichijo).

In the present invention, the radical polymerizing compound preferably has at least one of the partial structures represented by the following (P-1) to (P-4) from the viewpoint of heat resistance, It is more preferable to have a partial structure. * In the equation is the connecting hand.

[Chemical formula 10]

Specific examples of the radical polymerizable compound having the partial structure include trimethylolpropane tri (meth) acrylate, isocyanuric acid ethylene oxide modified di (meth) acrylate, isocyanuric acid ethylene oxide (Meth) acrylate, dipentaerythritol tetra (meth) acrylate, dimethylol propane tetra (meth) acrylate, dipentaerythritol tri (meth) acrylate, (Meth) acrylate, tetramethylolmethane tetra (meth) acrylate, and the like. In the present invention, these radically polymerizable compounds are particularly preferably used Can be used. Commercially available products include TAIC (registered trademark) (manufactured by Nippon Kayaku) and the like.

<<<<< Compounds Having Epoxy Groups >>>>>

In the present invention, a compound having an epoxy group (also referred to as an epoxy compound) may be used as the polymerizable compound.

The epoxy compound is preferably a compound having two or more epoxy groups. The number of epoxy groups is preferably 2 to 10, more preferably 2 to 5.

The epoxy compound preferably has an epoxy equivalent (= molecular weight of the epoxy compound / number of epoxy groups) of 500 g / eq or less, more preferably 100 to 400 g / eq, further preferably 100 to 300 g / eq.

The epoxy compound may be a low molecular weight compound (for example, having a molecular weight of less than 2,000, and further having a molecular weight of less than 1,000), and may be a high molecular weight compound (e.g., a molecular weight of 1000 or more, a weight average molecular weight of 1000 or more, Average molecular weight of 2000 or more). The weight average molecular weight of the epoxy compound is preferably 200 to 100,000, more preferably 500 to 50,000.

Specific examples of the epoxy compound include a bisphenol A type epoxy compound, a bisphenol F type epoxy compound, a phenol novolak type epoxy compound, a cresol novolak type epoxy compound, and an aliphatic epoxy compound. The aliphatic epoxy compound may be a compound having a straight chain and / or branched carbon chain and an epoxy group, and the carbon chain may be bonded with an oxygen atom, a nitrogen atom, a sulfur atom, a chlorine atom, etc. in addition to a hydrogen atom.

EPOC, NC, BREN, GAN, GOT, AK, RE, etc. series of epoxy compounds are commercially available from Kyoeisha Kagaku Co., Ltd., Nagase Chemtech Denacor EX, Nippon Kayaku EOCN (for example, EOCN 1020) , Mitsubishi Kagaku Epoxy Coat, DIC Epiclon, Nissan Kagaku Kogyo Co., Ltd., and the like. Two or more of these may be used in combination.

It is also possible to use the epoxy group-containing siloxane polymer described in paragraphs 0040 to 0044 of Japanese Laid-Open Patent Publication No. 2013-243350.

<<<< photopolymerization initiator >>>>

When the curable composition is photo-cured, it is preferable to further include a photopolymerization initiator.

The photopolymerization initiator can be appropriately selected from known photopolymerization initiators. For example, it is preferable to have photosensitivity to a visible ray from an ultraviolet ray region. It may also be an activator which generates an action with a photoexcited sensitizer and generates active radicals, or an initiator which initiates cationic polymerization depending on the kind of the monomer.

The photopolymerization initiator preferably contains at least one compound having a molar extinction coefficient of at least about 50 within a range of about 300 nm to 800 nm (more preferably 330 nm to 500 nm).

Examples of the photopolymerization initiator include halogenated hydrocarbon derivatives (for example, those having a triazine skeleton, those having an oxadiazole skeleton, etc.), acylphosphine compounds such as acylphosphine oxide, Organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketoxime compounds, aminoacetophenone compounds, hydroxyacetophenone compounds, and the like. As the halogenated hydrocarbon compound having a triazine skeleton, for example, Wakabayashi et al., Bull. Chem. Soc. Compounds described in GB-A-5313428, compounds described in German Patent Publication No. 3337024, compounds described in J. Org., &Lt; RTI ID = 0.0 &gt; . Chem .; 29, 1527 (1964), compounds described in Japanese Laid-Open Patent Publication No. 62-58241, compounds described in Japanese Laid-Open Patent Publication No. 5-281728, compounds described in Japanese Laid-Open Patent Publication No. 5-34920, Compounds described in Japanese Patent Publication No. 4212976, and the like.

The photopolymerization initiator is preferably at least one selected from the group consisting of a trihalomethyltriazine compound, a benzyldimethylketal compound, an? -Hydroxyketone compound, an? -Amino ketone compound, an acylphosphine compound, a phosphine oxide compound, A benzophenone compound, an acetophenone compound and a derivative thereof, a cyclopentadiene-benzene-iron complex and a salt thereof, a halomethyloxadiazole compound, an oxime compound, a triallylimidazole dimer, an onium salt compound, a benzothiazole compound, A compound selected from the group consisting of a 3-aryl substituted coumarin compound and a ketone compound is preferable, and an oxime compound, an acetophenone compound or an acylphosphine compound is more preferable, and an oxime compound is particularly preferable.

IRGACURE-OXE01 (manufactured by BASF), IRGACURE-OXE02 (manufactured by BASF) and TR-PBG-304 (manufactured by Changzhou Tronly New Electronic Materials Co., Ltd.) Adeka acid NCI-831 (manufactured by ADEKA), Adeka acid NCI-930 (manufactured by ADEKA), and the like. It is also possible to use a fluorine atom-containing oxime initiator. Specific examples of such initiators include compounds described in JP-A-2010-262028, compounds 24, 36 to 40 described in Japanese Patent Publication No. 2014-500852, paragraph 0345, JP-A-2013-164471 (C-3) described in paragraph 0101 of the title of the present application.

Examples of commercially available acetophenone compounds include IRGACURE-907, IRGACURE-369 and IRGACURE-379 (all trade names, manufactured by BASF).

Commercially available products of the acylphosphine compounds include IRGACURE-819 and DAROCUR-TPO (all trade names, manufactured by BASF).

As a commercially available product of the ketone compound, Kayacure-DTX (manufactured by Nippon Kayaku) may be used.

As the photopolymerization initiator, compounds described in paragraphs 0096 to 0115 of Japanese Laid-Open Patent Publication No. 2014-212292 may be used, and the contents thereof are hereby incorporated by reference.

When the curable composition contains a photopolymerization initiator, the content of the photopolymerization initiator is preferably from 0.1 to 30 mass% based on the total solid content of the curable composition. The lower limit is more preferably 0.5% by mass or more, and still more preferably 2.0% by mass or more. The upper limit is more preferably 20 mass% or less, and still more preferably 15 mass% or less.

<<<< Thermal polymerization initiator >>>>

When the curable composition is thermally cured, it is preferable to further include a thermal polymerization initiator. The thermal polymerization initiator is usually a thermal radical polymerization initiator. As the thermal radical polymerization initiator, a known thermal radical generator may be used.

The thermal radical polymerization initiator is a compound which generates radicals by the energy of heat and initiates or accelerates the polymerization reaction of the polymerizable compound.

Preferable examples of the thermal radical polymerization initiator include compounds capable of generating radicals by irradiation with actinic rays or radiation as described above. The thermal decomposition point is preferably 130 deg. C to 250 deg. C, more preferably 150 deg. C to 220 deg. Compounds may be used.

Examples of thermal radical polymerization initiators include aromatic ketones, onium salt compounds, organic peroxides, thio compounds, hexaarylbimidazole compounds, ketoxime ester compounds, borate compounds, azinium compounds, metallocene compounds, active ester compounds, A compound having a hydrogen bond, an azo compound, and the like. Among them, an organic peroxide or an azo-based compound is more preferable, and an organic peroxide is particularly preferable.

Specifically, the compounds described in paragraphs 0074 to 0118 of JP-A No. 2008-63554 can be mentioned.

As commercial products, percumyl H, perbutyl Z (niche emulsion) and bis (t-butylsulfonyl) diazomethane (manufactured by Wako Pure Chemical Industries, Ltd.) can be suitably used.

In the case where the curable composition of the present invention contains a thermal radical polymerization initiator, the curing temperature can be controlled in particular, and the adhesion at a high temperature (for example, 100 ° C) can be further improved.

When the curable composition of the present invention has a thermal radical polymerization initiator, the content of the thermal radical polymerization initiator is preferably 0.1 to 50 mass%, more preferably 0.1 to 30 mass%, based on the total solid content of the adhesive layer, More preferably 0.1 to 20% by mass.

The thermal radical polymerization initiator may be a single kind or two or more kinds. When two or more types of thermal radical polymerization initiators are used, the total amount is preferably in the above range.

<<<< Binders >>>>>

The curable composition preferably includes a binder. That is, the adhesive layer preferably includes a binder.

In the present invention, any binder may be used. The binder includes block copolymers, random copolymers and graft copolymers, and block copolymers are preferred. If the block copolymer is used, it is possible to suppress the flow of the adhesive layer during the heating process, so that the adhesion can be maintained even during the heating process, and the effect of the peelability after the heating process is not changed.

Further, in the present invention, the binder means a polymer having no polymerizable group. The polymer having a polymerizable group is a polymerizable compound. Examples of the polymerizable group include a group having an ethylenic unsaturated bond, a cyclic ether (epoxy, oxetane) group, and a methylol group.

The weight average molecular weight of the binder is preferably from 2,000 to 1,000,000, more preferably from 5,000 to 200,000.

Examples of the binder include, but are not limited to, polystyrene copolymers, polyester copolymers, polyolefin copolymers, polyuretene copolymers, polyamide copolymers, polyacrylic copolymers, silicone copolymers, Based copolymer or the like can be used. In particular, a polystyrene-based copolymer, a polyester-based copolymer and a polyamide-based copolymer are preferable, and a polystyrene-based copolymer is more preferable from the viewpoint of heat resistance and releasability. Among them, the binder is preferably a block copolymer of styrene and other monomers, and a styrene block copolymer in which one terminal or both terminals is a styrene block is particularly preferable.

The binder is preferably a hydrogenated product of a block copolymer. If the binder is a hydrogenated material, the thermal stability and the storage stability are improved. Further, the peelability and the removability of the adhesive layer after peeling are improved. The hydrogenated product means a polymer in which a block copolymer is hydrogenated.

In the present invention, the binder is preferably an elastomer.

As the block copolymer, the block copolymer described in the above-mentioned release layer can be used. That is, a polystyrene-based copolymer, a polyester-based copolymer, a polyolefin-based copolymer, a polyurethane-based copolymer, a polyamide-based copolymer, a polyacrylic copolymer, a silicone-based copolymer and a polyimide- .

The binder may be at least one selected from the group consisting of hydrocarbon resins, novolac resins, phenol resins, epoxy resins, melamine resins, urea resins, unsaturated polyester resins, alkyd resins, polyamide resins, polyimide resins, polyamideimide resins, A resin such as a resin, a polybenzoxazole resin, a polyvinyl chloride resin, a polyvinyl acetate resin, a polyacetal resin, a polycarbonate resin, a polyphenylene ether resin, a polystyrene terephthalate resin, a polyethylene terephthalate resin, , Polysulfone resin, polyethersulfone resin, polyarylate resin, polyetheretherketone resin, or the like may be used.

<<<<< Hydrocarbon resin >>>>>

As the hydrocarbon resin, any one can be used.

A hydrocarbon resin basically means a resin composed only of carbon atoms and hydrogen atoms. However, if the basic skeleton is a hydrocarbon resin, it may contain other atoms as side chains. That is, when a functional group other than a hydrocarbon group is directly bonded to a main chain such as an acrylic resin, a polyvinyl alcohol resin, a polyvinyl acetal resin, and a polyvinyl pyrrolidone resin to a hydrocarbon resin composed only of carbon atoms and hydrogen atoms In this case, the content of the repeating unit in which the hydrocarbon group is directly bonded to the main chain is preferably 30 mol% or more with respect to the total repeating units of the resin.

Examples of hydrocarbon resins conforming to the above conditions include terpene resins, terpene phenol resins, modified terpene resins, hydrogenated terpene resins, hydrogenated terpenephenol resins, rosins, rosin esters, hydrogenated rosins, hydrogenated rosin esters, An aliphatic petroleum resin, an aromatic petroleum resin, a hydrogenated petroleum resin, a modified petroleum resin, an alicyclic petroleum resin, a coumarone petroleum resin, an indene petroleum resin, a polystyrene -Olefin polymers (e.g., methylpentene copolymers), and cycloolefin polymers (e.g., norbornene copolymers, dicyclopentadiene copolymers, tetracyclododecene copolymers) .

The hydrocarbon resin is preferably a terpene resin, a rosin, a petroleum resin, a hydrogenated rosin, a polymerized rosin, an olefin polymer, or a cycloolefin polymer, more preferably a terpene resin, a rosin, an olefin polymer, or a cycloolefin polymer More preferably a terpene resin, a rosin, an olefin polymer, or a cycloolefin polymer, particularly preferably a terpene resin, a rosin, a cycloolefin polymer or an olefin polymer, and particularly preferably a cycloolefin polymer.

Examples of the cycloolefin polymer include norbornene polymers, polymers of monocyclic cycloolefins, polymers of cyclic conjugated dienes, vinyl alicyclic hydrocarbon polymers, and hydrides of these polymers. Preferable examples of the cycloolefin polymer include an addition (co) polymer containing at least one repeating unit represented by the following general formula (II), and a copolymer comprising at least one repeating unit represented by the general formula (I) (Co) polymer. Another preferred example of the cycloolefin polymer is a ring-opening (co) polymer containing at least one cyclic repeating unit represented by the general formula (III).

(11)

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, (CH ₂ ) n COOR ¹¹ , - (CH ₂ ) n OCOR 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 (-CO) ₂ O, (-CO) ₂ NR ¹⁷ composed of X ³ and Y ³ . Each of R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ and R ¹⁷ is a hydrogen atom or a hydrocarbon group (preferably a hydrocarbon group having 1 to 20 carbon atoms), Z is a hydrocarbon group W represents SiR ¹⁸ _p D _{3 -p} (R ¹⁸ represents a hydrocarbon group having 1 to 10 carbon atoms, D represents a halogen atom, -OCOR ¹⁸ or -OR ¹⁸ And p represents an integer of 0 to 3). n represents an integer of 0 to 10;

The norbornene polymer is disclosed in, for example, Japanese Unexamined Patent Application Publication No. 10-7732, Japanese Unexamined Patent Publication No. 2002-504184, US2004 / 229157A1, and WO2004 / 070463A1. The norbornene polymer can be obtained by addition polymerization of norbornene polycyclic unsaturated compounds. If necessary, norbornene polycyclic unsaturated compounds and ethylene, propylene, butene; Conjugated dienes such as butadiene, isoprene; And non-conjugated dienes such as ethylidene norbornene may be addition polymerized. This norbornene polymer is commercially available from Mitsui Chemicals, Inc. under the trade name APELPEL and has a glass transition temperature (Tg) of different grades such as APL8008T (Tg70 DEG C), APL6013T (Tg125 DEG C) or APL6015T (Tg145 DEG C) have. Pellets such as TOPAS 8007, 5013, 6013 and 6015 are available from polyplastics. Appear 3000 is also available from Ferrania.

The hydrides of the norbornene-based polymers are disclosed in JP-A-1-240517, JP-A-7-196736, JP-A-60-26024, JP-A-62-19801, As disclosed in, for example, Japanese Patent Application Laid-Open No. 2003-1159767 or Japanese Patent Application Laid-Open No. 2004-309979, by subjecting a polycyclic unsaturated compound to addition polymerization or metathesis ring-opening polymerization, followed by hydrogenation.

In the general formula (III), R ⁵ and R ⁶ are preferably a hydrogen atom or a methyl group, and X ³ and Y ³ are preferably a hydrogen atom, and other groups are appropriately selected. This norbornene polymer is commercially available from JSR under the trade name of Arton G or Aton F and is commercially available from Nippon Zeon under the trade names Zeonor ZF14, ZF16, Zeonex 250, Copper 280, Copper 480R , And these can be used.

<<<<< Polycarbonate resin >>>>>

The polycarbonate resin is preferably a resin having a repeating unit represented by the following general formula (1).

[Chemical Formula 12]

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

Ar ¹ and Ar ² in the general formula (1) each independently represent an aromatic group. Examples of the aromatic group include a benzene ring, a naphthalene ring, a pentane ring, an indene ring, an azole ring, a heptylene ring, an indene ring, a perylene ring, a pentacene ring, an acenaphthalene ring, a phenanthrene ring, an anthracene ring, a naphthacene ring, A thiophene ring, an imidazole ring, an oxazole ring, a thiazole ring, a pyridine ring, a pyrazine ring, a pyrimidine ring, a pyridazin ring, an indolizine ring, an indole ring A benzofuran ring, a benzothiophen ring, an isobenzofuran ring, a quinoline ring, a quinoline ring, a phthalazine ring, a naphthyridine ring, a quinoxaline ring, a quinoxazoline ring, an isoquinoline ring, a carbazole ring, a phenanthridine ring , An acridine ring, a phenanthroline ring, a thianthrene ring, a cromene ring, a zentylene ring, a phenoxathiine ring, a phenothiazine ring, and a phenanthrene ring. Among them, a benzene ring is preferable.

These aromatic groups may or may not have substituents.

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

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

The alkyl group includes an alkyl group having 1 to 30 carbon atoms. The alkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms. The alkyl group may be linear or branched. Further, a part or all of the hydrogen atoms of the alkyl group may be substituted with a halogen atom. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a fluorine atom is preferable.

As the alkoxy group, an alkoxy group having 2 to 30 carbon atoms is preferable. The carbon number of the alkoxy group is more preferably from 2 to 20, and still more preferably from 2 to 10. The alkoxy group may be linear, branched or cyclic.

The aryl group is preferably an aryl group having 6 to 30 carbon atoms, and more preferably an aryl group having 6 to 20 carbon atoms.

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

Examples of commercially available products of the polycarbonate resin include PCZ-200, PCZ-300, PCZ-500, PCZ-800 (Mitsubishi Gas Gas Company), APEC 9379 (Bayer), Panlite L-1225LM .

<<<<< Siloxane polymer >>>>>

The binder may be a siloxane polymer having a repeating unit represented by the following formula (1).

[Chemical Formula 13]

In the formula (1), R ¹ to R ⁴ represent monovalent hydrocarbon groups such as alkyl groups having 1 to 8 carbon atoms which may be the same or different. m is an integer of 1 to 100, B is a positive number, A is 0 or a positive number. X is a divalent organic group represented by the following formula (2).

[Chemical Formula 14]

In the formula (2), Z is a divalent organic group selected from any one of the following groups, and n is 0 or 1. R ⁵ and R ⁶ are each an alkyl group or an alkoxy group having 1 to 4 carbon atoms, and may be the same or different. and k is any one of 0, 1, and 2.

[Chemical Formula 15]

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

For details of the siloxane polymer, reference can be made to paragraphs 0038 to 0044 of Japanese Laid-Open Patent Publication No. 2013-243350, the contents of which are incorporated herein by reference.

When the curable composition comprises a binder, the content of the binder is preferably 5 to 99% by mass with respect to the total solid content of the curable composition. The lower limit is more preferably 10% by mass or more, and still more preferably 30% by mass or more. The upper limit is more preferably 90 mass% or less, and still more preferably 80 mass% or less.

When an elastomer is used as the binder, the elastomer is preferably contained in a proportion of 50.00 to 99.99 mass%, more preferably 70.00 to 99.99 mass%, and particularly preferably 88.00 to 99.99 mass% in the total solid content of the curable composition Do. When the content of the elastomer is within the above range, the adhesive property and the peelability are excellent. When two or more kinds of elastomers are used, the total amount is preferably in the above range.

When an elastomer is used as the binder, the content of the elastomer in the total mass of the binder is preferably 50 to 100% by mass, more preferably 70 to 100% by mass, still more preferably 80 to 100% To 100% by mass is still more preferable. The binder may be substantially only an elastomer. The content of the elastomer in the total mass of the binder is preferably 99% by mass or more, more preferably 99.9% by mass or more, still more preferably only the elastomer, and the binder is substantially only an elastomer.

In the curable composition, the mass ratio of the polymerizable compound and the binder is preferably from 95: 5 to 5:95, more preferably from 90:10 to 20:80, and from 85:15 to 30:80, 70 is more preferable. By setting the mass ratio of the polymerizable compound and the binder within the above range, the adhesiveness, the peelability, the warpage suppression, and the flat polishability can be improved.

<<<< Surfactant >>>>

The curable composition preferably contains a surfactant.

As the surfactant, any of anionic, cationic, nonionic or amphoteric surfactants may be used, but preferred surfactants are nonionic surfactants.

Examples of nonionic surfactants include polyoxyethylene higher alkyl ethers, polyoxyethylene higher alkyl phenyl ethers, higher fatty acid diesters of polyoxyethylene glycol, and silicone surfactants.

The adhesive layer preferably contains a silicone surfactant as a surfactant from the viewpoint of coatability. In general, when a composition having a high viscosity is used, it is difficult to apply the composition in a uniform thickness. However, since it is easy to coat the composition with a uniform thickness by containing a surfactant, it can be more preferably used.

As examples of these silicone surfactants, mention may be made of, for example, JP-A 62-36663, JP-A 61-226746, JP-A 61-226745, JP-A 62-170950, Japanese Patent Application Laid-Open Nos. 63-34540, 7-230165, 8-62834, 9-54432, 9-5988, Japanese Patent Application Laid-Open No. 2001-330953 discloses surfactants, and commercially available surfactants may be used.

Examples of commercially available silicone surfactants include KP-301, KP-306, KP-109, KP-310, KP-310B, KP-323, KP-326, KP- KP-365, KP-365, KP-358, KP-358, KP-361, KP-361, -368, KP-369, KP-330, KP-650, KP-651, KP-390, KP-391 and KP-392 available from Shin-Etsu Chemical Co.,

When the curable composition contains a surfactant, the content of the surfactant is preferably 0.001 to 5.0% by mass based on the total solid content of the curable composition. The lower limit is more preferably 0.005 mass% or more, and still more preferably 0.01 mass% or more. The upper limit is more preferably 3.0 mass% or less, and more preferably 1.0 mass% or less.

<<<< Antioxidants >>>>

The curable composition may contain an antioxidant. As the antioxidant, those described in the composition for forming a release layer can be mentioned, and preferable ranges are also the same. When the curable composition has an antioxidant, the content of the antioxidant is preferably 0.001 to 20.0 mass% with respect to the total solid content of the curable composition. The lower limit is more preferably 0.005 mass% or more, and still more preferably 0.01 mass% or more. The upper limit is more preferably 15 mass% or less, and further preferably 10 mass% or less.

<<<< Other Ingredients >>>>

In addition to the polymerizable compound, the curable composition may contain various compounds depending on the purpose insofar as the effect of the present invention is not impaired. For example, sensitizing dyes and chain transfer agents can be preferably used. When these additives are compounded, the total amount of the additives is preferably 3% by mass or less based on the total solid content of the curable composition.

<<<< Solvent >>>>>

The curable composition may contain a solvent. As the solvent, any of known solvents can be used without limitation, and organic solvents are preferable. Specific examples of the solvent include the solvents described in the composition for forming a release layer, and preferable ranges are also the same. The content of the solvent in the curable composition is preferably 10 mass% or less, more preferably 5 mass% or less, and most preferably 1 mass% or less. The lower limit is, for example, preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and most preferably 0.1% by mass or more.

Further, the composition for forming the adhesive layer preferably contains a solvent in addition to the curable composition. In the case where the composition for forming an adhesive layer has a solvent, the content of the solvent in the adhesive layer formation composition is preferably such that the total solid content concentration of the composition for forming a pressure-sensitive adhesive layer is from 1 to 80 mass% By mass to 70% by mass, and particularly preferably 10% by mass to 60% by mass.

The solvent may be a single kind or two or more types. When two or more kinds of solvents are used, the total amount is preferably in the above range.

The composition for forming a pressure-sensitive adhesive layer in the present invention preferably does not contain impurities such as metals. The content of the impurities contained in these materials is preferably 1 mass ppm or less, more preferably 1 mass ppb or less, more preferably 100 mass ppt or less, even more preferably 10 mass ppt or less, (Which is not more than the detection limit of the measuring apparatus) is particularly preferable.

A method for removing impurities such as metals from the composition for forming an adhesive layer and a method for reducing impurities such as metals contained in the adhesive layer forming composition may be the same as the method described for the composition for forming a release layer .

&Lt; Composition for releasing layer and method for preparing composition for forming adhesive layer >

The composition for forming the release layer and the composition for forming the adhesive layer can be prepared by mixing the respective components described above. The mixing of the respective components is usually carried out in the range of 0 ° C to 100 ° C. It is also preferable to mix the respective components and then filter them with a filter, for example. The filtration may be performed in multiple steps or repeated a plurality of times. In addition, the filtrate may be re-filtered.

The filter is not particularly limited as long as it is conventionally used for filtration and the like. For example, a fluororesin such as PTFE (polytetrafluoroethylene), a polyamide resin such as nylon-6 or nylon-6,6, a polyolefin resin such as polyethylene or polypropylene (PP) And the like). Of these materials, polypropylene (including high-density polypropylene) and nylon are preferred.

The pore diameter of the filter is suitably about 0.003 to 5.0 mu m, for example. By setting this range, it becomes possible to reliably remove fine foreign matters such as impurities and aggregates contained in the composition while suppressing filtration clogging.

When using a filter, other filters may be combined. At this time, the filtering by the first filter may be performed once, or may be performed twice or more. When filtering is performed two or more times in combination with other filters, it is preferable that the pore diameters of the second and subsequent pores are equal to or smaller than the pore diameters of the first filtering. The first filter having different pore diameters may be combined within the above-described range. The pore diameter here can refer to the nominal value of the filter manufacturer. As a commercially available filter, it is possible to select from among various filters provided by, for example, Nippon Poulouse, Advantech Co., Nippon Integrin Co., Ltd., or Kits Micro Filter.

<Kit>

Next, a kit for forming the adhesive laminate of the present invention will be described.

The kit of the present invention includes a composition for forming an adhesive layer comprising a curable composition and a composition for forming a release layer comprising a block copolymer and a compound having a fluorine atom.

The details of the composition for forming an adhesive layer and the composition for forming a release layer are the same as those described for the adhesive layer laminate.

&Lt; Method for producing laminate for adhesion >

The method for producing the adhesive laminate of the present invention is not particularly limited, but can be produced, for example, by the following method.

(1) A method for producing a release layer by applying a composition for forming an adhesive layer on a substrate to form an adhesive layer, and applying a composition for forming a release layer on the surface of the adhesive layer to form a release layer.

(2) A method for forming a release layer by applying a composition for forming a release layer on a substrate, and applying a composition for forming an adhesive layer on the surface of the release layer to form an adhesive layer.

(3) Two release substrates were prepared, and a release layer was formed by applying a composition for forming an adhesive layer on one of the substrates to form an adhesive layer and applying a release layer forming composition on the other substrate. Wherein the adhesive layer side of the substrate on which the adhesive layer is formed and the side of the release layer side of the substrate on which the release layer is formed are pressed.

Examples of application methods of the adhesive layer forming composition include spin coating, spraying, roller coating, flow coating, doctor coating, screen printing, and dip coating. Alternatively, the adhesive layer forming composition may be extruded from a slit-shaped opening under pressure to apply the adhesive composition onto the support.

The application amount of the adhesive layer forming composition varies depending on the application, but it is preferable that the applied amount is such that the average thickness of the adhesive layer after drying becomes 0.1 to 1000 mu m. The lower limit is preferably 1.0 탆 or more. The upper limit is preferably 300 mu m or less, more preferably 200 mu m or less.

Further, in the present invention, the average film thickness of the adhesive layer is preferably in the range from the one end face to the other end face in the cross section along one direction of the adhesive layer, The thickness is defined as the average of the values measured by the micrometer. In the present invention, &quot; a cross section along one direction of the adhesive layer &quot; means a cross section orthogonal to the long side direction when the adhesive layer is polygonal. In the case where the adhesive layer is of a square shape, a cross section orthogonal to either one of the sides is used. When the adhesive layer is circular or elliptical, it is a section passing through the center of gravity.

Examples of the substrate include drums and bands. A release film, a device wafer, a carrier substrate, or the like may also be used as the substrate.

The carrier substrate is not particularly limited, and examples thereof include a silicon substrate, a glass substrate, a metal substrate, and a compound semiconductor substrate. Among them, a silicon substrate is preferable in view of the fact that it is difficult to contaminate a silicon substrate which is typically used as a substrate of a semiconductor device, and an electrostatic chuck generally used in a semiconductor device manufacturing process can be used. When a silicon substrate is used as the carrier substrate, the adhesive layer made of the curable composition is preferably a thermosetting composition. When the adhesive layer is a photo-curable composition, it is preferable that the support is a transparent substrate such as a glass substrate capable of transmitting light.

The thickness of the carrier base material is not particularly limited, but is preferably 300 占 퐉 to 100 mm, more preferably 300 占 퐉 to 10 mm, for example.

As the device wafer, known ones can be used without limitation, and examples thereof include a silicon substrate and a compound semiconductor substrate. Specific examples of the compound semiconductor substrate include SiC substrate, SiGe substrate, ZnS substrate, ZnSe substrate, GaAs substrate, InP substrate, GaN substrate and the like.

A mechanical structure or a circuit may be formed on the surface of the device wafer. Examples of the device wafer on which the mechanical structure and the circuit are formed include MEMS (Micro Electro Mechanical Systems), a power device, an image sensor, a microsensor, a diode, an optical device, an interposer, a buried device, a micro device and the like.

It is preferable to dry after applying the composition for forming an adhesive layer. The drying conditions are preferably 10 to 600 seconds at 60 to 180 DEG C, for example. The drying temperature is more preferably 80 to 150 占 폚, and more preferably 100 to 120 占 폚. The drying time is more preferably 30 to 300 seconds, and more preferably 40 to 180 seconds. Drying may be carried out by increasing the temperature stepwise by dividing into two steps.

In the case of the production method of the above (1), after applying the adhesive layer formation composition, the composition for forming a release layer may be applied without drying the composition for forming the adhesive layer, and both may be simultaneously dried.

Drying is a treatment for removing the solvent from the composition for forming an adhesive layer, and it is preferable that drying is performed at a temperature lower than the temperature at which the curable composition contained in the adhesive composition is cured.

As a method of applying the composition for forming a release layer, a spin coating method, a spraying method, a roller coating method, a flow coating method, a doctor coating method, a screen printing method, a dip coating method and the like can be given.

The application amount of the composition for forming a release layer varies depending on the application, but is preferably an application amount such that the average film thickness of the release layer after drying becomes 0.01 to 50 占 퐉. The lower limit is preferably 0.1 탆 or more. The upper limit is preferably 40 占 퐉 or less, more preferably 10 占 퐉 or less.

It is preferable to dry after applying the composition for forming a release layer. The drying conditions are preferably 10 to 1000 seconds at 50 to 250 占 폚, for example. The drying temperature is more preferably 90 to 220 占 폚, and more preferably 100 to 200 占 폚. The drying time is preferably 20 to 600 seconds, more preferably 30 to 300 seconds. Drying may be carried out by increasing the temperature stepwise by dividing into two steps.

In the case of the production method of the above (2), after applying the composition for forming a release layer, the composition for forming a temporary adhesive layer may be applied without drying the composition for forming a release layer, and both may be simultaneously dried.

In the above methods (1) and (2), a film-like adhesive laminate can be obtained by mechanically peeling off the adhesive layer for lamination formed on the substrate from the substrate.

By performing these treatments continuously, a roll-shaped long film can be obtained. The length of the long film is not particularly limited, but the lower limit is preferably 5000 mm or more, for example, and more preferably 1000 mm or more. The upper limit is preferably 500000 mm or less, for example, and more preferably 200000 mm or less.

The release film (substrate) may be applied to both surfaces of the adhesive layer laminate obtained by the methods (1) and (2). It is possible to prevent troubles such as scratches on the surface of the adhesive laminate or sticking to the adhesive tape during storage by bonding the release film to one side or both sides of the adhesive laminate. The release film can be peeled and removed in use.

Further, even when a device wafer or a carrier substrate is used as the substrate, the adhesive layer laminate may be left as it is without peeling from the support.

<Laminate>

Next, the laminate of the present invention will be described.

The laminate of the present invention has the above-described laminate for adhesion of the present invention and a substrate on one side or both sides of the laminate for adhesion. Examples of the substrate include a release film, a device wafer, and a carrier substrate.

For example, by using a carrier substrate or a device wafer as the substrate, an adhesive substrate can be used. The adhesive substrate can be produced by the above-described method for producing a laminate for adhesion. It is also possible to produce the above-described adhesive layer laminate on a substrate by laminating it. For example, the laminating adhesive laminate is set on a vacuum laminator, the laminating adhesive laminate is placed on a substrate in this apparatus, the laminating adhesive laminate and the substrate are brought into contact with each other under vacuum, And a method of fixing (laminating) the adhesive laminate to the substrate. The adhesive layer laminate fixed to the substrate may be cut into a desired shape such as a circular shape.

&Lt; Device Wafer Laminate >

Next, the device wafer laminated body will be described. The device wafer stacking laminate has the above-described inventive adhesive laminate between the carrier substrate and the device wafer, wherein one surface of the adhesive laminate is in contact with the device surface of the device wafer, The surface is in contact with the surface of the carrier substrate.

The carrier substrate and the device wafer may be those described above.

The thickness of the device wafer before mechanical or chemical treatment is preferably 500 탆 or more, more preferably 600 탆 or more, and more preferably 700 탆 or more. The upper limit is preferably, for example, not more than 2000 mu m, and more preferably not more than 1500 mu m.

The thickness of the device wafer after thinning by mechanical or chemical treatment is preferably, for example, less than 500 mu m, more preferably 400 mu m or less, and further preferably 300 mu m or less. The lower limit is preferably 1 m or more, for example, and more preferably 5 m or more.

The device wafer laminate can be obtained by applying a composition for forming an adhesive layer on a surface of a device wafer or a carrier substrate to form a temporary adhesive layer and applying a composition for forming a mold release layer on the other substrate to form a mold release layer, Bonding the surface of the substrate on which the adhesive layer is formed to the adhesive layer side and the surface of the substrate on which the release layer is formed to the release layer side. The pressing condition is preferably a pressure of 0.01 to 1 MPa.

The device wafer and the carrier substrate can be adhered to each other by curing the adhesive layer by heating or irradiating light in the state in which the both are squeezed or the pressure is released after the pressure is released.

In the case of thermally curing the adhesive layer, it is preferably carried out under the conditions of, for example, a temperature of 150 to 250 DEG C and a time of 1 to 120 minutes.

When the adhesive layer is photo-cured, ultraviolet rays such as g line and i line (i line is particularly preferable) are preferably used as the radiation (light) which can be used at the time of exposure. Irradiation dose (exposure dose), the polymerization can be appropriately set according to the type of compound, for example, 30 ~ 1500mJ / cm ² are preferred, and 50 ~ 1000mJ / cm ² is more preferably, 80 ~ 500mJ / cm ² the most desirable.

In the present invention, it is preferable to form a releasing layer by applying a composition for forming a releasing layer on the surface of a device wafer, and to form an adhesive layer by applying a pressure-sensitive adhesive composition on the surface of the carrier substrate. By forming the release layer on the side of the device wafer, it is difficult for the adhesive layer to contact directly with the device surface when the device wafer and the carrier substrate are adhered to each other, and more excellent peelability can be achieved. Therefore, when the carrier substrate is peeled off from the device wafer after the device wafer is adhered to the carrier substrate, the laminate including at least the carrier substrate and the adhesive layer peels off from the device wafer, so that the adhesive layer remains on the device wafer side And it is possible to simplify the troubles such as cleaning of the device wafer after the adhesion between the device wafer and the carrier substrate is released.

The device wafer stacking laminate may be manufactured by pressing the surface of the above-mentioned adhesive base material on the side where the adhesive laminate is formed and the device wafer or the carrier base material.

It is also possible to arrange the above-described laminate for adhesion of the present invention between the carrier substrate and the device wafer, and press-bond the laminate.

<Method of Manufacturing Semiconductor Device>

Hereinafter, one embodiment of a method of manufacturing a semiconductor device will be described with reference to Fig. The present invention is not limited to the following embodiments.

1 (A) to 1 (D) are schematic cross-sectional views (Figs. 1A and 1B) for explaining adherence between a carrier substrate and a device wafer, a state in which a device wafer adhered to a carrier substrate is thinned 1 (C)), and a state after the adhesive layered product is removed from the device wafer (Fig. 1 (D)).

As shown in Fig. 1 (A), an adhesive layer 11 is formed on a carrier substrate 12, and a release layer 15 is formed on a device wafer.

The device wafer 60 is formed by providing a plurality of device chips 62 on the surface 61a of the silicon substrate 61. [

The thickness of the silicon substrate 61 is preferably 200 to 1200 占 퐉, for example. The device chip 62 is preferably, for example, a metal structure, and the height is preferably 10 to 100 mu m.

Next, as shown in Fig. 1 (B), the adhesive layer 11 on the carrier substrate 12 and the release layer 15 on the device wafer are pressed to form the adhesive laminate 20, (12) and the device wafer (60).

It is preferable that the adhesive laminate 20 completely covers the device chip 62. When the height of the device chip is X m and the thickness of the adhesive layer (adhesive film) is Y m, Y > X &quot; is satisfied.

The reason why the adhesive laminate 20 completely covers the device chip 62 is that the TTV (total thickness variation) of the thin device wafer is to be further lowered (i.e., the flatness of the thin device wafer is further improved If you want to do so).

That is, when the device wafer is thinned, it is possible to substantially eliminate the irregularities on the contact surface with the carrier base 12 by protecting the plurality of device chips 62 with the adherent laminate 20. Therefore, even if the substrate is thinned in such a supported state, the possibility that the shape derived from the plurality of device chips 62 is transferred to the back surface 61b1 of the thin device wafer is reduced, and as a result, Can be lowered.

Subsequently, as shown in Fig. 1 (C), the back surface 61b of the silicon substrate 61 is subjected to mechanical or chemical treatment (not particularly limited, for example, thinning such as grinding or chemical mechanical polishing Treatment with high temperature and vacuum such as chemical vapor deposition (CVD) or physical vapor deposition (PVD), treatment with chemicals such as organic solvents, acidic treatment solution or basic treatment solution, plating treatment, irradiation with active rays, heating (For example, the average thickness is preferably less than 500 탆 and more preferably 1 to 200 탆) as shown in Fig. 1 (C) To obtain a thin device wafer 60a.

As a mechanical or chemical treatment, after the thinning process, a through hole (not shown) penetrating the silicon substrate is formed from the back surface 61b1 of the thin device wafer 60a, and a silicon penetrating electrode (Not shown) may be formed.

In the mechanical or chemical treatment, the maximum attainable temperature in the heat treatment is preferably 130 ° C to 400 ° C, more preferably 180 ° C to 350 ° C. It is preferable that the maximum reaching temperature in the heat treatment is lower than the decomposition temperature of the adhesion layer. The heat treatment is preferably heating for 30 seconds to 30 minutes at the maximum attained temperature, and more preferably for 1 minute to 10 minutes at the maximum attained temperature.

Subsequently, the carrier substrate 12 is removed from the thin device wafer 60a. Although the method of desorbing is not particularly limited, it is preferable to pull up the end portion of the thin device wafer 60a in the vertical direction with respect to the thin device wafer 60a and peel it off without any treatment.

After the thin film device wafer 60a is brought into contact with the peeling liquid and then the thin film device wafer 60a is slid with respect to the carrier substrate 12 as required, It can be pulled up in the vertical direction to peel off.

<Release liquid>

Hereinafter, the release liquid will be described in detail.

As the peeling solution, water and a solvent (organic solvent) can be used.

As the exfoliation liquid, an organic solvent which dissolves the adhesive layer 11 is preferable. Examples of the organic solvent include aliphatic hydrocarbons (such as hexane, heptane, isophora E, H and G (produced by Esso Chemicals)), aromatic hydrocarbons such as toluene and xylene, (Methylene dichloride, ethylene dichloride, trichlorethylene, monochlorobenzene, etc.) and polar solvents. Examples of the polar solvent include alcohols (such as methanol, ethanol, propanol, isopropanol, 1-butanol, 1-pentanol, 1-hexanol, 1-heptanol, But are not limited to, 1-hexanol, 1-nonanol, 1-decanol, benzyl alcohol, ethylene glycol monomethyl ether, 2-ethoxy ethanol, diethylene glycol monoethyl ether, diethylene glycol monohexyl Ether, triethylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether, polyethylene glycol monomethyl ether, polypropylene glycol, tetraethylene glycol Ethylene glycol monobutyl ether, ethylene glycol monophenyl ether, propylene glycol monophenyl ether, methylphenyl carbinol, n-amyl alcohol, methyl amyl alcohol Etc.), ketones (acetone, methyl ethyl ketone, ethyl butyl ketone, methyl isobutyl ketone, cyclohexanone, etc.) And examples thereof include esters (such as ethyl acetate, propyl acetate, butyl acetate, amyl acetate, benzyl acetate, methyl lactate, butyl lactate, ethylene glycol monobutyl acetate, propylene glycol monomethyl ether acetate, diethylene glycol acetate, N-phenyldiethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, 4-ethyldiethanolamine, 4-ethylhexylamine, - (2-hydroxyethyl) morpholine, N, N-dimethylacetamide, N-methylpyrrolidone, etc.).

From the viewpoint of releasability, the release liquid may contain an alkali, an acid, and a surfactant. When these components are blended, the blending amount is preferably 0.1 to 5.0% by mass of the peeling liquid, respectively.

From the viewpoint of releasability, a mode of mixing two or more kinds of organic solvents and water, two or more kinds of alkali, acid and surfactant is also preferable. If necessary, additives such as antifoaming agents and water softening agents may be contained.

As the alkali, acid and surfactant, reference can be made to the description in paragraphs 0170 to 0176 of Japanese Laid-Open Patent Publication No. 2014-189696, the contents of which are incorporated herein by reference.

2 (D), a thin device wafer can be obtained by removing the adhesive layer 20 from the thin device wafer 60a.

The method of removing the adhesive laminate is, for example, a method in which the adhesive laminate is peeled off (film peeled off) while remaining in a film form, a method in which the adhesive laminate is peeled off after swelling the peeling liquid A method of dissolving and removing the adhesive laminate by dissolving the adhesive laminate in a peeling liquid, a method of decomposing and vaporizing the adhesive laminate by irradiation with an actinic ray, radiation or heat And a method of removing the water. A method in which the adhesive laminate is peeled off and removed in the form of a film, and a method of dissolving and removing the adhesive laminate in an aqueous solution or an organic solvent can be preferably used. From the viewpoint of reducing the amount of the solvent used, it is preferable to remove the film in the form of a film.

When the carrier substrate 12 is detached from the thin device wafer 60a, the adherent laminate 20 is peeled from the interface between the thin device wafer 60a and the adherent laminate 20 , The above-described removal treatment of the laminating adhesive 20 for attachment can be omitted.

After the carrier substrate 12 is removed from the thin device wafer 60a, various known processes are performed on the thin device wafer 60a as necessary to manufacture a semiconductor device having the thin device wafer 60a do.

When the residue of the adhesive layer adheres to the carrier substrate, the carrier substrate can be regenerated by removing the residue. Examples of the method for removing the residue include a method of physically removing the residue by spraying a brush, an ultrasonic wave, an ice particle, or an aerosol, a method of dissolving and removing it by dissolving in an aqueous solution or an organic solvent, and decomposing and vaporizing by irradiation with actinic rays, And the like. However, depending on the carrier substrate, conventionally known cleaning methods can be used.

For example, when a silicon substrate is used as the carrier substrate, conventionally known silicon wafer cleaning methods can be used. Examples of the aqueous solution or organic solvent that can be used for chemical removal include strong acids, strong bases, strong oxidizing agents And specific examples thereof include acids such as sulfuric acid, hydrochloric acid, hydrofluoric acid, nitric acid and organic acids, bases such as tetramethylammonium, ammonia and organic bases, oxidizing agents such as hydrogen peroxide, A mixture of hydrochloric acid and hydrogen peroxide, a mixture of sulfuric acid and hydrogen peroxide, a mixture of hydrofluoric acid and hydrogen peroxide, a mixture of hydrofluoric acid and ammonium fluoride, and the like.

From the viewpoint of adhesiveness when a recycled carrier substrate is used, it is preferable to use a cleaning liquid.

It is preferable that the cleaning liquid contains an acid (strong acid) having a pKa of less than 0 and hydrogen peroxide. The acid having a pKa of less than 0 is selected from an inorganic acid such as hydrogen iodide, perchloric acid, hydrogen bromide, hydrogen chloride, nitric acid, sulfuric acid, or an organic acid such as alkylsulfonic acid or arylsulfonic acid. From the viewpoint of the cleaning property of the adhesive layer on the carrier substrate, it is preferably an inorganic acid, and sulfuric acid is most preferable.

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

Example

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to the following examples unless it is beyond the ordinary knowledge. Unless otherwise specified, &quot; part &quot; and &quot;% &quot; are based on mass.

&Lt; Measurement of weight average molecular weight (Mw)

The weight average molecular weight was measured by the following method.

Columns: TSK gel Super HZ HZM-M (Tosoh Corporation), TSK gel Super HZ 2000 (Tosoh Corporation), TSK gel Super HZ 300 (Toso Corporation), and TSK gel Super HZ 4000 One column

Developing solvent: tetrahydrofuran

Column temperature: 40 DEG C

Flow rate: 0.35 ml / min

Injection volume: 10 μl

Device name: HLC-8220GPC (Tosoh Corporation)

Calibration base resin: polystyrene

(Test Example 1)

&Lt; Composition of adhesive layer forming composition >

Binder: The compound shown in Table 1 and the addition amount

Polymerizable compound: The compound shown in Table 1 and the amount added

Antioxidant: IRGANOX 1010 (manufactured by BASF) 0.05 parts by mass

Sumilizer TP-D (Sumitomo Chemical Co., Ltd.) 0.05 parts by mass

Solvent: The compound shown in Table 1 and the amount added

Thermal radical polymerization initiator: The compound shown in Table 1 and the amount added

Further, the composition of the adhesive layers 1 to 11 and R1 is a thermosetting composition.

[Table 1]

(A-1) PCZ-300 (Mitsubishi Gas Chemical Company, Polycarbonate, MW = 83,000)

(A-2) APEC 9379 (Bayer, polycarbonate, MW = 51,000)

(A-3) Septon 2104 (Kurarayze, polystyrene-based elastomer, MW = 73,000)

(A-4) A siloxane polymer (synthesized according to paragraph 0070 of Japanese Laid-Open Patent Publication No. 2013-243350, MW = 45,000) obtained by polymerizing M-1, M-2 and M-

[Chemical Formula 16]

(B-1) NK Ester A-9300 (trifunctional acrylate, radically polymerizable compound, manufactured by Shin Nakamura Kagaku Kogyo Co., Ltd.)

(B-2) NK Ester A-DPH (manufactured by Shin Nakamura Kagaku Kogyo Co., Ltd., hexafunctional acrylate, radical polymerizable compound)

(B-3) TAIC (triallyl isocyanurate, radically polymerizable compound)

(B-4) NK ester A-BPE-4 (bifunctional acrylate, radically polymerizable compound, manufactured by Shin Nakamura Kagaku Kogyo Co., Ltd.)

(B-5) EOCN-1020 (Nippon Kayaku, O-cresol novolac epoxy resin)

(C-1): cyclopentanone

(C-2): Anisole

(C-3): mesitylene

(D-1): perbutyl Z (tert-butylperoxybenzoate, decomposition temperature (10 hours half-life temperature = 104 占 폚,

(D-2): bis (t-butylsulfonyl) diazomethane (manufactured by Wako Pure Chemical Industries, Ltd.)

&Lt; Composition for forming a release layer >

Block copolymer: The compound shown in Table 2 and the addition amount

占 Component: The compound shown in Table 2 and the amount of addition

Antioxidant: IRGANOX 1010 (manufactured by BASF) 1 part by weight

Sumilizer TP-D (Sumitomo Chemical Co., Ltd.) 1 part by weight

Solvent: The compound shown in Table 2 and the amount added

[Table 2]

(A'-1) Septon 2002 (content of recurring units derived from styrene, polystyrene-based block copolymer, manufactured by Kuraray Co., Ltd. = 30%

(A'-2) Septon 2004 (content of recurring units derived from styrene, polystyrene-based block copolymer, trade name: 18% by mass)

(A'-3) Septon 2006 (content of recurring units derived from styrene, polystyrene-based block copolymer) = 35% by mass)

(A'-4) Septon 4033 (content of recurring units derived from styrene, polystyrene-based block copolymer, Kuraray) = 30% by mass)

(A'-5) Septon 8004 (content of recurring units derived from styrene, polystyrene-based block copolymer) was 31% by mass)

(A'-6) Septon 8007 (content of recurring unit derived from styrene / maleic anhydride copolymer, polystyrene-based block copolymer = 30% by mass)

(A'-7) Kraton G1650 (content of recurring units derived from Kraton, polystyrene-based block copolymer, styrene = 30% by mass)

(A'-8) Kraton G1654 (content of recurring units derived from Kraton, polystyrene block copolymer, styrene = 31% by mass)

(A'-9) Septon 2104 (content of recurring unit derived from styrene / maleic anhydride-styrene block copolymer = 65% by mass)

(A'-10) Septon 8104 (content of recurring units derived from styrene, polystyrene block copolymer, manufactured by Kuraray Co., Ltd. = 60% by mass)

(A'-11) Tuftec P2000 (content of repeating units derived from styrene from polystyrene block copolymer: Asahi Chemical Industry Co., Ltd. = 67% by mass)

(A'-12) Guranti LA4210e (Gurareze, acrylic block copolymer)

(RA'-1) polystyrene (made by Aldrich)

(RA'-2) Styrene MS200 (styrene-methyl methacrylate copolymer manufactured by Shin-Nittsu Sumikin Kagaku Co., Ltd.)

(B'-1) Megafac F553 (DIC, fluorine compound, oil-containing group, (meth) acrylic polymer)

(B'-2) Megafac F554 (DIC, fluorine compound, oil-containing group, (meth) acrylic polymer)

(B'-3) Megafac F556 (DIC, fluorine compound, oil-containing group, (meth) acrylic polymer)

(B'-4) Megafac F557 (DIC, fluorine atom and silicon atom-containing compound, oil-containing group, (meth) acrylic polymer)

(B'-5) Megafac F559 (DIC agent, fluorine compound, oil-containing group, (meth) acrylic polymer)

(B'-6) Fotogen 710 FL (manufactured by Neos, Inc., fluorine compound, containing a hydrophilic group)

(B'-7): Surflon S243 (fluorine-containing ethylene oxide adduct, lipophilic liquid-phase compound, AGC seimichemical)

(C'-1) mesitylene

(C'-2) PGEMA (propylene glycol monomethyl ether acetate)

(C'-3) p-mentine

(C'-4) toluene

(C'-5) Anisole

&Lt; Preparation of Adhesive Laminate >

The composition for forming an adhesive layer was spin-coated on a 100 mm Si wafer (first substrate) having a diameter of 100 mm and a thickness of 525 탆, heated at 100 캜 for 1 minute, further heated at 150 캜 for 5 minutes, Thereby forming an adhesive layer.

Next, a composition for forming a release layer was spin-coated on a 100 mm Si wafer (second base material) having a diameter of 100 mm and a thickness of 525 탆, heated at 110 캜 for 3 minutes, further heated at 190 캜 for 3 minutes, To form a releasing layer.

A first release layer on the adhesive layer, and a second substrate on the substrate, in a vacuum at 190 ℃, at a pressure of 0.11MPa, 3 bungan crimping, and also N ₂ atmosphere, the curing conditions shown in Table 3 (Curing temperature and curing Hour) to prepare a laminate.

C-SAM (ultrasonic microscope) measurement was carried out on the laminate for adhesion of the obtained laminate, visibility of voids was visually observed, and the adhesiveness was evaluated according to the following criteria. In addition, the peelability was evaluated by the following method.

The second base material of the obtained laminate was polished until the thickness became 35 μm, and the flat polishing performance was evaluated based on the following criteria.

The laminate after the polishing of the second substrate was heated at 280 DEG C for 30 minutes, and warpage was evaluated based on the following criteria.

&Lt; Evaluation of adhesiveness >

The shear adhesive force of the laminate produced under the conditions described in the following table was measured in a direction along the surface of the adhesive layer at a rate of 250 mm / min using a tensile tester (Imada Digital Force Gauge, Model: ZP-50N) And evaluated according to the following criteria.

A: The wafer was strongly adhered enough to break up.

B: Peeled off with a force of 10 N or more and 50 N or less.

C: Peeled off with a force of 10 N or less.

&Lt; Evaluation of flat abrasive property &

The second base material of the produced laminate was polished until the thickness became 35 탆. The abrasive surface of the second base material was visually observed to confirm whether or not a concave portion having a diameter of 1 mm or more was present.

A: No concave part is visible at all.

B: The concave part is slightly generated, but it is acceptable.

C: The concave portion is generated in a large amount and can not be accepted.

&Lt; Evaluation of warpage &

The laminate after the polishing of the second base material was heated at 280 占 폚 for 30 minutes to prepare a test body.

The prepared specimen was heated from room temperature to 200 캜 by setting the temperature raising rate and the cooling rate at 10 캜 / min using FLX-2320 made by KLA-Tencor, and then cooled to room temperature to measure the Bow value.

A: Bow value is 40μm or less

B: Bow value exceeding 40μm but less than 80μm

C: Bow value of 80μm or more

&Lt; Evaluation of peelability &

The laminate produced under the conditions described in the following table was stretched in the vertical direction (lamination direction of each layer) of the laminate under the condition of 250 mm / min to confirm the peelability. After heating the produced laminate at 250 占 폚 for 30 minutes, the laminate was similarly stretched in the vertical direction of the laminate under the condition of 250 mm / min to confirm the peelability after the heating process, and evaluated according to the following criteria. The presence or absence of breakage of the Si wafer was visually confirmed.

A: Peeling force was less than 20N at the maximum.

B: The maximum peeling force was 20 N or more and less than 30 N, and peeling was possible.

C: The peeling force was 30 N or more and less than 50 N.

D: The maximum peeling force was 50 N or more, or the Si wafer was broken.

[Table 3]

From the above results, it can be concluded that the examples were able to combine peelability, flat polishing performance, and warpage suppression. Further, the adhesive property was also excellent.

On the other hand, the comparative example was inferior in either of peelability, flat abrasion resistance and warpage inhibition.

(Test Example 2)

&Lt; Composition of adhesive layer forming composition >

Binder: The compound shown in Table 4 and the additive amount

Polymerizable compound: The compound shown in Table 4 and the amount added

Antioxidant: IRGANOX 1010 (manufactured by BASF) 0.05 parts by mass

Sumilizer TP-D (Sumitomo Chemical Co., Ltd.) 0.05 parts by mass

Photopolymerization initiator: The compound shown in Table 4 and the amount added

Solvent: The compound shown in Table 4 and the amount added

The composition of the adhesive layers 21 to 30 and R2 is a photo-curable composition.

[Table 4]

(A-1) PCZ-300 (Mitsubishi Gas Chemical Company, Polycarbonate, MW = 83,000)

(A-2) APEC 9379 (Bayer, polycarbonate, MW = 51,000)

(A-3) Septon 2104 (Kurarayze, polystyrene-based elastomer, MW = 73,000)

(B-1) NK Ester A-9300 (trifunctional acrylate, radically polymerizable compound, manufactured by Shin Nakamura Kagaku Kogyo Co., Ltd.)

(B-2) NK Ester A-DPH (manufactured by Shin Nakamura Kagaku Kogyo Co., Ltd., hexafunctional acrylate, radical polymerizable compound)

(B-3) TAIC (triallyl isocyanurate, radically polymerizable compound)

(B-4) NK ester A-BPE-4 (bifunctional acrylate, radically polymerizable compound, manufactured by Shin Nakamura Kagaku Kogyo Co., Ltd.)

(C-1): cyclopentanone

(C-2): Anisole

(C-3): mesitylene

(D-3): IRGACURE-OXE02 (manufactured by BASF)

(D-4): Kaya cure-DETX (Nippon Kayaku)

&Lt; Preparation of Adhesive Laminate >

The composition for forming the adhesive layer was spin-coated on a 100 mm glass support (first substrate) having a diameter of 100 mm and a thickness of 525 탆, heated at 100 캜 for 1 minute, further heated at 150 캜 for 5 minutes, Thereby forming an adhesive layer.

Next, a composition for forming a release layer was spin-coated on a 100 mm Si wafer (second base material) having a diameter of 100 mm and a thickness of 525 탆, heated at 110 캜 for 3 minutes, further heated at 190 캜 for 3 minutes, To form a releasing layer.

The adhesive layer on the first base material and the release layer on the second base material were pressed for 3 minutes under a vacuum of 190 DEG C and a pressure of 0.11 MPa. Further, from the glass support side, light irradiation was performed at a wavelength of 365 nm using an ultraviolet ray exposure apparatus (LC8 manufactured by Hamamatsu Photonics Co., Ltd.) at an exposure amount shown in the table to produce a laminate.

C-SAM (ultrasonic microscope) measurement was carried out on the laminate for adhesion of the obtained laminate, visibility of voids was visually observed, and the adhesiveness was evaluated according to the following criteria. In addition, the peelability was evaluated by the following method.

The second base material of the obtained laminate was polished until the thickness became 35 μm, and the flat polishing performance was evaluated based on the following criteria.

The laminate after the polishing of the second substrate was heated at 280 DEG C for 30 minutes, and warpage was evaluated based on the following criteria.

&Lt; Evaluation of adhesiveness >

The shear adhesive force of the laminate produced under the conditions described in the following table was measured in a direction along the surface of the adhesive layer at a rate of 250 mm / min using a tensile tester (Imada Digital Force Gauge, Model: ZP-50N) And evaluated according to the following criteria.

A: The wafer was strongly adhered enough to break up.

B: Peeled off with a force of 10 N or more and 50 N or less.

C: Peeled off with a force of 10 N or less.

&Lt; Evaluation of flat abrasive property &

The second base material of the produced laminate was polished until the thickness became 35 탆. The abrasive surface of the second base material was visually observed to confirm whether or not a concave portion having a diameter of 1 mm or more was present.

A: No concave part is visible at all.

B: The concave part is slightly generated, but it is acceptable.

C: The concave portion is generated in a large amount and can not be accepted.

&Lt; Evaluation of warpage &

The laminate after the polishing of the second base material was heated at 280 占 폚 for 30 minutes to prepare a test body.

The prepared specimen was heated from room temperature to 200 캜 by setting the temperature raising rate and the cooling rate at 10 캜 / min using FLX-2320 made by KLA-Tencor, and then cooled to room temperature to measure the Bow value.

A: Bow value is 40μm or less

B: Bow value exceeding 40μm but less than 80μm

C: Bow value of 80μm or more

&Lt; Evaluation of peelability &

The laminate produced under the conditions described in the following table was stretched in the vertical direction (lamination direction of each layer) of the laminate under the condition of 250 mm / min to confirm the peelability. After the laminate was heated at 250 占 폚 for 30 minutes, it was similarly stretched in the vertical direction of the laminate under the condition of 250 mm / min to confirm the peelability after the heat treatment and evaluated according to the following criteria. The presence or absence of breakage of the Si wafer was visually confirmed.

A: Peeling force was less than 20N at the maximum.

B: The maximum peeling force was 20 N or more and less than 30 N, and peeling was possible.

C: The peeling force was 30 N or more and less than 50 N.

D: The peeling force at the maximum was 50 N or more, but the wafer was broken.

[Table 5]

From the above results, it can be concluded that the examples were able to combine peelability, flat polishing performance, and warpage suppression. Further, the adhesive property was also excellent.

11:
12: carrier substrate
15:
20:
60: device wafer
60a: thin device wafer
61: silicon substrate
62: Device chip

Claims (17)

An adhesive layer made of a curable composition,
A block copolymer, and a compound having a fluorine atom. The method according to claim 1,
Wherein the fluorine atom-containing compound is a (meth) acrylic polymer. The method according to claim 1 or 2,
Wherein the block copolymer comprises a repeating unit derived from styrene. The method according to any one of claims 1 to 3,
Wherein the block copolymer is an elastomer. The method according to any one of claims 1 to 4,
Wherein the block copolymer is a hydrogenation product. The method according to any one of claims 1 to 5,
Wherein the block copolymer is a block copolymer in which one terminal or both terminals is a styrene block. The method according to any one of claims 1 to 6,
Wherein the fluorine atom-containing compound has a mineral oil. The method according to any one of claims 1 to 7,
Wherein the curable composition comprises a radically polymerizable compound. The method of claim 8,
Wherein the radically polymerizable compound is a compound having two or more radically polymerizable groups. The method according to any one of claims 1 to 9,
Wherein the curable composition comprises a binder. The method according to any one of claims 1 to 10,
Wherein the curable composition is a thermosetting composition. A laminate having a substrate on one side or both sides of the adhesive layer laminate according to any one of claims 1 to 11. The method of claim 12,
Wherein the base material has the base material on both sides of the adhesive laminate, one of the base material is a carrier base material and the other is a device wafer. 14. The method of claim 13,
Wherein one surface of the adhesive laminate is in contact with the surface of the device wafer and the other surface of the adhesive laminate is in contact with the surface of the carrier substrate. 15. The method of claim 14,
Wherein the release layer of the adhesive laminate is in contact with the surface of the device wafer. A composition for forming an adhesive layer comprising a curable composition,
A block copolymer, and a compound having a fluorine atom. 18. The method of claim 16,
The kit according to any one of claims 1 to 11, wherein the adhesive laminate is a laminate for adhesive lamination.

Images