TWI732764B - Temporary adhesive, adhesive film, adhesive support, laminate and adhesive kit - Google Patents

Abstract

The present invention provides a temporary adhesive having excellent releasability at room temperature and excellent adhesiveness, and an adhesive film, adhesive support, laminate, and set using the temporary adhesive. A temporary adhesive containing: a compound that is liquid at 25°C and contains silicon atoms, and contains the elasticity of a styrene-derived repeating unit in a proportion of 50% by mass or more and 95% by mass or less of all repeating units Body X.

Description

Temporary adhesive, adhesive film, adhesive support, laminate and adhesive kit

The present invention relates to a temporary adhesive, adhesive film, adhesive support, laminate and set. More specifically, it relates to a temporary adhesive, adhesive film, adhesive support, laminate, and set that can be preferably used in the manufacture of semiconductor devices and the like.

In the manufacturing process of semiconductor devices such as Integrated Circuit (IC) or Large Scale Integrated Circuit (LSI), multiple IC chips are formed on the device wafer and dicing And monolithic.

With the demand for further miniaturization and high performance of electronic equipment, IC chips mounted on electronic equipment are also required to be further miniaturized and high-integrated. However, the integrated circuit in the surface direction of the element wafer is high. Integration is close to the limit.

As a method of electrical connection from the integrated circuit in the IC chip to the external terminal of the IC chip, wire bonding has been widely known from the past. However, in order to realize the miniaturization of the IC chip, it has been known in recent years. A method in which a through hole is provided in the element wafer and a metal plug as an external terminal is connected to an integrated circuit through the through hole (a so-called Through-Silicon Via (TSV) method). However, the method of forming silicon through-electrodes alone cannot adequately cope with the demand for further high integration of IC chips in recent years.

In view of the above, there is known a technique for increasing the integration degree per unit area of the element wafer by multilayering the integrated circuits in the IC chip. However, the multi-layered integrated circuit increases the thickness of the IC chip, so it is necessary to reduce the thickness of the components constituting the IC chip. As the thinning of such components, for example, the thinning of element wafers has been studied, which not only leads to the miniaturization of IC wafers, but also saves labor in the process of manufacturing through-holes of element wafers in the manufacture of silicon through electrodes. Considered promising. In addition, in semiconductor devices such as power devices and image sensors, attempts have been made to reduce the thickness from the viewpoint of increasing the degree of integration or increasing the degree of freedom of the device structure.

As element wafers, those having a thickness of about 700 μm to 900 μm are widely known, but in recent years, attempts have been made to thin the thickness of the element wafers to 200 μm or less for the purpose of miniaturization of IC wafers and the like. However, the device wafer with a thickness of 200 μm or less is very thin, and the semiconductor device manufacturing member using it as the base material is also very thin. Therefore, it is difficult to perform further processing on this kind of member or to move only this kind of member. Support the components stably and without causing damage.

In order to solve the above-mentioned problems, it is known that a temporary adhesive is used to temporarily bond a device wafer with a device on its surface before thinning to a support, and then grind the back surface of the device wafer to make it thinner. Support peeling technology. For example, Patent Document 1 discloses an adhesive composition having a polystyrene elastomer and a surface modifier. In addition, Patent Document 2 discloses a temporary fixing material containing a cycloolefin-based polymer and a compound having a structure such as a dialkyl silicone structure and a polyoxyalkylene structure. Furthermore, Patent Document 3 describes that a release layer and a protective layer are used for temporary bonding of the element wafer and the support substrate, and a material containing fluorine atoms and/or silicon atoms is used for the release layer. [Prior Art Document] [Patent Document]

[Patent Document 1] U.S. Patent No. 2014/0178701A1 [Patent Document 2] Japanese Patent Laid-open No. 2013-241568 [Patent Document 3] Japanese Patent Laid-Open No. 2015-065401

[Problems to be Solved by the Invention] However, the inventors conducted research, and as a result, it was found that the adhesive composition described in Patent Document 1 and the temporary fixing material described in Patent Document 2 are used to thin the element wafer After chemicalization, it is difficult to peel the device wafer from the support at room temperature. In addition, in general, if it is desired to improve the releasability, the adhesiveness tends to deteriorate. The present invention was made to solve the above-mentioned problems, and its object is to provide a temporary adhesive that has excellent releasability at room temperature and excellent adhesiveness, and an adhesive film, an adhesive support, and an adhesive film using the temporary adhesive. Laminated body and set. [Means to solve the problem]

Based on the above-mentioned problems, the inventors conducted diligent studies. As a result, they found that a compound that is liquid at 25°C and contains silicon atoms is blended into a styrene-based elastomer with a high proportion of styrene-derived repeating units. The above-mentioned problems are solved, and the present invention has been completed. Specifically, the above-mentioned problem is solved by the following means <1>, preferably by the following means <2> to <25>. <1> A temporary adhesive containing: a compound that is liquid at 25°C and contains silicon atoms, and contains repeats derived from styrene in a proportion of 50% by mass or more and 95% by mass or less in all repeating units The elastomer X of the unit. <2> The temporary adhesive as described in <1>, wherein the silicon atom-containing compound has a 10% thermal mass reduction temperature at 20°C/min from 25°C of 250°C or higher. <3> The temporary adhesive as described in <1> or <2>, wherein the elastomer X is based on the method of Japanese Industrial Standards (JIS) K6253 and uses Type A durometer The measured hardness is 80 or more. <4> The temporary adhesive as described in any one of <1> to <3>, which further contains a styrene-derived repeating unit in a ratio of 10% by mass or more and less than 50% by mass in all repeating units The elastomer Y. <5> The temporary adhesive as described in <4>, wherein the mass ratio of the elastomer X to the elastomer Y is 5:95 to 95:5. <6> The temporary adhesive according to any one of <1> to <5>, wherein at least one of the elastomers contained in the temporary adhesive is heated from 25°C at 20°C/min by 5% heat The mass reduction temperature is 250°C or higher. <7> The temporary adhesive according to any one of <1> to <6>, wherein the amount of unsaturated double bonds of at least one type of elastomer contained in the temporary adhesive is 7 mmol/g or less. <8> The temporary adhesive according to any one of <1> to <7>, wherein at least one of the elastomers contained in the temporary adhesive is a hydride. <9> The temporary adhesive according to any one of <1> to <8>, wherein at least one of the elastomers contained in the temporary adhesive is a block copolymer. <10> The temporary adhesive according to any one of <1> to <9>, wherein at least one of the elastomers contained in the temporary adhesive has a single end or both ends are embedding derived from styrene Segment copolymer. <11> The temporary adhesive according to any one of <1> to <10>, wherein the content of the compound containing silicon atoms is 0.01% by mass or more with respect to the total amount of elastomers in the temporary adhesive And less than 2.5% by mass. <12> The temporary adhesive according to any one of <1> to <11>, wherein the silicon atom-containing compound is selected from the group consisting of dimethylpolysiloxane, methylphenylpolysiloxane, and Phenyl polysiloxane and polyether modified polysiloxane. <13> The temporary adhesive as described in any one of <1> to <12>, which further contains at least one of an antioxidant and a solvent. <14> The temporary adhesive according to any one of <1> to <13>, wherein the temporary adhesive is a temporary adhesive for semiconductor device manufacturing. <15> An adhesive film having an adhesive layer containing the temporary adhesive as described in any one of <1> to <14>. <16> An adhesive support having an adhesive layer containing the temporary adhesive as described in any one of <1> to <14>, and a support. <17> A laminate having a support, an adhesive layer containing the temporary adhesive as described in any one of <1> to <14>, and a substrate. <18> The laminate according to <17>, wherein the adhesive layer is located on the surface of the support, and the substrate is located on the surface of the adhesive layer on the opposite side to the support. <19> The laminate according to <17>, in which the support, the adhesive layer, and the base material are layered in the order described, and between the support and the adhesive layer The second adhesive layer having a different composition. <20> The laminate according to <17>, wherein the support, the adhesive layer, and the base material are layered in the order described, and the adhesive layer and the base material have and The second adhesive layer having a different composition. <21> The laminate according to <19> or <20>, wherein the second adhesive layer contains repeating units derived from styrene in a ratio of 50% by mass or more and 95% by mass or less in all repeating units The elastomer X. <22> The laminate according to any one of <19> to <21>, in which the second adhesive layer is contained in all repeating units at a ratio of 10% by mass or more and less than 50% by mass. Elastomer Y is a repeating unit of ethylene. <23> The laminate according to any one of <19> to <22>, wherein the content of the compound containing silicon atoms in the second adhesive layer that is liquid at 25° C. is that of the adhesive layer 10% by mass or less of the content of the compound that is liquid at 25° C. and contains silicon atoms contained in it. <24> The laminate according to any one of <17> to <23>, wherein the substrate is an element wafer. <25> A set comprising: the temporary adhesive as described in any one of <1> to <14>; and a second adhesive contained in all repeating units at 50% by mass or more and 95% by mass The following ratio contains elastomer X derived from styrene-derived repeating units, and is different from the composition of the temporary adhesive. [Effects of the invention]

According to the present invention, it is possible to provide a temporary adhesive having excellent releasability at room temperature and excellent adhesiveness, and an adhesive film, adhesive support, laminate, and set using the temporary adhesive.

Hereinafter, the content of the present invention will be described in detail. In addition, in this specification, "-" is used in the meaning including the numerical value described before and after it as a lower limit and an upper limit. In the expression of the group (atomic group) in this specification, the expression that does not describe substituted and unsubstituted includes a group (atomic group) without a substituent, and also includes a group (atomic group) having a substituent. For example, the term "alkyl" includes not only an unsubstituted alkyl group (unsubstituted alkyl group) but also a substituted alkyl group (substituted alkyl group). The "actinic rays" or "radiation rays" in this specification refer to, for example, visible rays, ultraviolet rays, extreme ultraviolet rays, electron beams, X-rays, and the like. In this specification, the so-called "light" refers to actinic rays or radiation. In this manual, the term "exposure", unless otherwise specified, includes not only exposure using mercury lamps, ultraviolet rays, extreme ultraviolet rays represented by excimer lasers, X-rays, extreme ultraviolet light (Extreme Ultra-Violet), etc. , Also includes drawing using particle beams such as electron beams and ion beams. In this specification, "(meth)acrylate" means acrylate and methacrylate, "(meth)acrylic" means acrylic and methacrylic acid, and "(meth)acryloyl" means acryloyl and Methacrylic acid group. In this specification, the weight average molecular weight and the number average molecular weight are defined as polystyrene conversion values measured by Gel Permeation Chromatography (GPC). In this specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) can be used, for example, by using HLC-8220 (manufactured by Tosoh (stock)) and using TSK gel Super AWM-H (Tosoh (Tosoh) ) (Stock), 6.0 mm (inner diameter) × 15.0 cm) as the column, and use 10 mmol/L lithium bromide N-methyl pyrrolidinone (N-methyl pyrrolidinone, NMP) solution as the washing solution . In this specification, the "lipophilic group" refers to a functional group that does not contain a hydrophilic group. In addition, the "hydrophilic group" refers to a functional group that shows affinity with water. In addition, in the embodiments described below, for members and the like that have already been described in the referenced drawings, the description is simplified or omitted because the same symbols or symbols equivalent to them are attached in the drawings.

<Temporary Adhesive> The temporary adhesive of the present invention is characterized by containing: a compound that is liquid at 25°C and contains silicon atoms (hereinafter sometimes referred to as "silicon-based liquid compound"), and in all repeating units Elastomer X containing repeating units derived from styrene in a ratio of 50% by mass or more and 95% by mass or less. According to the temporary adhesive of the present invention, when a substrate such as a device wafer is subjected to mechanical or chemical treatment, it is possible to form an adhesive layer that can stably perform temporary adhesion to the substrate and can easily release the temporary adhesion to the substrate . The temporary adhesive of the present invention contains the above-mentioned silicon-based liquid compound. Therefore, the silicon-based liquid compound tends to be concentrated on the surface layer of the adhesive layer, and the concentration of the silicon-based liquid compound in the surface layer of the adhesive layer can be increased. Therefore, even if the amount of the silicon-based liquid compound is small relative to the solid content of the temporary adhesive, it is possible to form an adhesive layer with excellent releasability to the substrate or support. In addition, since Elastomer X containing repeating units derived from styrene in a proportion of 50% by mass or more and 95% by mass or less in all repeating units is included, it forms a source in a part or all of the adhesive layer containing the temporary adhesive. From the hard region of the elastomer X, the peelability is improved. The temporary adhesive of the present invention can be particularly preferably used as a temporary adhesive for semiconductor device manufacturing. Hereinafter, the temporary adhesive of the present invention will be specifically described.

<<Silicon-based liquid compound>> The temporary adhesive of the present invention contains a silicon-based liquid compound. In the present invention, the term “liquid compound” refers to a compound having fluidity at 25°C, for example, a compound having a viscosity of 1 mPa·s to 100,000 mPa·s at 25°C. The viscosity of the silicon-based liquid compound at 25°C is more preferably 10 mPa·s to 20,000 mPa·s, and particularly preferably 100 mPa·s to 15,000 mPa·s. If the viscosity of the silicon-based liquid compound is in the above range, the silicon-based liquid compound is more likely to be present on the surface layer of the adhesive layer, which is preferable.

In the present invention, the silicon-based liquid compound can also be preferably used in any form of oligomer and polymer. In addition, it may be a mixture of oligomer and polymer. The mixture may further contain monomer (monomer). In addition, the silicon-based liquid compound may also be a monomer. From the viewpoint of heat resistance and the like, the silicon-based liquid compound is preferably an oligomer, a polymer, and a mixture of these. As the oligomer and polymer, for example, an addition polymer, a polycondensate (polycondensate), an addition condensate, etc. can be used without particular limitation, but a polycondensate is particularly preferred. The weight average molecular weight of the silicon-based liquid compound is preferably 500 to 100,000, more preferably 1,000 to 50,000, and still more preferably 2,000 to 20,000.

In the present invention, the silicon-based liquid compound is preferably a compound that does not change when the substrate for temporary bonding is processed. For example, it is preferably a compound that can exist in a liquid state even after heating at 250° C. or higher or processing the substrate with various chemical liquids. As a specific example, it is preferable to heat from a state of 25°C to 250°C at a temperature increase of 10°C/min, and then cool to 25°C. The viscosity at 25°C is 1 mPa·s to 100,000 mPa·s. It is more preferably 10 mPa·s to 20,000 mPa·s, and particularly preferably 100 mPa·s to 15,000 mPa·s. As the silicon-based liquid compound having such characteristics, a non-thermosetting compound having no reactive group is preferred. The reactive group mentioned here refers to the entire group that reacts by heating at 250°C, and includes a polymerizable group, a hydrolyzable group, and the like. Specifically, for example, a (meth)acrylic group, an epoxy group, an isocyanate group, etc. may be mentioned. In addition, the 10% thermal mass reduction temperature of the silicon-based liquid compound at a temperature rise of 20°C/min from 25°C is preferably 250°C or higher, more preferably 280°C or higher. In addition, the upper limit is not particularly limited. For example, it is preferably 1000°C or lower, and more preferably 800°C or lower. According to this aspect, it is easy to form an adhesive layer excellent in heat resistance. In addition, the so-called thermal mass reduction temperature refers to a value measured by a thermogravimetric analyzer (TGA) under a nitrogen stream under the above-mentioned heating conditions.

The silicon-based liquid compound used in the present invention preferably contains a lipophilic group. Examples of the lipophilic group include linear or branched alkyl groups, cycloalkyl groups, aromatic groups, and the like.

The carbon number of the alkyl group is preferably 1-30, more preferably 1-10, and still more preferably 1-3. Specific examples of the alkyl group include, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tetradecyl, Octadecyl, isopropyl, isobutyl, second butyl, tertiary butyl, 1-ethylpentyl, 2-ethylhexyl.

The alkyl group may have a substituent. As a substituent, a halogen atom, an alkoxy group, an aromatic group, etc. are mentioned. As a halogen atom, a chlorine atom, a fluorine atom, a bromine atom, an iodine atom, etc. are mentioned, A fluorine atom is preferable.

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

Cycloalkyl groups may be monocyclic or polycyclic. The carbon number of the cycloalkyl group is preferably 3-30, more preferably 4-30, still more preferably 6-30, and particularly preferably 6-20. Examples of monocyclic cycloalkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl. Examples of polycyclic cycloalkyl groups include adamantyl, norbornyl, bornyl, camphenyl, decahydronaphthyl, tricyclodecyl, tetracyclodecyl, and camphenyl Group (camphoroyl), dicyclohexyl and pinenyl. Cycloalkyl groups may have such substituents.

（chrysene）環、聯伸三苯（triphenylene）環、茀環、聯苯環、吡咯環、呋喃環、噻吩環、咪唑環、噁唑環、噻唑環、吡啶環、吡嗪環、嘧啶環、噠嗪環、吲哚嗪環、吲哚環、苯并呋喃環、苯并噻吩環、異苯并呋喃環、喹嗪環、喹啉環、酞嗪環、萘啶環、喹噁啉環、喹唑啉環、異喹啉環、咔唑環、啡啶（phenanthridine）環、吖啶環、啡啉環、噻蒽（thianthrene）環、苯并哌喃（chromene）環、氧雜蒽（xanthene）環、啡噁噻（phenoxathiin）環、啡噻嗪（phenothiazine）環及啡嗪環，較佳為苯環。 芳香族基可具有所述取代基。作為取代基，較佳為直鏈烷基。The aromatic group may be monocyclic or polycyclic. The number of carbon atoms in the aromatic group is preferably 6-20, more preferably 6-14, and particularly preferably 6-10. The aromatic group preferably does not contain heteroatoms (for example, nitrogen atoms, oxygen atoms, sulfur atoms, etc.) in the elements constituting the ring. Specific examples of aromatic groups include: benzene ring, naphthalene ring, pentalene ring, indene ring, azulene ring, heptalene ring, and indecene ring , Perylene ring, pentacene ring, acenaphthene ring, phenanthrene ring, anthracene ring, fused tetraphenyl ring,

(Chrysene) ring, triphenylene ring, pyridine ring, biphenyl ring, pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyridine ring, pyrazine ring, pyrimidine ring, pyridine ring Pyrazine ring, indoleazine ring, indole ring, benzofuran ring, benzothiophene ring, isobenzofuran ring, quinazine ring, quinoline ring, phthalazine ring, naphthyridine ring, quinoxaline ring, quinoline Oxazoline ring, isoquinoline ring, carbazole ring, phenanthridine ring, acridine ring, phenanthridine ring, thianthrene ring, chromene ring, xanthene The ring, the phenoxathiin ring, the phenothiazine ring and the phenothiazine ring are preferably a benzene ring. The aromatic group may have such a substituent. As the substituent, a linear alkyl group is preferred.

所述通式中的R¹ 及R² 分別獨立地為直鏈或分支的烷基、環烷基或芳香族基，R¹ 及R² 的一者亦可為包含聚醚鏈的有機基。 另外，L¹ 表示-O-、或者包含聚醚鏈的連結基。The silicon-based liquid compound is preferably a compound represented by the following general formula. [化1]

^{R 1} and R ^{2 in} the general formula are each independently a linear or branched alkyl group, a cycloalkyl group, or an aromatic group, and one of R ¹ and R ² may also be an organic group including a polyether chain. In addition, L ¹ represents -O- or a linking group containing a polyether chain.

The preferred range of the straight-chain or branched alkyl group, cycloalkyl group or aromatic group ^{as R 1} and R ² in the general formula is the same as the straight-chain or branched alkyl group described in the lipophilic group, The cycloalkyl group or the aromatic group has the same meaning, and the preferred range is also the same. In addition, in the general formula, one of R ¹ and R ² may be an organic group including a polyether chain as a preferable aspect. The polyether structure in the organic group containing the polyether chain is not particularly limited as long as it has a plurality of ether bonds, and examples include polyethylene glycol structure (polyethylene oxide structure), Polypropylene glycol structure (polypropylene oxide structure), polybutylene glycol (polytetramethylene glycol) structure, polyether structure derived from a variety of alkylene glycols (or alkylene oxides) (such as poly(propylene glycol/ethylene two Alcohol) structure, etc.) and other polyoxyalkylene structures. Furthermore, the addition form of each alkanediol in the polyether structure derived from a plurality of alkanediols may be a block type (block copolymerization type) or a random type (random copolymerization type).

The organic group containing the polyether chain may be an organic group containing only the polyether structure, or an organic group having the following structure, and the structure is one or more than two of the polyether structure, and one Or two or more linking groups (divalent groups with more than one atom) are connected. As the linking group in the organic group containing the polyether chain, for example, a divalent hydrocarbon group (especially a linear or branched alkylene group), a sulfide group (-S-), and an ester group ( -COO-), amide group (-CONH-), carbonyl group (-CO-), carbonate group (-OCOO-), groups formed by bonding two or more of these groups, etc.

In addition, as the ^{polyether chain of L 1} in the general formula, it is not particularly limited as long as it includes the structure having a plurality of ether bonds, but the structure having a plurality of ether bonds can be preferably used. . In addition, the polyether chain may be an organic group containing only a polyether structure, or may be an organic group having a structure that is one or more than two of the polyether structure, and one or more connections A group (a divalent group with more than one atom) is connected. As the linking group in the organic group containing the polyether chain, for example, a divalent hydrocarbon group (especially a linear or branched alkylene group), a sulfide group (-S-), and an ester group ( -COO-), amide group (-CONH-), carbonyl group (-CO-), carbonate group (-OCOO-), groups formed by bonding two or more of these groups, etc.

The silicon-based liquid compound in the present invention is more preferably at least one selected from the group consisting of dimethyl polysiloxane, methyl phenyl polysiloxane, diphenyl polysiloxane, and polyether modified polysiloxane. A sort of.

Examples of the silicon-based liquid compound include Japanese Patent Laid-Open No. 62-36663, Japanese Patent Laid-Open No. 61-226746, Japanese Patent Laid-Open No. 61-226745, Japanese Patent Laid-Open No. 62-170950, Japanese Patent Japanese Patent Application Publication No. 63-34540, Japanese Patent Application Publication No. 7-230165, Japanese Patent Application Publication No. 8-62834, Japanese Patent Application Publication No. 9-54432, Japanese Patent Application Publication No. 9-5988, Japanese Patent Application Publication No. 2001- Among the surfactants described in the respective publications of No. 330953, those that are liquid at 25°C. As commercially available products, the product names "BYK-300", "BYK-301/302", "BYK-306", and "BYK-307" can be used , "BYK-310", "BYK-315", "BYK-313", "BYK-320", "BYK-322" , "BYK-323", "BYK-325", "BYK-330", "BYK-331", "BYK-333" , "BYK-337", "BYK-341", "BYK-344", "BYK-345/346", "BYK- 347", "BYK-348", "BYK-349", "BYK-370", "BYK-375", "BYK- 377", "BYK-378", "BYK-UV3500", "BYK-UV3510", "BYK-UV3570", "BYK- 3550", "BYK-SILCLEAN 3700", "BYK-SILCLEAN 3720" (manufactured by BYK-Chemie Japan (stock) above); Trade names "AC FS 180", "AC FS 360", "AC S 20" (manufactured by Algin Chemie above); trade names "Polyflow KL-400X", "Polyflow "Polyflow (Polyflow) KL-400HF", "Polyflow (Polyflow) KL-401", "Polyflow (Polyflow) KL-402", "Polyflow (Polyflow) KL-403", "Polyflow Polyflow KL-404", "Polyflow KL-700" (manufactured by Kyoeisha Chemical Co., Ltd. above); trade names "KP-301", "KP-306", "KP -109", "KP-310", "KP-310B", "KP-323", "KP-326", "KP-341", "KP-104", "KP-110", "KP-112 ”, “KP-360A”, “KP-361”, “KP-354”, “KP-355”, “KP-356”, “KP-357”, “KP-358”, “KP-359”, "KP-362", "KP-365", "KP-366", "KP-368", "KP-369", "KP-330", "KP-6 50", "KP-651", "KP-390", "KP-391", "KP-392" (manufactured by Shin-Etsu Chemical Co., Ltd. above); product names "LP-7001", "LP-7002" , "SH28PA", "8032 additives (ADDITIVE)", "57 additives (ADDITIVE)", "L-7604", "FZ-2110", "FZ-2105", "67 additives (ADDITIVE)", "8618 additives (ADDITIVE)", "3 additives (ADDITIVE)", "56 additives (ADDITIVE)" (manufactured by Toray Dow Corning (stock) above); "TEGO wetting agent (TEGO) WET 270" (manufactured by Evonik Degussa Japan (stock)); "NBX-15" (manufactured by NEOS (stock)) and other commercially available products.

The content of the silicon-based liquid compound in the temporary adhesive of the present invention is preferably 0.009% by mass or more, more preferably 0.01% by mass or more, and still more preferably 0.05% by mass or more, particularly preferably 0.1% by mass or more, and even more preferably 0.2% by mass or more. In addition, as the upper limit, it is preferably 10% by mass or less, more preferably 5% by mass or less, still more preferably less than 2.5% by mass, particularly preferably 1% by mass or less, and still more preferably 0.6% by mass or less. When the content of the silicon-based liquid compound is within the above range, the adhesiveness and peelability are more excellent. Particularly in the present invention, even if the amount of the temporary adhesive is small, the effect of the present invention can be achieved. The silicon-based liquid compound may be one kind alone, or two or more kinds may be used in combination. When two or more types are used in combination, it is preferable that the total content is in the above-mentioned range.

<<Elastomer>> The temporary adhesive of the present invention contains an elastomer. By using an elastomer, it is also possible to follow the fine unevenness of the support or the base material, and use a moderate anchor effect to form an adhesive layer with excellent adhesiveness. In addition, when the support is peeled from the base material, the support can be peeled from the base material without applying stress to the base material, etc., and it is possible to prevent breakage or peeling of elements and the like on the base material. In addition, in this specification, the term "elastomer" refers to a polymer compound that exhibits elastic deformation. That is, it is defined as a polymer compound that has the following properties: when an external force is applied, it deforms instantly in response to the external force, and when the external force is removed, it returns to its original shape in a short time.

The elastomer contained as an essential component in the present invention is elastomer X containing styrene-derived repeating units in a proportion of 50% by mass or more and 95% by mass or less in all repeating units, and is preferably also included in all repeating units. The repeating unit contains the elastomer Y of the repeating unit derived from styrene in a ratio of 10% by mass or more and less than 50% by mass. The combination of Elastomer X and Elastomer Y provides excellent releasability and good flatness of the polished surface of the substrate (hereinafter also referred to as flat abrasiveness), which can effectively suppress the warpage of the polished substrate. produce. The mechanism for obtaining this effect can be presumed to be derived from the following. That is, the elastic body X is a relatively hard material, so by including the elastic body X, an adhesive layer with excellent peelability can be produced. In addition, since the elastic body Y is a relatively soft material, it is easy to form an adhesive layer having elasticity. Therefore, when the temporary adhesive of the present invention is used to produce a laminate of a substrate and a support, and the substrate is polished to form a thin film, even if the pressure during polishing is applied locally, the adhesive layer can be elastically deformed and easily Restore to its original shape. As a result, excellent flat abrasiveness is obtained. In addition, even if the polished layered body is heated and then cooled, the internal stress generated during cooling can be relieved by the adhesive layer, so that the occurrence of warpage can be effectively suppressed. In addition, even if the elastomer Y is blended into the elastomer X, there are regions where the elastomer X is phase-separated, and the like, whereby the excellent peelability by the elastomer X can be sufficiently achieved.

Hereinafter, the common preferable conditions of the elastomer X and the elastomer Y (these are collectively referred to as "polystyrene elastomer") will be described.

There is no restriction|limiting in particular as a polystyrene-type elastomer, According to the objective, it can select suitably. Examples include: styrene-butadiene-styrene block copolymer (SBS), styrene-isoprene-styrene block copolymer (SIS), styrene-ethylene-butylene-styrene block copolymer Segment copolymer (SEBS), styrene-butadiene-butene-styrene copolymer (SBBS) and their hydrogenated products, styrene-ethylene-propylene-styrene block copolymer (SEPS), styrene -Ethylene-ethylene-propylene-styrene block copolymer, etc.

The weight average molecular weight of the polystyrene elastomer is preferably 2,000 to 200,000, more preferably 10,000 to 200,000, and still more preferably 50,000 to 100,000. By being within this range, the solubility of the temporary adhesive in the solvent becomes excellent, and the coatability is improved. In addition, when the remaining adhesive layer is removed after the support is peeled from the substrate, the solubility in the solvent is also excellent, so there is an advantage that the residue does not remain on the substrate or the support.

In the present invention, as polystyrene elastomers, block copolymers, random copolymers, and graft copolymers can be cited. Block copolymers are preferred, and one or both ends are styrene. The block copolymer is particularly preferably a block copolymer having styrene at both ends. If both ends of the polystyrene elastomer are made into block copolymers of styrene (repeating units derived from styrene), the thermal stability tends to be further improved. The reason is that a repeating unit derived from styrene with high heat resistance exists at the terminal. In particular, it is preferable that the block portion of the repeating unit derived from styrene is a reactive polystyrene-based hard block, which tends to be more excellent in heat resistance and chemical resistance. In addition, it is considered that if these are used as block copolymers, phase separation occurs in the hard block and the soft block at 200°C or higher. It is considered that this phase-separated shape contributes to suppressing the occurrence of irregularities on the surface of the base material of the element wafer. In addition, from the viewpoint of solubility in a solvent and resistance in a resist solvent, such an elastomer is also more preferable.

In the present invention, the polystyrene elastomer is preferably a hydride. If the polystyrene-based elastomer is a hydride, the thermal stability or storage stability is improved. Furthermore, the releasability and the cleaning removability of the adhesive layer after peeling are improved. In addition, the term "hydrogenated product" refers to a polymer having a hydrogenation structure of an elastomer.

The 5% thermal mass reduction temperature of the polystyrene elastomer at a temperature rise of 20°C/min from 25°C is preferably 250°C or higher, more preferably 300°C or higher, still more preferably 350°C or higher, particularly preferably 400°C or higher . In addition, the upper limit is not particularly limited. For example, it is preferably 1000°C or lower, and more preferably 800°C or lower. According to this aspect, it is easy to form an adhesive layer excellent in heat resistance. The polystyrene elastomer preferably has the following properties: when the original size is set to 100%, it can be deformed to 200% with a small external force at room temperature (20°C), and when the external force is removed, Recovered to below 130% in a short time.

The amount of unsaturated double bonds of the polystyrene elastomer is preferably less than 15 mmol/g, more preferably 7 mmol/g or less, and still more preferably less than 5 from the viewpoint of releasability after the processing step. mmol/g, particularly preferably less than 0.5 mmol/g. There is no particular restriction on the lower limit, but it can be set to 0.001 mmol/g or more, for example. Furthermore, the amount of unsaturated double bonds mentioned here does not include the unsaturated double bonds in the benzene ring derived from styrene. The amount of unsaturated double bonds can be calculated by nuclear magnetic resonance (Nuclear Magnetic Resonance, NMR) measurement.

In addition, in this specification, the "repeating unit derived from styrene" is a structural unit derived from styrene or styrene contained in the polymer when a styrene derivative is polymerized, and may have a substituent. Examples of styrene derivatives include α-methylstyrene, 3-methylstyrene, 4-propylstyrene, 4-cyclohexylstyrene, and the like. As a substituent, a C1-C5 alkyl group, a C1-C5 alkoxy group, a C1-C5 alkoxyalkyl group, an acetoxy group, a carboxyl group, etc. are mentioned, for example.

Examples of commercially available polystyrene elastomers include: Tufprene A, Tufprene 125, Tufprene 126S, and Solprene T, Asaprene T-411, Asaprene T-432, Asaprene T-437, Asaprene T-438, Asaprene (Asaprene) T-439, Tuftec H1272, Tuftec P1500, Tuftec H1052, Tuftec H1062, Tuftec H1062 M1943, Tuftec M1911, Tuftec H1041, Tuftec MP10, Tuftec M1913, Tuftec H1051, Tuftec H1051 Tuftec H1053, Tuftec P2000, Tuftec H1043 (the above are trade names, manufactured by Asahi Kasei); Elastomer AR-850C, Elastomer AR-815C, Elastomer AR-840C, Elastomer AR-830C, Elastomer AR-860C, Elastomer AR-875C, Elastomer AR-885C, Elastic Elastomer AR-SC-15, Elastomer AR-SC-0, Elastomer AR-SC-5, Elastomer AR-710, Elastomer AR-SC- 65. Elastomer AR-SC-30, Elastomer AR-SC-75, Elastomer AR-SC-45, Elastomer AR-720, Elastomer AR -741, Elastomer AR-731, Elastomer AR-750, Elastomer AR-760, Elastomer AR-770, Elastomer AR-781, Elastomer (Elastomer) AR-791, elastomer (Elastomer) AR-FL-75N, elastomer (Elastomer) AR-FL-85N, elastomer (Elastomer) mer) AR-FL-60N, Elastomer AR-1050, Elastomer AR-1060, Elastomer AR-1040 (the above are trade names, manufactured by Aronkasei); Section Kraton D1111, Kraton D1113, Kraton D1114, Kraton D1117, Kraton D1119, Kraton D1124, Kraton D1126, Kraton (Kraton) D1161, Kraton D1162, Kraton D1163, Kraton D1164, Kraton D1165, Kraton D1183, Kraton D1193, Kraton ( Kraton DX406, Kraton D4141, Kraton D4150, Kraton D4153, Kraton D4158, Kraton D4270, Kraton D4271, Kraton ) D4433, Kraton D1170, Kraton D1171, Kraton D1173, Cariflex IR0307, Cariflex IR0310, Cariflex IR0401 , Kraton D0242, Kraton D1101, Kraton D1102, Kraton D1116, Kraton D1118, Kraton D1133, Kraton D1152

Kraton D1153, Kraton D1155, Kraton D1184, Kraton D1186, Kraton D1189, Kraton D1191, Kraton D1192 Kraton DX405, Kraton DX408, Kraton DX410, Kraton DX414, Kraton DX415, Kraton A1535, Kraton A1536, Kraton (Kraton) FG1901, Kraton FG1924, Kraton G1640, Kraton G1641, Kraton G1642, Kraton G1643, Kraton G1645, Kraton ( Kraton G1633, Kraton G1650, Kraton G1651, Kraton G1652, Kraton G1654, Kraton G1657, Kraton G1660, Kraton ) G1726, Kraton G1701, Kraton G1702, Kraton G1730, Kraton G1750, Kraton G1765, Kraton G4609, Kraton G4610 (the above are trade names, manufactured by Kraton); TR2000, TR2001, TR2003, TR2250, TR2500, TR2601, TR2630, TR2787, TR2827, TR1086, TR1600, SIS5002, SIS5200, SIS5250, SIS5405, SIS5505, Dyna Dynaron 6100P, Dynaron 4600P, Dynaron 6200P, Dynaron 4630P, Dynaron 8601P, Dynaron 8630P, Dynaron ( Dynaron 8600P, Dynaron 8903P, Dynaron 6201B, Dynaron 1321P, Dynaron 1320P, Dynaron 2324P, Dynaron 9901P (the above are trade names, manufactured by JSR (stock)); Denka STR series (trade names, manufactured by Electrochemical Industry (stock)); Quintac 3520, Quintac 3433N, Quintac 3421, Quintac 3620, Quintac 3450, Quintac 3460 (the above are Trade name, manufactured by ZEON, Japan); TPE-SB series (the above are trade names, manufactured by Sumitomo Chemical Co., Ltd.); Rabalon series (trade name, manufactured by Mitsubishi Chemical Co., Ltd.); Saipu Septon 1001, Septon 8004, Septon 4033, Septon 2104, Septon 8007, Septon 2007, Septon ( Septon 2004, Septon 2063, Septon HG252, Septon 8076, Septon 2002, Septon 1020, Septon 8104, Septon 2005, Septon 2006, Septon 4055, Septon 4044, Septon 4077, Septon 4099, Septon 8006, Septon V9461, Septon V9475, Septon V9827, Hybrar 7311, Hybrar 7125, Hybrar Hybrar 5127, Hybrar 5125 (the above are trade names, manufactured by Kuraray); Sumiflex (trade names, manufactured by Sumitomo Bakelite (stock)) ; Leostomer, Actymer (the above are trade names, manufactured by Riken Ethylene Industry), etc.

Next, the specific preferable range in "Elastomer X" will be described. Elastomer X is an elastomer containing styrene-derived repeating units in a proportion of 50% by mass or more and 95% by mass or less in all repeating units. The content of styrene-derived repeating units is preferably more than 50% by mass and 95% by mass or less, more preferably more than 50% by mass and 90% by mass or less, still more preferably more than 50% by mass and 80% by mass or less, particularly preferably 55% to 75% by mass, and particularly preferably 56% by mass to 70% by mass. The hardness of the elastomer X is preferably 83 or more, more preferably 85 or more, and still more preferably 90 or more. The upper limit is not specifically defined, but is 99 or less, for example. In addition, the hardness is a value measured by the A-type hardness tester based on the method of JIS (Japanese Industrial Standard) K6253.

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

In the present invention, elastomers other than Elastomer X and Elastomer Y may also be blended. As other elastomers, polyester elastomers, polyolefin elastomers, polyurethane elastomers, polyamide elastomers, polyacrylic elastomers, silicone elastomers, and polyamides can be used. Imine-based elastomers, rubber-modified epoxy resins, etc.

The total amount of elastomer X, elastomer Y, and other elastomers in the temporary adhesive agent of the present invention is preferably 50.00% by mass to 99.99% by mass, and more preferably 70.00% by mass, relative to the mass of the temporary adhesive other than the solvent. %-99.99% by mass, particularly preferably 88.00% by mass to 99.99% by mass. If the content of the elastomer is in the above range, the adhesiveness and releasability are more excellent. In addition, the elastomer X, the elastomer Y, and other elastomers in the temporary adhesive of the present invention may be a combination of multiple types, respectively.

In the content of the elastomer contained in the temporary adhesive of the present invention, the total amount of elastomer X and elastomer Y is preferably 90% by mass or more of the whole, more preferably 95% by mass or more, and particularly preferably 98% by mass or more. In the case of compounding elastomer Y, the better quality of said elastomer X and said elastomer Y is elastomer X: elastomer Y=5:95-95:5, more preferably 20:80-90: 10. Especially preferred is 40:60～85:15. If it is the said range, the warpage is suppressed more effectively, and peelability will be acquired.

<<Antioxidant>> From the viewpoint of preventing demolition or gelation of the elastomer due to oxidation during heating, the temporary adhesive of the present invention may contain an antioxidant. As the antioxidant, phenol-based antioxidants, sulfur-based antioxidants, phosphorus-based antioxidants, quinone-based antioxidants, amine-based antioxidants, and the like can be used. Examples of phenolic antioxidants include p-methoxyphenol, 2,6-di-tert-butyl-4-methylphenol, and "Irganox" manufactured by BASF (Co., Ltd.) 1010", "Irganox 1330", "Irganox 3114", "Irganox 1035", "Sumilizer" manufactured by Sumitomo Chemical Co., Ltd. ) MDP-S", "Sumilizer GA-80", etc. Examples of sulfur-based antioxidants include: Distearyl 3,3'-thiodipropionate, "Sumilizer TPM" manufactured by Sumitomo Chemical Co., Ltd., and "Sumilizer ( Sumilizer TPS", "Sumilizer TP-D" and so on. Examples of phosphorus-based antioxidants include tris(2,4-di-tert-butylphenyl) phosphite, bis(2,4-di-tert-butylphenyl) pentaerythritol diphosphite, Poly(dipropylene glycol) phenyl phosphite, diphenyl isodecyl phosphite, 2-ethylhexyl diphenyl phosphite, triphenyl phosphite, manufactured by BASF (Stock) "Irgafos (Irgafos) 168", "Irgafos (Irgafos) 38" and so on. As quinone antioxidants, p-benzoquinone, 2-tert-butyl-1,4-benzoquinone, etc. are mentioned, for example. As the amine antioxidant, for example, dimethylaniline, phenothiazine, and the like can be cited. Among the antioxidants, preferably Irganox 1010, Irganox 1330, 3,3'-thiodipropionate distearyl ester, Sumilizer TP-D, more preferably Irganox 1010, Irganox 1330, and particularly preferably Irganox 1010. In addition, among the antioxidants, preferred are phenol-based antioxidants and sulfur-based antioxidants or phosphorus-based antioxidants, and particularly preferred are phenol-based antioxidants and sulfur-based antioxidants. In particular, when a polystyrene-based elastomer is used as the elastomer, a phenol-based antioxidant and a sulfur-based antioxidant are preferred. With such a combination, it can be expected that the deterioration of the elastomer due to the oxidation reaction can be suppressed efficiently. In the case of phenol-based antioxidants and sulfur-based antioxidants, the quality of phenol-based antioxidants and sulfur-based antioxidants is better. Phenolic antioxidants: sulfur-based antioxidants=95:5～5:95, better From 25:75 to 75:25. The combination of antioxidants is preferably Irganox 1010 and Sumilizer TP-D, Irganox 1330 and Sumilizer TP-D and Sumilizer TP-D. Sumilizer GA-80 and Sumilizer TP-D, more preferably Irganox 1010 and Sumilizer TP-D, Irganox ) 1330 and Sumilizer TP-D, particularly good ones are Irganox 1010 and Sumilizer TP-D.

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

When the temporary adhesive has an antioxidant, the content of the antioxidant is preferably 0.001% by mass to 20.0% by mass, and more preferably 0.005% by mass to 10.0% by mass relative to the total solid content of the temporary adhesive. There may be only one type of antioxidant, or two or more types. When there are two or more kinds of antioxidants, it is preferable that the total of them is in the above-mentioned range.

<<Solvent>> The temporary adhesive of the present invention preferably contains a solvent. In particular, when forming an adhesive layer by applying the temporary adhesive of the present invention, it is preferable to prepare a solvent. A known solvent can be used without limitation, and an organic solvent is preferred. Examples of organic solvents include ethyl acetate, n-butyl acetate, isobutyl acetate, pentyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, Ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, alkyl oxyacetate (for example: methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate (for example, methoxyacetic acid) Methyl ester, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.), 3-oxypropionic acid alkyl esters (for example: 3-oxy Methyl propionate, ethyl 3-oxypropionate, etc. (such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-ethyl Oxypropionate, etc.)), 2-oxypropionic acid alkyl esters (for example: 2-oxypropionic acid methyl ester, 2-oxypropionic acid ethyl ester, 2-oxypropionic acid propyl ester, etc. (For example, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate Ester)), methyl 2-oxy-2-methylpropionate and ethyl 2-oxy-2-methylpropionate (such as methyl 2-methoxy-2-methylpropionate, 2- Ethoxy-2-methyl propionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetylacetate, ethyl acetylacetate, methyl 2-oxobutyrate , 2-oxobutyrate ethyl ester, 1-methoxy-2-propyl acetate and other esters; Diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, Methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether Acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate and other ethers; methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone, N-methyl-2-pyrrole Ketones such as pyridone and γ-butyrolactone; toluene, xylene, anisole, mesitylene, ethylbenzene, propylbenzene, cumene, n-butylbenzene, sec-butylbenzene, isobutyl Benzene, tertiary butylbenzene, pentylbenzene, isopentylbenzene, (2,2-dimethylpropyl)benzene, 1-phenylhexane, 1-phenylheptane, 1-phenyloctane , 1-phenylnonane, 1-phenyldecane, cyclopropylbenzene, cyclohexylbenzene, 2-ethyltoluene, 1,2-diethylbenzene, o-isopropyl toluene, indan, 1 , 2,3,4-Tetrahydronaphthalene, 3-ethyltoluene, m-isopropyl toluene, 1,3-diisopropylbenzene, 4-ethyltoluene, 1,4-diethylbenzene, p- -Cumene, 1,4-Diisopropylbenzene, 4-tert-butyltoluene, 1,4-di-tert-butylbenzene, 1,3-diethylbenzene, 1,2,3 -Trimethylbenzene, 1,2,4-trimethylbenzene, 4-tert-butyl-o-xylene, 1,2,4-triethylbenzene, 1,3,5-triethylbenzene, 1,3,5-Triisopropylbenzene, 5-tert-butyl-m-xylene, 3,5-di-tert-butyltoluene, 1,2,3,5-tetramethylbenzene, 1, Aromatic hydrocarbons such as 2,4,5-tetramethylbenzene, pentamethylbenzene; limonene, p-menthane, nonane, Hydrocarbons such as decane, dodecane, decalin, etc. Among these, mesitylene, tertiary butylbenzene, 1,2,4-trimethylbenzene, p-menthane, γ-butyrolactone, anisole, and methyl 3-ethoxypropionate are preferred. , Ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone , Cyclohexanone, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether, and propylene glycol methyl ether acetate, more preferably mesitylene.

From the viewpoint of improving coating surface properties, etc., these solvents are also preferably in a form in which two or more kinds of them are mixed. In this case, it is particularly preferable to be a mixed solution containing selected from mesitylene, tertiary butylbenzene, 1,2,4-trimethylbenzene, p-menthane, γ-butyrolactone, and benzyl Ether, 3-ethoxy methyl propionate, 3-ethoxy ethyl propionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, 3-methyl Two or more of methyl oxypropionate, 2-heptanone, cyclohexanone, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether, and propylene glycol methyl ether acetate .

When the temporary adhesive contains a solvent, from the viewpoint of coatability, the content of the solvent of the temporary adhesive is preferably such that the total solid content concentration of the temporary adhesive becomes 5 mass% to 80 mass %, and more It is preferably 10% by mass to 50% by mass, and particularly preferably 15% by mass to 40% by mass. The solvent may be only one type or two or more types. When there are two or more kinds of solvents, it is preferable that the total amount is the above-mentioned range. In addition, as described later, when the temporary adhesive of the present invention is used in the adhesive layer of an adhesive film or an adhesive support, the solvent content is preferably 1% by mass or less, more preferably 0.1% by mass or less , It is especially good to not contain.

<<radical polymerizable compound>> The temporary adhesive of the present invention also preferably contains a radical polymerizable compound. By using a temporary adhesive containing a radically polymerizable compound, it is easy to suppress flow deformation of the adhesive layer during heating. Therefore, for example, when heat-treating the laminated body after polishing the base material, the flow deformation of the adhesive layer during heating can be suppressed, and the occurrence of warpage can be effectively suppressed. In addition, an adhesive layer having hardness can be formed. Therefore, even if pressure is applied locally when polishing the base material, the adhesive layer is not easily deformed, and the flat abrasiveness is excellent.

In the present invention, the radically polymerizable compound is a compound having a radically polymerizable group, and a known radically polymerizable compound that can be polymerized by radicals can be used. Such compounds are widely known in the art, and they can be used in the present invention without particular limitation. These may be, for example, monomers, prepolymers, oligomers, mixtures of these, and any of these multimers. As a radically polymerizable compound, the description of paragraph 0099 to paragraph 0180 of JP-A-2015-087611 can be referred to, and these contents are incorporated in this specification.

In addition, as the radically polymerizable compound, preferred are Japanese Patent Publication No. 48-41708, Japanese Patent Publication No. 51-37193, Japanese Patent Publication No. 2-32293, and Japanese Patent Publication No. 2 The urethane acrylates described in -16765, or Japanese Patent Publication No. 58-49860, Japanese Patent Publication No. 56-17654, Japanese Patent Publication No. 62-39417, Japanese Patent Publication No. 62 Urethane compounds having an ethylene oxide-based skeleton described in Bulletin -39418. Furthermore, it is also possible to use the amine structure or thioether structure described in Japanese Patent Laid-Open No. 63-277653, Japanese Patent Laid-Open No. 63-260909, and Japanese Patent Laid-Open No. 1-105238. The addition polymerizable monomers are used as radical polymerizable compounds.

Commercial products of radical polymerizable compounds include: urethane oligomer UAS-10, UAB-140 (manufactured by Sanyo Kokusaku Pulp); NK ester M-40G, NK ester 4G, NK ester A-9300, NK ester M-9300, NK ester A-TMMT, NK ester A-DPH, NK ester A-BPE-4, UA-7200 (manufactured by Shin Nakamura Chemical Co.); DPHA-40H (Japan Chemical Pharmaceuticals Corporation); UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoeisha Chemical Co., Ltd.); Blemmer PME400 (Nippon Oil (Stock) Manufacturing) and so on.

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

[化2]

As specific examples of the radically polymerizable compound having the partial structure, for example, trimethylolpropane tri(meth)acrylate, isocyanurate ethylene oxide modified di(meth)acrylate, Isocyanuric acid ethylene oxide modification tri(meth)acrylate, triallyl isocyanurate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dimethylolpropane Tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tetramethylolmethane tetra(meth)acrylate, etc., can be particularly preferred in the present invention These radically polymerizable compounds are used.

In the temporary adhesive of the present invention, from the viewpoints of good adhesiveness, flat abrasiveness, releasability, and warpage suppression, compared to the mass of the temporary adhesive other than the solvent, when a radically polymerizable compound is added The content is preferably 1% by mass to 50% by mass, more preferably 1% by mass to 30% by mass, and still more preferably 5% by mass to 30% by mass. A radically polymerizable compound may be used individually by 1 type, and may mix and use 2 or more types. In addition, in the temporary adhesive of the present invention, the mass ratio of elastomer to radical polymerizable compound when the radical polymerizable compound is added is preferably elastomer: radical polymerizable compound=98:2-10:90, More preferably, it is 95:5 to 30:70, particularly preferably 90:10 to 50:50. If the mass ratio of the elastomer to the radical polymerizable compound is in the above range, an adhesive layer excellent in adhesiveness, flat abrasiveness, releasability, and warpage suppression can be formed.

<<Polymer compound>> In order to adjust coatability, adhesiveness, mold releasability, heat resistance, etc., the temporary adhesive of the present invention may optionally have a polymer compound other than the silicon-based liquid compound and elastomer. In addition, the coatability mentioned here refers to the uniformity of the film thickness after coating or the film formability after coating. In the present invention, any polymer compound can be used. The polymer compound is a compound that does not contain a polymerizable group. The weight average molecular weight of the polymer compound is preferably 10,000 to 1,000,000, more preferably 50,000 to 500,000, and still more preferably 100,000 to 300,000. Specific examples of polymer compounds include, for example, hydrocarbon resins, novolac resins, phenol resins, epoxy resins, melamine resins, urea resins, unsaturated polyester resins, alkyd resins, polyimide resins, and polychlorinated resins. Vinyl resin, polyvinyl acetate resin, Teflon (registered trademark), polyamide resin, polyacetal resin, polycarbonate resin, polyphenylene ether resin, polybutylene terephthalate resin, Polyethylene terephthalate resin, polyphenylene sulfide resin, polysulfide resin, polyether sulfide resin, polyarylene ester resin, polyether ether ketone resin, polyamide imide resin, etc. Among them, preferred are hydrocarbon resins, novolac resins, and polyimide resins, and more preferred are hydrocarbon resins. The polymer compound can also be used in combination of two or more types as required.

Any one can be used as the hydrocarbon resin. The hydrocarbon resin basically refers to a resin containing only carbon atoms and hydrogen atoms, and if the basic skeleton is a hydrocarbon resin, it may contain other atoms as a side chain. That is, in addition to hydrocarbon resins containing only carbon atoms and hydrogen atoms, such as acrylic resins, polyvinyl alcohol resins, polyvinyl acetal resins, and polyvinylpyrrolidone resins, functional groups other than hydrocarbon groups are directly bonded to The case of the main chain is also included in the hydrocarbon resin of the present invention. In this case, the content of the repeating unit formed by directly bonding the hydrocarbon group to the main chain is preferably 30 mol% or more with respect to all the repeating units of the resin. . Examples of hydrocarbon resins that meet the above conditions include terpene resins, terpene phenol resins, modified terpene resins, hydrogenated terpene resins, hydrogenated terpene phenol resins, rosin, rosin esters, hydrogenated rosin, Hydrogenated rosin ester, polymerized rosin, polymerized rosin ester, modified rosin, rosin modified phenol resin, alkylphenol resin, aliphatic petroleum resin, aromatic petroleum resin, hydrogenated petroleum resin, modified petroleum resin, alicyclic petroleum resin , Coumarone petroleum resin, indene petroleum resin, etc. Among them, the hydrocarbon resin is preferably terpene resin, rosin, petroleum resin, hydrogenated rosin, and polymerized rosin, and more preferably terpene resin and rosin.

From the viewpoint of improving coatability, mold releasability, and heat resistance, a polymer compound containing a non-three-dimensional crosslinked structure having a fluorine atom is preferred. The so-called non-three-dimensional cross-linked structure means that the compound does not contain a cross-linked structure, or the ratio of the cross-linked structure forming the three-dimensional cross-linked structure to all the cross-linked structures in the compound is 5% or less, preferably 1% or less. As the polymer compound having a non-three-dimensional crosslinked structure of fluorine atoms, a polymer containing one or two or more fluorine-containing monofunctional monomers can be preferably used. More specifically, at least one fluorine-containing resin selected from the following polymers can be cited: selected from tetrafluoroethylene, hexafluoropropylene, tetrafluoroethylene oxide, hexafluoropropylene oxide, and perfluoroalkylethylene A homopolymer of one or two or more of fluorine-containing monofunctional monomers or copolymers of these monomers among the fluorine-containing monofunctional monomers among the base ethers, chlorotrifluoroethylene, vinylidene fluoride, and (meth)acrylates containing perfluoroalkyl groups A copolymer of one or more of fluorine-containing monofunctional monomers and ethylene, and a copolymer of one or more of fluorine-containing monofunctional monomers and chlorotrifluoroethylene.

As a polymer compound having a non-three-dimensional crosslinked structure having a fluorine atom, a (meth)acrylic resin containing a perfluoroalkyl group which can be synthesized from a (meth)acrylate containing a perfluoroalkyl group is preferred. As the (meth)acrylate containing a perfluoroalkyl group, specifically, the compound represented by following formula (101) is preferable.

Formula (101) [Change 3]

In the general formula (101), R ¹⁰¹ , R ¹⁰² , and R ¹⁰³ each independently represent a hydrogen atom, an alkyl group, or a halogen atom. Y ¹⁰¹ represents a single bond or a divalent linking group selected from the group consisting of -CO-, -O-, -NH-, a divalent aliphatic group, a divalent aromatic group, and a combination of these. Rf is a fluorine atom or a monovalent organic group having at least one fluorine atom.

In the general formula (101), ^{examples of the alkyl groups represented by R 101} , R ¹⁰² , and R ¹⁰³ are preferably alkyl groups having 1 to 8 carbon atoms, for example, methyl, ethyl, propyl, octyl, Isopropyl, tert-butyl, isopentyl, 2-ethylhexyl, 2-methylhexyl, cyclopentyl, etc. Examples of the aryl group are preferably aryl groups having 6 to 12 carbons, and examples thereof include phenyl, 1-naphthyl, 2-naphthyl, and the like. Among them, R ¹⁰¹ to R ^{103 are} preferably a hydrogen atom or a methyl group.

Y ¹⁰¹ represents a single bond, or a divalent linking group selected from the group consisting of -CO-, -O-, -NH-, a divalent aliphatic group, a divalent aromatic group, and a combination of these, regarding The divalent aliphatic group is preferably a chain structure compared to a cyclic structure, and furthermore, a linear structure is preferable compared to a branched chain structure. The number of hydrogen atoms of the divalent aliphatic group is preferably 1-20, more preferably 1-15, still more preferably 1-12, particularly preferably 1-10, still more preferably 1-8, particularly preferably 1. ~4. Examples of the divalent aromatic group include phenylene, substituted phenylene, naphthylene, and substituted naphthylene, and phenylene is preferred. As Y ¹⁰¹ , an aliphatic group having a divalent linear structure is preferable.

The monovalent organic group having a fluorine atom represented by Rf is not particularly limited, but is preferably a fluorinated alkyl group having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and particularly preferably 1 to 15 carbon atoms的Fluorinated alkyl group. The fluorine-containing alkyl group can be straight chain {e.g. -CF ₂ CF ₃ , -CH ₂ (CF ₂ ) ₄ H, -CH ₂ (CF ₂ ) ₈ CF ₃ , -CH ₂ CH ₂ (CF ₂ ) ₄ H, etc. }, can also have a branched structure {e.g. -CH(CF ₃ ) ₂ , -CH ₂ CF(CF ₃ ) ₂ , -CH(CH ₃ )CF ₂ CF ₃ , -CH(CH ₃ )(CF ₂ ) ₅ CF ₂ H etc.}, in addition, it may have an alicyclic structure (preferably a 5-membered ring or a 6-membered ring, such as perfluorocyclohexyl, perfluorocyclopentyl or alkyl substituted by these, etc.), and May have ether bonds (for example -CH ₂ OCH ₂ CF ₂ CF ₃ , -CH ₂ CH ₂ OCH ₂ C ₄ F ₈ H, -CH ₂ CH ₂ OCH ₂ CH ₂ C ₈ F ₁₇ , -CH ₂ CF ₂ OCF ₂ CF ₂ OCF ₂ CF ₂ H, etc.). In addition, it may be a perfluoroalkyl group.

The (meth)acrylic resin containing a perfluoroalkyl group specifically has a repeating unit represented by the following formula (102). Formula (102) [化4]

In the general formula ^{(102), R 101, R} 102, R 103, Y 101, Rf each state the general formula R ^{101 (101) is, R 102, R 103, Y} 101, Rf is the same meaning, preferably The same is true.

From the standpoint of releasability, in addition to the (meth)acrylate containing a perfluoroalkyl group, the (meth)acrylic resin containing a perfluoroalkyl group can optionally select a copolymer component. Examples of radical polymerizable compounds that can form copolymerization components include acrylates, methacrylates, N,N-2 substituted acrylamides, and N,N-2 substituted methacrylamides. , Styrene, acrylonitrile, methacrylonitrile and other radical polymerizable compounds.

More specifically, for example, acrylic acid esters (such as methyl acrylate, ethyl acrylate, propyl acrylate, and butyl acrylate) such as alkyl acrylate (preferably one having 1 to 20 carbon atoms in the alkyl group) are mentioned. , Amyl acrylate, ethylhexyl acrylate, octyl acrylate, third octyl acrylate, chloroethyl acrylate, 2,2-dimethylhydroxypropyl acrylate, 5-hydroxypentyl acrylate, trimethylol Propane monoacrylate, pentaerythritol monoacrylate, glycidyl acrylate, benzyl acrylate, methoxybenzyl acrylate, furfuryl acrylate, tetrahydrofurfuryl acrylate, etc.); aryl acrylate (such as acrylic acid Phenyl esters, etc.); methacrylates such as alkyl methacrylates (preferably those with 1 to 20 carbon atoms in the alkyl group) (for example, methyl methacrylate, ethyl methacrylate, methyl Propyl acrylate, isopropyl methacrylate, pentyl 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, glycidyl methacrylate, furfuryl methacrylate, tetrahydrofurfuryl methacrylate, etc.); aryl methacrylate (such as phenyl methacrylate, methacrylic acid) Cresyl ester, naphthyl methacrylate, etc.); styrene, alkyl styrene and other styrenes (such as methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, diethyl styrene, etc.) Styrene, isopropyl styrene, butyl styrene, hexyl styrene, cyclohexyl styrene, decyl phenethyl, benzyl styrene, chloromethyl styrene, trifluoromethyl styrene, ethoxy Methyl styrene, acetoxy methyl styrene, etc.), alkoxy styrene (such as methoxy styrene, 4-methoxy-3-methyl styrene, dimethoxy styrene, etc.) ), halogen styrene (such as chlorostyrene, dichlorostyrene, trichlorostyrene, tetrachlorostyrene, pentachlorostyrene, bromostyrene, dibromostyrene, iodostyrene, fluorostyrene, trifluorostyrene Styrene, 2-bromo-4-trifluoromethylstyrene, 4-fluoro-3-trifluoromethylstyrene, etc.); Acrylonitrile; Methacrylonitrile; Free radical polymerizable compounds containing acrylic acid and carboxylic acid (Acrylic acid, methacrylic acid, itaconic acid, crotonic acid, methacrylic acid, maleic acid, p-carboxystyrene, and metal salts and ammonium salt compounds of these acid groups, etc.), from the standpoint of releasability In particular, (meth)acrylates having a hydrocarbon group having 1 to 24 carbon atoms are particularly preferred, and examples include methyl, butyl, 2-ethylhexyl, lauryl, and stearyl (meth)acrylates. Esters, glycidyl esters, etc. are preferably (meth)acrylates of higher alcohols such as 2-ethylhexyl, lauryl, and stearyl, and particularly preferably acrylates.

The polymer compound having a non-three-dimensional crosslinked structure of fluorine atoms can also be commercially available. Examples include: Teflon (registered trademark) (Du Pont), Tefzel (Du Pont), Fluon (Asahi Glass Company), Hey Heira (SolvaySolexis), Heiler (SolvaySolexis), Lumiflon (Asahi Glass Company), Afras (Aflas) (Asahi Glass Company), Cytop (Asahi Glass Company), Cefralsoft (Central Glass Company), Cefralcoat (Central Glass) Company), Dyneon (3M Company) and other fluororesins; Viton (Du Pont), Kalrez (Du Pont), Hifuler ( SIFEL (Shin-Etsu Chemical Industry Co., Ltd.) and other brand names of fluoroelastomers; Krytox (Du Pont), Fomblin (Daitoku Tech), Daim Demnum (Daikin Industrial Company) and various fluorine oils represented by perfluoropolyether oil; or Daifree FB series (Daikin Industrial Company), Megafa ( Megafac) series (DIC company) and other brand names containing fluorine-containing mold release agents.

The weight average molecular weight of the non-three-dimensional crosslinked polymer compound having a fluorine atom in terms of polystyrene obtained by the gel permeation chromatography (GPC) method is preferably 100,000 to 2,000, more preferably 50,000 to 2,000, most preferably It is 10000～2000.

When the temporary adhesive of the present invention contains the silicon-based liquid compound and a polymer compound other than the elastomer, its content is preferably 0.01% by mass to 60% by mass relative to the total solid content of the temporary adhesive. It is more preferably 0.05% by mass to 50% by mass, and still more preferably 0.1% by mass to 30% by mass.

<<Surfactant>> The temporary adhesive of the present invention may contain a surfactant. The surfactants described here do not contain silicon-based liquid compounds. As the surfactant, any of anionic, cationic, nonionic, or amphoteric can be used, and a preferred surfactant is a nonionic surfactant. Preferred examples of nonionic surfactants include: polyoxyethylene higher alkyl ethers, polyoxyethylene higher alkyl phenyl ethers, higher fatty acid diesters of polyoxyethylene glycol, and fluorine-based interface Active agent. As a specific example of the surfactant, the description of paragraph 0173 to paragraph 0177 of JP-A-2015-065401 can be referred to, and these contents are incorporated into this specification. From the viewpoint of coatability, relative to the total solid content of the temporary adhesive, the content of the surfactant in the temporary adhesive is preferably 0.001% by mass to 5% by mass, and more preferably 0.005% by mass to 1% by mass %, particularly preferably 0.01% by mass to 0.5% by mass. The surfactant may be only one type or two or more types. When there are two or more surfactants, it is preferable that the sum total is the said range.

<<Fluorine-based liquid compound>> From the viewpoint of improving coatability or mold releasability, the temporary adhesive of the present invention also preferably contains a fluorine-based liquid compound. Here, the liquid compound refers to a compound having fluidity at 25°C, for example, a compound having a viscosity of 1 mPa·s to 100,000 mPa·s at 25°C. The viscosity at 25°C of the fluorine-based liquid compound is, for example, more preferably 10 mPa·s to 20,000 mPa·s, and particularly preferably 100 mPa·s to 15,000 mPa·s. If the viscosity of the fluorine-based liquid compound is in the above range, the fluorine-based liquid compound tends to be concentrated on the surface layer of the adhesive layer.

As the fluorine-based liquid compound, compounds in any form of oligomers and polymers can also be preferably used. In addition, it may be a mixture of oligomer and polymer. The mixture may further contain monomers. In addition, the fluorine-based liquid compound may be a monomer. From the viewpoint of heat resistance and the like, the fluorine-based liquid compound is preferably an oligomer, a polymer, and a mixture of these. Examples of oligomers and polymers include radical polymers, cationic polymers, and anionic polymers, and any of them can be preferably used. Particularly preferred is a vinyl-based polymer. The weight average molecular weight of the fluorine-based liquid compound is preferably 500 to 100,000, more preferably 1,000 to 50,000, and still more preferably 2,000 to 20,000.

The fluorine-based liquid compound is preferably a compound that does not change when the substrate for temporary bonding is processed. For example, it is preferably a compound that can exist in a liquid state even after heating at 250° C. or higher or processing the substrate with various chemical liquids. As a specific example, it is preferable to heat from a state of 25°C to 250°C at a temperature increase of 10°C/min, and then cool to 25°C. The viscosity at 25°C is 1 mPa·s to 100,000 mPa·s. It is more preferably 10 mPa·s to 20,000 mPa·s, and particularly preferably 100 mPa·s to 15,000 mPa·s. As the fluorine-based liquid compound having such characteristics, a non-thermosetting compound having no reactive group is preferred. The reactive group mentioned here refers to the entire group that reacts by heating at 250°C, and includes a polymerizable group, a hydrolyzable group, and the like. Specifically, for example, a (meth)acrylic group, an epoxy group, an isocyanate group, etc. may be mentioned. In addition, the 10% thermal mass reduction temperature of the fluorine-based liquid compound raised from 25°C at 20°C/min is preferably 250°C or higher, more preferably 280°C or higher. In addition, the upper limit is not particularly limited. For example, it is preferably 1000°C or lower, and more preferably 800°C or lower. According to this aspect, it is easy to form an adhesive layer excellent in heat resistance. In addition, the thermal mass reduction temperature refers to a value measured by a thermogravimetry device (TGA) under a nitrogen stream under the above-mentioned temperature increase condition.

The fluorine-based liquid compound preferably contains a lipophilic group. Examples of the lipophilic group include linear or branched alkyl groups, cycloalkyl groups, aromatic groups, and the like.

The number of carbon atoms in the alkyl group is preferably 2-30, more preferably 4-30, still more preferably 6-30, and particularly preferably 12-30. Specific examples of the alkyl group include, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tetradecyl, Octadecyl, isopropyl, isobutyl, second butyl, tertiary butyl, 1-ethylpentyl, 2-ethylhexyl. The alkyl group may have a substituent. As a substituent, a halogen atom, an alkoxy group, an aromatic group, etc. are mentioned. As a halogen atom, a chlorine atom, a fluorine atom, a bromine atom, an iodine atom, etc. are mentioned, A fluorine atom is preferable. The carbon number of the alkoxy group is preferably 1-30, more preferably 1-20, and still more preferably 1-10. The alkoxy group is preferably a linear alkoxy group or a branched alkoxy group. The aromatic group may be monocyclic or polycyclic. The carbon number of the aromatic group is preferably 6-20, more preferably 6-14, most preferably 6-10.

Cycloalkyl groups may be monocyclic or polycyclic. The carbon number of the cycloalkyl group is preferably 3-30, more preferably 4-30, still more preferably 6-30, most preferably 6-20. Examples of monocyclic cycloalkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl. As the polycyclic cycloalkyl group, for example, adamantyl group, norbornyl group, bornyl group, camphenyl group, decahydronaphthyl group, tricyclodecyl group, tetracyclodecyl group, camphenyl group, two Cyclohexyl and pinenyl. Cycloalkyl groups may have such substituents.

環、聯伸三苯環、茀環、聯苯環、吡咯環、呋喃環、噻吩環、咪唑環、噁唑環、噻唑環、吡啶環、吡嗪環、嘧啶環、噠嗪環、吲哚嗪環、吲哚環、苯并呋喃環、苯并噻吩環、異苯并呋喃環、喹嗪環、喹啉環、酞嗪環、萘啶環、喹噁啉環、喹唑啉環、異喹啉環、咔唑環、啡啶環、吖啶環、啡啉環、噻蒽環、苯并哌喃環、氧雜蒽環、啡噁噻環、啡噻嗪環及啡嗪環。 芳香族基可具有所述取代基。The aromatic group may be monocyclic or polycyclic. The carbon number of the aromatic group is preferably 6-20, more preferably 6-14, most preferably 6-10. The aromatic group preferably does not contain heteroatoms (for example, nitrogen atoms, oxygen atoms, sulfur atoms, etc.) in the elements constituting the ring. Specific examples of aromatic groups include benzene ring, naphthalene ring, pentylene ring, indene ring, azulene ring, heptene ring, benzobiindene ring, perylene ring, fused pentabenzene ring, acenaphthene ring, Phenanthrene ring, anthracene ring, fused tetraphenyl ring,

Ring, biphenyl ring, pyrrole ring, biphenyl ring, pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, indoleazine Ring, indole ring, benzofuran ring, benzothiophene ring, isobenzofuran ring, quinazine ring, quinoline ring, phthalazine ring, naphthyridine ring, quinoxaline ring, quinazoline ring, isoquine The phenanthrene ring, the carbazole ring, the phenanthridine ring, the acridine ring, the phenanthroline ring, the thianthrone ring, the benzopyran ring, the xanthene ring, the phenoxathi ring, the phenanthrazine ring, and the phenanthrazine ring. The aromatic group may have such a substituent.

The fluorine-based liquid compound may be a compound containing only one kind of lipophilic group, or may contain two or more kinds. In addition, the lipophilic group may contain a fluorine atom. That is, the fluorine-based liquid compound in the present invention may be a compound in which only the lipophilic group contains a fluorine atom. In addition, it may also be a compound containing a group having a fluorine element (also referred to as a fluorine group) in addition to the lipophilic group. Preferably, it is a compound containing a lipophilic group and a fluorine group. When the fluorine-based liquid compound is a compound containing a lipophilic group and a fluorine group, the lipophilic group may or may not contain a fluorine atom. Preferably, the lipophilic group does not contain a fluorine atom. The fluorine-based liquid compound has one or more lipophilic groups in one molecule, preferably 2 to 100, and particularly preferably 6 to 80.

As the fluorine group, a known fluorine group can be used. For example, a fluorine-containing alkyl group, a fluorine-containing alkylene group, etc. can be mentioned. In addition, the fluorine group that functions as a lipophilic group is included in the lipophilic group. The carbon number of the fluoroalkyl group is preferably 1-30, more preferably 1-20, and still more preferably 1-15. The fluorine-containing alkyl group may be linear, branched, or cyclic. In addition, it may have an ether bond. In addition, the fluorine-containing alkyl group may be a perfluoroalkyl group in which all of the hydrogen atoms are substituted with fluorine atoms. The carbon number of the fluorine-containing alkylene group is preferably 2-30, more preferably 2-20, and still more preferably 2-15. The fluorine-containing alkylene group may be linear, branched, or cyclic. In addition, it may have an ether bond. In addition, the fluorine-containing alkylene group may be a perfluoroalkylene group in which all of the hydrogen atoms are substituted with fluorine atoms.

The fluorine-based liquid compound preferably has a fluorine atom content of 1% by mass to 90% by mass, more preferably 2% by mass to 80% by mass, and still more preferably 5% by mass to 70% by mass. If the fluorine content is in the above range, the releasability is excellent. The content of fluorine atoms is defined by "{(number of fluorine atoms in a molecule ´ mass of fluorine atoms)/mass of all atoms in a molecule}´ 100".

Commercial products can also be used for the fluorine-based liquid compound. For example, it may be better to cite: F-251, F-281, F-477, F-553, F-554, F-555, F-556, F-251, F-281, F-477, F-553, F-554, F-555, F-556, F-251, F-281, F-477, F-553, F-554, F-555, F-556, and F-557, F-558, F-559, F-560, F-561, F-563, F-565, F-567, F-568, F-571, R-40, R-41, R- 43. R-94; or 710F, 710FM, 710FS, 730FL, 730LM of the Ftergent series manufactured by NEOS.

In the case of using a fluorine-based liquid compound in the temporary adhesive of the present invention, its content is preferably 0.01% by mass to 10% by mass, more preferably 0.02% by mass relative to the mass of the temporary adhesive excluding the solvent ～5% by mass. The lower limit is preferably 0.03% by mass or more. The upper limit is preferably 1% by mass or less, and more preferably less than 0.5% by mass. When the content of the fluorine-based liquid compound is within the above range, the adhesiveness and releasability are excellent. The fluorine-based liquid compound may be used alone or in combination of two or more. When two or more types are used in combination, it is preferable that the total content is in the above-mentioned range.

＜＜Other components＞＞ In the range that does not impair the effect of the invention, the temporary adhesive of the invention can be blended with various additives as necessary, such as plasticizers, hardeners, catalysts, fillers, adhesion promoters, UV absorbers, anti-agglomeration agents, elastomers or other polymer compounds, etc. In the case of blending these additives, the blending amounts are preferably 3% by mass or less of the total solid content of the temporary adhesive, and more preferably 1% by mass or less. The lower limit at the time of blending is preferably 0.0001% by mass or more. In addition, the total blending amount of these additives is preferably 10% by mass or less of the total solid content of the temporary adhesive, and more preferably 3% by mass or less. The lower limit of the total blending amount when blending these components is preferably 0.0001% by mass or more.

The temporary adhesive of the present invention preferably does not contain impurities such as metals. The content of impurities contained in the adhesive is preferably 1 ppm or less, more preferably 1 ppb or less, still more preferably 100 ppt or less, particularly preferably 10 ppt or less, particularly preferably substantially free of (measurement device Below the detection limit). As a method of removing impurities such as metals from the temporary adhesive, for example, filtration using a filter can be cited. The pore size of the filter is preferably 10 nm or less, more preferably 5 nm or less, and still more preferably 3 nm or less. Regarding the material of the filter, a filter made of polytetrafluoroethylene, polyethylene, or nylon is preferable. The filter can be cleaned in advance with an organic solvent. In the filter filtration step, multiple filters can be connected in series or in parallel for use. When multiple filters are used, filters with different pore sizes and/or materials can be used in combination. In addition, the adhesive may be filtered multiple times, and the step of multiple filtering may also be a cyclic filtering step. In addition, as a method of reducing impurities such as metals contained in the temporary adhesive, methods such as the following: selecting a raw material with a low metal content as the raw material constituting the temporary adhesive; filtering the raw material constituting the temporary adhesive; The use of polytetrafluoroethylene is equivalent to the formation of a lining in the device and the distillation is carried out under the condition of suppressing contamination as much as possible. The preferable conditions in the filter filtration of the raw material constituting the temporary adhesive are the same as the above-mentioned conditions. In addition to filter filtration, adsorption materials can be used to remove impurities, and filter filtration and adsorption materials can also be used in combination. As the adsorbent, well-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.

<Preparation of Temporary Adhesive> The temporary adhesive of the present invention can be prepared by mixing the above-mentioned components. The mixing of each component is usually performed in the range of 0°C to 100°C. Moreover, after mixing each component, it is preferable to filter with a filter, for example. Filtration can be carried out in multiple stages, or iteratively many times. In addition, the filtered liquid can also be refiltered. As a filter, if it is a filter which has been used for filtration purposes etc., it can use without a restriction|limiting in particular. Examples include the use of fluororesins such as polytetrafluoroethylene (PTFE), polyamide resins such as nylon-6, nylon-6, and 6, and polyolefin resins such as polyethylene and polypropylene (Polypropylene, PP) (including high Density, ultra-high molecular weight polyolefin resin) and other raw materials filters. Among these raw materials, polypropylene (including high-density polypropylene) and nylon are preferred. The pore diameter of the filter is suitably about 0.003 μm to 5.0 μm, for example. By setting it in this range, filter clogging can be suppressed, and fine foreign substances such as impurities and aggregates contained in the composition can be reliably removed. When using filters, different filters can be combined. At this time, the filtration by the first filter may be performed only once, or may be performed more than twice. When performing filtration two or more times in combination with different filters, it is preferable that the pore size after the second filtration is the same as the pore size of the first filtration or smaller than the pore size of the first filtration. In addition, it is also possible to combine first filters with different pore diameters within the above range. The pore size here can refer to the nominal value of the filter manufacturer. As commercially available filters, for example, available from Japan PALL Co., Ltd., Advantec Toyo Co., Ltd., Japan Entegris Co., Ltd. (formerly Japan Micori ( Choose from various filters provided by Mykrolis Co., Ltd. or Kitz Microfilter Co., Ltd. etc.

<Use of Temporary Adhesive> The temporary adhesive of the present invention can form an adhesive layer excellent in adhesiveness and releasability. Therefore, when mechanical or chemical processing is performed on the element wafer, for example, the element wafer and the support can be temporarily bonded stably, and the temporary bonding of the element wafer can be easily released. The temporary adhesive of the present invention can be preferably used as a temporary adhesive for semiconductor device manufacturing.

<Adhesive Film> Next, the adhesive film of the present invention will be described. The adhesive film of the present invention has an adhesive layer containing the temporary adhesive of the present invention. In the adhesive film of the present invention, the silicon-based liquid compound is eccentrically present on the surface layer of the adhesive layer. Therefore, the peelability is excellent. In addition, the adhesive layer contains an elastomer, so it can follow the fine irregularities of the support or the base material, and use a moderate anchoring effect to obtain excellent adhesion. Therefore, it can have both adhesiveness and peelability. In the adhesive layer of the adhesive film of the present invention, it is preferable that the concentration of the silicon-based liquid compound is in the range of 5% of the thickness of the adhesive layer from any surface of the adhesive layer, and more than 5% in the thickness direction. And the area of the range of 50% or less is different. The concentration of the silicon-based liquid compound in the subsequent layer can be measured, for example, by the following method: the method of X-ray photoelectron spectroscopy (Electron Spectroscopy for Chemical Analysis, ESCA) measurement while etching; or the bevel cutting and flight time Type of secondary ion mass analysis (Time of Flight-Secondary Ion Mass Spectroscopy, TOF-SIMS) determination method.

The solvent content of the adhesive film of the present invention is preferably 1% by mass or less, more preferably 0.1% by mass or less, and particularly preferably not containing. Furthermore, the solvent content of the adhesive film can be measured by gas chromatography.

In the adhesive film of the present invention, the average thickness of the adhesive layer is not particularly limited. For example, it is preferably 0.1 μm to 500 μm, more preferably 0.1 μm to 200 μm, still more preferably 10 μm to 200 μm, and particularly preferably 50 μm～200 μm. If the average thickness of the adhesive layer is in the above range, it is easy to form an adhesive film excellent in flatness. In the present invention, the average thickness of the adhesive layer is defined as the average value of each point obtained by measuring 5 points by ellipsometry.

The adhesive film of the present invention may be a single adhesive layer, or may have other layers on one or both sides of the adhesive layer. As the other layer, a release layer can be exemplified. The average thickness of the release layer is preferably 0.001 μm to 1 μm, more preferably 0.01 μm to 0.5 μm. If it is the said range, the adhesive film has moderate adhesive force, the adhesiveness with a base material or a support body is good, and the adhesive film can be peeled easily from a base material or a support body. In addition, in the present invention, the average thickness of the release layer is defined as the average value per point measured by the ellipsometry at 5 points. The release layer preferably contains a compound containing fluorine atoms. For the details of the release layer, reference can be made to the description of paragraph 0068 to paragraph 0145 of JP 2014-066385 A, and these contents are incorporated into this specification. Moreover, the adhesive film of this invention may be set as the structure which does not contain a mold release layer. The reason is that the adhesive layer itself containing the temporary adhesive agent of the present invention has peelability.

The adhesive film of the present invention can also be made into an "adhesive film with a release film" by bonding the release film on one or both sides of the adhesive layer. According to this aspect, it is possible to prevent the long adhesive film from being rolled up. When it is taken into a roll shape, scratches are generated on the surface of the adhesive layer, and sticking problems occur during storage. The release film can be peeled off during use. For example, in the case of bonding the release film on both sides, peel off the one-sided release film, laminate the adhesive surface on a substrate or support, etc., and then peel off the remaining release film, This can keep the sheet surface as clean as possible.

<The manufacturing method of an adhesive film> The adhesive film of this invention can be manufactured by a conventionally well-known method. For example, it can be produced by a melt film forming method, a solution film forming method, or the like. The melt film forming method is to heat and melt the raw material composition to achieve fluidity, use an extrusion molding device or an injection molding device to form the solution into a sheet, and then cool it to obtain a film (sheet) method. In the extrusion molding method, a roll-shaped long film can be obtained. In the injection molding method, it is difficult to obtain a long film, but a high film thickness accuracy is obtained. Other additives can also be added by mixing, melting, and stirring. The release film can be attached to one or both sides of the film to make an "adhesive film with a release film". The solution film forming method is a method of dissolving the raw material composition in a solvent to achieve fluidity, applying the solution to a support such as a membrane, drum or belt, and forming a sheet, and drying to obtain a film (sheet) . Examples of coating include: a method of applying pressure by squeezing the solution from a slit-shaped opening, a method of applying the solution by transferring the solution with a gravure or anilox roll, and spraying the solution from a sprayer or a dispenser. A method of scanning coating, a method of storing the solution in a storage tank and passing it through a film, drum, or belt, and a method of applying dip coating, a method of coating while drawing the solution while squeezing the solution with a wire rod. Other additives can also be added by using a solution that is dissolved, mixed, and stirred. After the solution is applied to the support, it is dried to become a solidified sheet, and then the sheet is mechanically peeled off from the support, thereby obtaining a single film (sheet). As a treatment for imparting releasability to the support in advance for easy peeling, coating of a release layer, immersion treatment, gas treatment, electromagnetic wave irradiation treatment, plasma irradiation treatment, etc. can be performed. Or it is also possible to make the "adhesive film with a release film" in the state where the film is adhered to the film support without peeling off the film from the support and leaving it. By continuously performing these treatments, a roll-shaped long film can be obtained. In addition, a release film can be attached to both sides of the adhesive film to form a "sheet with a release film on both sides".

<Adhesive Support> Next, the adhesive support of the present invention will be described. The adhesive support of the present invention has a support and an adhesive layer containing the temporary adhesive of the present invention. The subsequent layer preferably includes the elastomer X and the elastomer Y as elastomers. The average thickness of the subsequent layer varies depending on the application, and for example, it is preferably 0.1 μm to 500 μm. The subsequent layer can be dried (baked) by applying the temporary adhesive of the present invention to the surface of the support by using a spin coating method, a spray method, a roll coating method, a flow coating method, a knife coating method, a dipping method, etc. ) And formed. Drying is performed, for example, at 60°C to 150°C for 10 seconds to 2 minutes. The average thickness of the adhesive layer in this case is not particularly limited. For example, it is preferably 1 μm to 100 μm, and more preferably 1 μm to 10 μm. In addition, the adhesive layer may be formed by laminating the adhesive film of the present invention on a support. The adhesive film is used to form the adhesive layer, and by this, it is also possible to form the adhesive layer using materials such as elastomers that have poor solubility in solvents. Therefore, it is easy to form an adhesive layer excellent in heat resistance or chemical resistance. In addition, an adhesive layer having a thick film of 10 μm or more can be formed flatly without thickness unevenness. The average thickness of the adhesive layer in this case is not particularly limited. For example, it is preferably 0.1 μm to 200 μm, more preferably 10 μm to 200 μm, and particularly preferably 50 μm to 200 μm. In order to use the adhesive film to form the adhesive layer on the support, for example, the adhesive film is placed on a vacuum laminator, the adhesive film is placed on the support by this device, and the adhesive film is brought into contact with the support under vacuum. A method of fixing (laminating) the adhesive film on the support by pressure bonding with a roller or the like. In addition, the adhesive film (adhesive layer) fixed to the support can be cut into a desired shape such as a circular shape, for example.

In the adhesive support of the present invention, the adhesive layer is preferably such that the concentration of the silicon-based liquid compound is greater than that of the self-supporting body. The surface on the opposite side is high in an area exceeding 5% and 50% or less in the thickness direction of the adhesive layer. According to this aspect, when the adhesive support is temporarily attached to a base material such as a device wafer and then peeled from the device wafer, the peelability is improved. Furthermore, the adhesive layer can be easily removed from the surface of the substrate or the device wafer by a method such as mechanical peeling. The concentration of the silicon-based liquid compound is preferably greater than 5% in the thickness direction of the adhesive layer from the surface on the opposite side of the support than in the thickness direction of the adhesive layer from the surface on the opposite side of the support. The area in the range of% and 50% or less is 10% by mass or more, and more preferably 30% by mass or more.

In the adhesive support of the present invention, the support (also referred to as carrier support) is not particularly limited, and examples thereof include silicon substrates, glass substrates, metal substrates, and compound semiconductor substrates. Among them, a silicon substrate is preferable in view of the fact that it is difficult to contaminate a silicon substrate that is typically used as a substrate of a semiconductor device or that it can be used in an electrostatic chuck widely used in the manufacturing process of a semiconductor device. The thickness of the support is not particularly limited. For example, it is preferably 300 μm to 100 mm, and more preferably 300 μm to 10 mm. The support may have a release layer on its surface. That is, the support may be a support with a mold release layer having a mold release layer on the surface of a substrate such as a silicon substrate. The release layer is preferably a low surface energy layer containing fluorine atoms and/or silicon atoms, and preferably contains a material having fluorine atoms and/or silicon atoms. The fluorine content of the release layer is preferably 30% by mass to 80% by mass, more preferably 40% by mass to 76% by mass, and particularly preferably 60% by mass to 75% by mass. As the material of the release layer, the same material as the release layer that can be formed on the surface layer of the adhesive film can be used.

<Laminate> Next, the laminate of the present invention will be described. The laminate of the present invention has a support, an adhesive layer containing the temporary adhesive of the present invention, and a substrate. Hereinafter, a preferred embodiment of the laminate of the present invention will be described based on FIGS. 1 and 2. Of course, the embodiment of the laminate of the present invention is not limited to these embodiments. In addition, in FIG. 1 and FIG. 2, 1 indicates a substrate, 2 indicates a support, and 3, 3A, and 3B indicate adhesive layers, respectively.

In the first embodiment of the laminate of the present invention, as shown in FIG. 1, the adhesive layer 3 is located on the surface of the support 2 and the base material 1 is located on the surface of the adhesive layer 3 on the opposite side of the support. In this way, in terms of increasing the throughput of the laminate formation, it is preferable to have the adhesive layer 3 between the substrate and the support, and the adhesive layer 3 is in contact with the substrate and the support. That is, in the layered body, it is possible to exemplify an aspect in which the release layer is not included between the base material and the support, but only the adhesive layer. In the first embodiment, the peel strength A between the support and the adhesive layer containing the temporary adhesive of the present invention, and the peel strength B between the adhesive layer and the substrate containing the temporary adhesive of the present invention preferably satisfy the following formula (1) and formula (2). A＜B …Formula (1) B≦4 N/cm …Formula (2) With the peel strength A and peel strength B satisfying the relationship of the formula (1), when the support is peeled from the substrate, it can be self-supporting The interface between the body and the adhesive layer containing the temporary adhesive of the present invention is peeled off. Furthermore, since the peel strength B satisfies the relationship of the above-mentioned formula (2), the adhesive layer can be easily peeled from the surface of the base material in a film-like state. That is, the adhesive layer can be easily peeled off by mechanical peeling. The peel strength B is preferably 3 N/cm or less, more preferably 2 N/cm or less. In addition, the peeling strength in this invention is a value obtained by measuring the strength applied when pulling up in a 90 degree direction. The peel strength A represents the force applied when the substrate is fixed and the end of the support is pulled up in the 90° direction at a speed of 50 mm/min. The peel strength B represents the force applied when the substrate is fixed and the film-like adhesive layer is pulled up in the 90° direction at a speed of 50 mm/min.

Regarding the laminate of the present invention, when the support is peeled from the base material, it is preferable to peel the adhesive layer containing the temporary adhesive of the present invention from the interface between the base material and the adhesive layer, in the area of the peeling surface between the base material and the adhesive layer The residue of the silicon-based liquid compound adheres to 50% or more of the range, or the adhesive layer is peeled from the interface between the support and the adhesive layer, in the range of 50% or more of the area of the peeling surface between the support and the adhesive layer The residue of the silicon-based liquid compound adheres. In addition, it is preferable that the residue derived from the elastomer does not adhere to the range of 50% or more of the area of the peeling surface, and it is more preferable that it does not adhere to the range of 99% or more. The residue of the silicon-based liquid compound and the residue derived from the elastomer can be observed by visual inspection, optical microscope, scanning electron microscope, X-ray photoelectron spectroscopy, etc. In the present invention, it is particularly set by X-ray photoelectron spectroscopy. Spectroscopically measure the peeled surface. In addition, in this specification, "the residue of the silicon-based liquid compound" refers to the silicon-based liquid compound component of the adhesive layer, and the "residue from the elastomer" refers to the elastomer component of the adhesive layer.

The laminate of the present invention can be produced by heating and compressing the surface of the adhesive support of the present invention on the side on which the adhesive layer is formed and the base material. The heating and compression bonding conditions are preferably, for example, a temperature of 100°C to 200°C, a pressure of 0.01 MPa to 1 MPa, and a time of 1 minute to 15 minutes.

The second embodiment of the laminated body of the present invention is the aspect shown in FIG. 2, and the support 2, the adhesive layer 3A, and the base material 1 are laminated in the stated order, and are located between the support 2 and the adhesive layer 3A The second adhesive layer 3B has a composition different from that of the adhesive layer 3A. In this embodiment, the substrate 1 and the adhesive layer 3A, the adhesive layer 3A and the second adhesive layer 3B, and the second adhesive layer 3B and the support 2 are preferably in contact on the surface. As shown in the second embodiment, by making the adhesive layer into two or more layers, there is an advantage that it is easy to bond the support and the base material with good insertability (without voids). In particular, the adhesive layer 3B is provided on the side of the support 2 and the second adhesive layer 3A is provided on the side of the base material 1 and bonded together, whereby the embedding property can be more effectively improved.

In the third embodiment of the laminate of the present invention, the support 2, the adhesive layer 3A, and the base material 1 are laminated in the order described, and there is a second adhesive layer between the adhesive layer 3A and the base material that is different from the composition of the adhesive layer. The state of the layer. In this embodiment, the support 2 and the adhesive layer 3A, the adhesive layer 3A and the second adhesive layer 3B, and the second adhesive layer 3B and the base material are preferably in surface contact.

Next, the second adhesive layer in the second embodiment and the third embodiment will be described in detail. The second adhesive layer 3B is not particularly defined as long as it is an adhesive layer having a composition different from that of the adhesive layer 3A containing the temporary adhesive of the present invention. Therefore, the second adhesive layer 3B may be an adhesive layer containing the same constituents as the temporary adhesive of the present invention. However, in this case, the composition of the adhesive layer 3A and the adhesive layer 3B are different from each other. In the present invention, the second adhesive layer preferably contains elastomer X containing styrene-derived repeating units in a ratio of 50% by mass or more and 95% by mass or less in all repeating units. By using such an adhesive layer, the adhesiveness can be further improved. Furthermore, the content of the compound that is liquid at 25°C and contains silicon atoms in the second adhesive layer is preferably 10 mass of the content of the compound that is liquid at 25°C and contains silicon atoms contained in the adhesive layer %the following. By using such a second adhesive layer, it becomes easier to adjust the peeling interface. For example, in the substrate (device wafer)/second adhesive layer/adhesive layer containing the temporary adhesive of the present invention/support (carrier), the force required to separate the substrate and the second adhesive layer If the force required to peel off the adhesive layer containing the temporary adhesive agent of the present invention and the support is greater, the support body and the adhesive layer containing the temporary adhesive agent of the present invention can be peeled off. With this configuration, peeling becomes easier. In addition, the second adhesive layer in the present invention preferably contains elastomer Y containing styrene-derived repeating units in a ratio of 10% by mass or more and less than 50% by mass in all repeating units. With such a configuration, the warpage of the wafer can be effectively suppressed. The elastomer X and the elastomer Y in the second adhesive layer and their blending ratio have the same meanings as those described in the temporary adhesive of the present invention, and the preferred ranges are also the same. In addition, various additives and the like described in the temporary adhesive of the present invention may be blended in the second adhesive layer.

The fourth embodiment of the layered body of the present invention has other layers in the first to third embodiments. As the other layer, a layer called a release layer, a release layer, or a separation layer can be exemplified. As the peeling layer, for example, the description of paragraph 0025 to paragraph 0055 of JP 2014-212292 A can be referred to, and these contents are incorporated in this specification. In addition, as the separation layer, reference can be made to the description of paragraph 0069 to paragraph 0124 of International Publication WO2013/065417, and these contents are incorporated into this specification.

The substrate can preferably be a device wafer. Known ones can be used for the device wafer without limitation, and examples thereof include silicon substrates, compound semiconductor substrates, and the like. Specific examples of compound semiconductor substrates include SiC substrates, SiGe substrates, ZnS substrates, ZnSe substrates, GaAs substrates, InP substrates, GaN substrates, and the like. On the surface of the device wafer, mechanical structures or circuits may be formed. Examples of device wafers on which mechanical structures or circuits are formed include: Micro Electro Mechanical Systems (MEMS), power devices, image sensors, micro sensors, and light emitting diodes (Light Emitting Diode, LED), optical components, interposer (Interposer), embedded components, micro components, etc. The device wafer preferably has a structure such as metal bumps. According to the present invention, even with the element wafer having the above-mentioned structure on the surface, the temporary bonding can be stably performed, and the temporary bonding with the element wafer can be easily released. The height of the structure is not particularly limited. For example, it is preferably 1 μm to 150 μm, and more preferably 5 μm to 100 μm. The film thickness of the device wafer before the mechanical or chemical treatment is preferably 500 μm or more, more preferably 600 μm or more, and still more preferably 700 μm or more. The upper limit is preferably 2000 μm or less, and more preferably 1500 μm or less, for example. The film thickness of the device wafer after being thinned by mechanical or chemical treatment is, for example, preferably less than 500 μm, more preferably 400 μm or less, and still more preferably 300 μm or less. The lower limit is, for example, preferably 1 μm or more, and more preferably 5 μm or more.

In the laminate of the present invention, the support (carrier support) has the same meaning as the support described in the adhesive support, and the preferred range is also the same. In addition, the adhesive layer 3A may be provided on the substrate, and the adhesive layer 3B may be provided on the support and then bonded. In this case, the adhesive layer 3A and the adhesive layer 3B may be the same or different. Under different circumstances, by changing the types of compounds containing silicon atoms, or changing the types or amounts of other additives such as compounds containing lipophilic groups and fluorine atoms, the peeling selectivity (substrate interface and support The peeling selectivity of the body interface) or peeling force. In addition, the adhesive sheet of the present invention may be arranged between the support and the base material, and heated and pressure-bonded to produce it.

In addition, the laminate of the present invention may also use the temporary adhesive of the present invention on one of the support and the substrate to form an adhesive layer, and use the temporary adhesive or the temporary adhesive of the present invention on the other of the support and the substrate. The other temporary adhesive is used to form the adhesive layer, and the support and the substrate on which the adhesive layer is formed are heated and pressure-bonded to each other. According to this method, since the adhesive layers are bonded to each other, the support and the base material can be bonded to each other with good insertability.

Furthermore, the laminate of the present invention may also be formed of one or more adhesive layers 3A and 3B using the temporary adhesive of the present invention and the other temporary adhesive on one of the support and the base material. The adhesive layer is manufactured by disposing the other of the support and the substrate on the adhesive layer, and heat-pressing and bonding the support and the substrate.

<Method of Manufacturing Semiconductor Device> <<First Embodiment>> Hereinafter, referring to FIGS. 3(A) to 3(E), one embodiment of a method of manufacturing a semiconductor device that has undergone the steps of manufacturing a laminate will be described. instruction. In addition, the present invention is not limited to the following embodiments. Figures 3(A) to 3(E) are schematic cross-sectional views (Figure 3(A) and Figure 3(B)) for explaining the temporary connection of the support and the device wafer, respectively, showing the temporary connection to the support The thinned element wafer state (Figure 3(C)), the state where the support and the element wafer are peeled off (Figure 3(D)), the state after the adhesive layer is removed from the element wafer (Figure 3(E) )) is a schematic cross-sectional view.

In this embodiment, as shown in FIG. 3(A), first, an adhesive support 100 in which an adhesive layer 11 is provided on a support 12 is prepared. The subsequent layer 11 preferably does not contain a solvent substantially. The element wafer 60 (base material) is formed by arranging a plurality of element wafers 62 on the surface 61 a of the silicon substrate 61. The thickness of the silicon substrate 61 is preferably 200 μm to 1200 μm, for example. The element wafer 62 is preferably a metal structure, for example, and the height is preferably 10 μm-100 μm. In the process of forming the adhesive layer 11, a step of cleaning the back surface of the support 12 or the device wafer 60 with a solvent may be provided. Specifically, by using a solvent to dissolve the adhesive layer to remove residues of the adhesive layer attached to the support 12 or the end face and back surface of the device wafer 60, contamination of the device can be prevented, and the overall thinning of the device wafer can be reduced. Total Thickness Variation (TTV). As the solvent used in the step of cleaning the support 12 or the back surface of the element wafer 60 with a solvent, the solvent contained in the temporary adhesive can be used.

Then, as shown in FIG. 3(B), the adhesive support 100 and the element wafer 60 are pressure-bonded to temporarily bond the support 12 and the element wafer 60. The subsequent layer 11 preferably completely covers the element wafer 62, and when the height of the element wafer is X μm and the thickness of the adhesive layer is Y μm, the relationship of "X+100≧Y>X" is preferably satisfied. The case where the layer 11 completely covers the device wafer 62 is effective when the TTV (Total Thickness Variation) of the thin device wafer is to be further reduced (that is, when the flatness of the thin device wafer is further improved). That is, when the device wafer is thinned, by using the adhesive layer 11 to protect the plurality of device wafers 62, the uneven shape in the contact surface with the support 12 can be substantially eliminated. Therefore, even if thinning is carried out in such a supported state, the risk that the shape derived from the plurality of element wafers 62 is transferred to the back surface 61b1 of the thin element wafer is reduced. As a result, the resulting thin element can be further reduced. TTV of the wafer.

Then, as shown in FIG. 3(C), the back surface 61b of the silicon substrate 61 is subjected to mechanical or chemical treatment (not particularly limited, for example, a thin film treatment such as sliding grinding or chemical mechanical polishing (Chemical Mechanical Polishing, CMP), etc.). High temperature and vacuum processing such as Chemical Vapor Deposition (CVD) or Physical Vapor Deposition (PVD), and processing using chemicals such as organic solvents, acidic processing liquids, or alkaline processing liquids , Plating treatment, actinic ray irradiation, heating and cooling treatment, etc.), so that the thickness of the silicon substrate 61 is reduced (for example, the average thickness is preferably less than 500 μm, and more preferably 1 μm to 200 μm) to obtain Thin element wafer 60a. After the element wafer is thinned, in the stage before the high temperature and vacuum processing, a step of cleaning the adhesive layer that extends to the outside compared to the area of the base surface of the element wafer with a solvent can be provided. Specifically, after the device wafer is thinned, the excess adhesive layer is removed using a solvent that dissolves the adhesive layer, thereby preventing deformation and deterioration of the adhesive layer caused by the direct treatment of the adhesive layer under high temperature and vacuum. . As the solvent used in the step of cleaning the adhesive layer that extends to the outside from the area of the substrate surface of the element wafer with a solvent, the solvent contained in the temporary adhesive can be used. That is, in the present invention, the area of the film surface of the adhesive layer is preferably smaller than the area of the substrate surface of the support. In the present invention, when the diameter of the substrate surface of the support is C μm, the diameter of the substrate surface of the element wafer is D μm, and the diameter of the film surface of the adhesive layer is T μm, It is better to satisfy (C-200)≧T≧D. Furthermore, when the diameter of the substrate surface of the support is set to C μm, the diameter of the substrate surface of the element wafer is set to D μm, and the diameter of the film surface of the adhesive layer on the side in contact with the support is set to T _C μm, when the diameter of the film surface of the adhesive layer on the side in contact with the element wafer is set to T _D μm, it is preferable to satisfy (C-200)≧T _C >T _D ≧D. By adopting such a configuration, it is possible to further suppress the deformation and deterioration of the adhesive layer caused by directly performing high-temperature and vacuum processing on the adhesive layer. In addition, the area of the film surface of the adhesive layer refers to the area when viewed from a direction perpendicular to the support, and the unevenness of the film surface is not considered. The same applies to the substrate surface of the device wafer. That is, the substrate surface of the element wafer described here is, for example, a surface corresponding to 61a in FIGS. 3(A) to 3(E). The same applies to the diameter of the film surface of the adhesive layer. In addition, the diameter T of the film surface of the adhesive layer refers to the diameter of the film surface of the adhesive layer on the side in contact with the element wafer _{when the diameter of the film surface of the adhesive layer in contact with the support is set to T C μm.} When it is set to T _D μm, T=(T _C +T _D )/2. The diameter of the substrate surface of the support and the diameter of the substrate surface of the element wafer refer to the diameter of the surface on the side in contact with the adhesive layer. In addition, although the support body and the like are defined as the "diameter", the support body and the like do not necessarily have to be circular (perfect circle) in the mathematical sense, as long as they are substantially circular. When it is not a perfect circle, the diameter when converted to a perfect circle of the same area is set as the above-mentioned diameter. In addition, as a mechanical or chemical treatment, the following treatment may be performed after the thinning treatment: a through hole (not shown) is formed through the silicon substrate from the back surface 61b1 of the thin element wafer 60a, and formed in the through hole Silicon through electrode (not shown). The heat treatment may be performed during the period after the support 12 and the element wafer 60 are temporarily bonded and before peeling. As an example of the heat treatment, heat treatment in mechanical or chemical treatment can be cited. The maximum reached temperature in the heat treatment is preferably 80°C to 400°C, more preferably 130°C to 400°C, and still more preferably 180°C to 350°C. The highest reached temperature in the heat treatment is preferably set to a temperature lower than the decomposition temperature of the adhesive layer. The heating treatment is preferably heating for 30 seconds to 30 minutes at the highest reaching temperature, and more preferably heating for 1 minute to 10 minutes at the highest reaching temperature.

Then, as shown in FIG. 3(D), the support 12 is detached from the thin element wafer 60a. The method of detachment is not particularly limited, and it is preferable to pull up from the end of the thin device wafer 60a in a direction perpendicular to the thin device wafer 60a without performing any processing to peel off. At this time, the peeling interface is preferably peeled from the interface between the support 12 and the adhesive layer 11. In this case, it is preferable that the peeling strength A of the interface between the support 12 and the adhesive layer 11 and the peeling strength B of the element wafer surface 61a and the adhesive layer 11 satisfy the following formula. A＜B …Equation (1)

In addition, the adhesive layer 11 is brought into contact with a peeling liquid described later, and then, if necessary, after the thin element wafer 60a is slid relative to the support 12, the thin element wafer 60a may be moved from the end of the thin element wafer 60a to the element wafer. Pull up in the vertical direction to peel off.

<Peeling liquid> Hereinafter, the peeling liquid will be described in detail. As the peeling liquid, water and a solvent (organic solvent) can be used. In addition, as the peeling liquid, an organic solvent that dissolves the adhesive layer 11 is preferable. Examples of organic solvents include: aliphatic hydrocarbons (hexane, heptane, Isopar E, H, G (manufactured by ESSO Chemical Co., Ltd.), limonene, p-menthane, nonane Alkane, decane, dodecane, decahydronaphthalene, etc.), aromatic hydrocarbons (toluene, xylene, anisole, mesitylene, ethylbenzene, propylbenzene, cumene, n-butylbenzene, Dibutylbenzene, isobutylbenzene, tertiary butylbenzene, pentylbenzene, isopentylbenzene, (2,2-dimethylpropyl)benzene, 1-phenylhexane, 1-phenylheptane Alkane, 1-phenyloctane, 1-phenylnonane, 1-phenyldecane, cyclopropylbenzene, cyclohexylbenzene, 2-ethyltoluene, 1,2-diethylbenzene, o-iso Propyl toluene, indane, 1,2,3,4-tetrahydronaphthalene, 3-ethyltoluene, m-isopropyl toluene, 1,3-diisopropylbenzene, 4-ethyltoluene, 1, 4-diethylbenzene, p-isopropyltoluene, 1,4-diisopropylbenzene, 4-tert-butyltoluene, 1,4-di-tert-butylbenzene, 1,3-diethyl Benzene, 1,2,3-trimethylbenzene, 1,2,4-trimethylbenzene, 4-tert-butyl-o-xylene, 1,2,4-triethylbenzene, 1,3 ,5-Triethylbenzene, 1,3,5-Triisopropylbenzene, 5-tert-butyl-m-xylene, 3,5-di-tert-butyltoluene, 1,2,3,5 -Tetramethylbenzene, 1,2,4,5-tetramethylbenzene, pentamethylbenzene, etc.), halogenated hydrocarbons (dichloromethane, dichloroethane, trichloroethylene, monochlorobenzene, etc.) , Polar solvents. As polar solvents, particularly alcohols (methanol, ethanol, propanol, isopropanol, 1-butanol, 1-pentanol, 1-hexanol, 1-heptanol, 1-octanol, 2- Octanol, 2-ethyl-1-hexanol, 1-nonanol, 1-decanol, benzyl alcohol, ethylene glycol monomethyl ether, 2-ethoxyethanol, diethylene glycol monoethyl ether, diethyl 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 mono Benzyl ether, ethylene glycol monophenyl ether, propylene glycol monophenyl ether, methyl phenyl methanol, n-pentanol, methyl pentanol, etc.), ketones (acetone, methyl ethyl ketone, ethyl butyl, etc.) Ketones, cyclohexanone, etc.), esters (ethyl acetate, propyl acetate, butyl acetate, amyl acetate, benzyl acetate, methyl lactate, butyl lactate, ethylene glycol monobutyl ether acetate, Propylene glycol monomethyl ether acetate, diethylene glycol acetate, diethyl phthalate, butyl acetyl propionate, etc.), others (triethyl phosphate, tricresyl phosphate, N -Phenylethanolamine, N-phenyldiethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, 4-(2-hydroxyethyl)morpholine, N,N-dimethylacetamide, N -Methylpyrrolidone, etc.) and so on.

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

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

As the acid, inorganic acids such as halogenated hydrocarbons, sulfuric acid, nitric acid, phosphoric acid, and boric acid, or methanesulfonic acid, ethanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, trifluoromethanesulfonic acid, acetic acid, citric acid, formic acid, etc. can be used. Organic acids such as gluconic acid, lactic acid, oxalic acid, and tartaric acid.

As the surfactant, anionic, cationic, nonionic, and zwitterionic surfactants can be used. In this case, the content of the surfactant relative to the total amount of the alkaline aqueous solution is preferably 1% by mass to 20% by mass, more preferably 1% by mass to 10% by mass. By setting the content of the surfactant within the above range, there is a tendency that the peelability between the adhesive layer 11 and the thin device wafer 60a can be further improved.

The anionic surfactant is not particularly limited, and examples thereof include fatty acid salts, rosinates, hydroxyalkane sulfonates, alkane sulfonates, dialkylsulfosuccinates, and linear alkanes. Base benzene sulfonates, branched chain alkyl benzene sulfonates, alkyl naphthalene sulfonates, alkyl diphenyl ether (two) sulfonates, alkyl phenoxy polyoxyethylene alkyl sulfonates Acid salts, polyoxyethylene alkylsulfophenyl ether salts, sodium N-alkyl-N-oleyl taurate, disodium N-alkylsulfosuccinic acid monoamide, petroleum Sulfonates, sulfated castor oil, sulfated tallow oil, sulfate ester salts of fatty acid alkyl esters, alkyl sulfate ester salts, polyoxyethylene alkyl ether sulfate ester salts, fatty acid monoglyceride sulfate ester salts Types, polyoxyethylene alkyl phenyl ether sulfate ester salts, polyoxyethylene styryl phenyl ether sulfate ester salts, alkyl phosphate ester salts, polyoxyethylene alkyl ether phosphate ester salts, polyoxyethylene Alkyl phenyl ether phosphate salts, partial saponification products of styrene-maleic anhydride copolymer, partial saponification products of olefin-maleic anhydride copolymer, naphthalenesulfonate formaldehyde condensate, etc. . Among them, alkyl benzene sulfonates, alkyl naphthalene sulfonates, and alkyl diphenyl ether (di) sulfonates can be particularly preferably used.

It does not specifically limit as a cationic surfactant, A conventionally well-known thing can be used. Examples include alkylamine salts, quaternary ammonium salts, alkylimidazolium salts, polyoxyethylene alkylamine salts, and polyethylene polyamine derivatives.

The nonionic surfactant is not particularly limited, and examples include polyethylene glycol type higher alcohol ethylene oxide adducts, alkylphenol ethylene oxide adducts, and alkylnaphthol ethylene oxide adducts. Alkyl adduct, phenol ethylene oxide adduct, naphthol ethylene oxide adduct, fatty acid ethylene oxide adduct, polyhydric alcohol fatty acid ester ethylene oxide adduct, higher alkyl amine Ethylene oxide adduct, fatty acid amide ethylene oxide adduct, oil and fat ethylene oxide adduct, polypropylene glycol ethylene oxide adduct, dimethylsiloxane-ethylene oxide Block copolymers, dimethylsiloxane-(propylene oxide-ethylene oxide) block copolymers, fatty acid esters of polyol type glycerin, fatty acid esters of pentaerythritol, sorbitol and sorbitol Fatty acid esters of anhydrides, fatty acid esters of sucrose, alkyl ethers of polyhydric alcohols, and fatty acid amides of alkanolamines. Among them, those having an aromatic ring and an ethylene oxide chain are preferred, and phenol ethylene oxide adducts with substituted or unsubstituted alkyl groups or naphthol epoxy resins with substituted or unsubstituted alkyl groups are more preferred. Ethane adduct.

The zwitterionic surfactant is not particularly limited, and examples thereof include amine oxide systems such as alkyl dimethyl amine oxide, betaine systems such as alkyl betaine, and amino acid systems such as sodium alkylamino fatty acid sodium. In particular, an optionally substituted alkyl dimethyl amine oxide, an optionally substituted alkyl carboxy betaine, and an optionally substituted alkyl sultaine can be preferably used. Specifically, the compound represented by the formula (2) of the paragraph number [0256] of JP 2008-203359 A, and the formula of the paragraph number [0028] of JP 2008-276166 can be used ( I) The compound represented by the formula (II) and the formula (VI), the compound represented by paragraph numbers [0022] to [0029] of JP 2009-47927 A.

Furthermore, the peeling liquid may contain additives such as a defoamer and a hard water softener if necessary.

Furthermore, as shown in FIG. 3(E), by removing the adhesive layer 11 from the thin device wafer 60a, a thin device wafer can be obtained. Examples of methods for removing the adhesive layer 11 include: a method of peeling and removing the adhesive layer in a film-like state (mechanical peeling); a method of peeling and removing the adhesive layer after swelling the adhesive layer with a peeling liquid; The method of destroying and removing; the method of dissolving and removing the adhesive layer by dissolving it in the peeling liquid; the method of decomposing, vaporizing and removing the adhesive layer by irradiation of actinic rays, radiation or heating. A method of peeling and removing the adhesive layer in a film-like state can be preferably used; a method of dissolving and removing the adhesive layer by dissolving the adhesive layer in an aqueous solution or an organic solvent. As the organic solvent, the organic solvents described in the peeling liquid can be used. From the viewpoint of reducing the amount of solvent used, it is preferable to remove in a film-like state. In addition, from the viewpoint of reducing damage to the surface of the element wafer, it is preferable to dissolve and remove. In order to remove in a film-like state, it is preferable that the peel strength B of the element wafer surface 61a and the adhesive layer 11 satisfy the following formula (2). B≦4 N/cm …Equation (2)

When the peeling strength of the interface between the support 12 and the adhesive layer 11 is set to A, and the peeling strength of the surface 61a of the device wafer and the adhesive layer 11 is set to B, the above formula (1) and formula ( 2) When the support 12 is peeled from the thin device wafer 60a, the end of the thin device wafer 60a can be pulled up from the end of the thin device wafer 60a in a direction perpendicular to the device wafer to be peeled off without any processing. The adhesive layer 11 on the surface 61a of the element wafer is removed in a film-like state. After the support 12 is detached from the thin device wafer 60a, various well-known processes are performed on the thin device wafer 60a as necessary to manufacture a semiconductor device having the thin device wafer 60a.

In addition, when the adhesive layer is attached to the support, the support can be regenerated by removing the adhesive layer. Examples of methods for removing the adhesive layer include peeling in a film-like state; physical removal by brush, ultrasonic, ice particles, or aerosol blowing; and dissolving in an aqueous solution or organic solvent The method of dissolving and removing; the method of decomposing and vaporizing by irradiation of actinic rays, radiation, heat and other chemical removal methods; depending on the support, previously known cleaning methods can be used. For example, in the case of using a silicon substrate as a support, a previously known cleaning method for silicon wafers can be used. For example, as aqueous solutions or organic solvents that can be used for chemical removal, strong acids, strong bases, strong oxidants, or mixtures of these can be cited. Specifically, sulfuric acid, hydrochloric acid, hydrofluoric acid, nitric acid, and organic acids can be cited. And other acids; bases such as tetramethylammonium, ammonia, organic bases; hydrogen peroxide and other oxidants; or a mixture of ammonia and hydrogen peroxide, a mixture of hydrochloric acid and hydrogen peroxide, a mixture of sulfuric acid and hydrogen peroxide, hydrogen Mixtures of hydrofluoric acid and hydrogen peroxide water, mixtures of hydrofluoric acid and ammonium fluoride, etc.

From the viewpoint of adhesiveness in the case of using a regenerated support, it is preferable to use a support cleaning solution. The support cleaning solution preferably contains an acid (strong acid) with a pKa of less than 0 and hydrogen peroxide. The acid having a pKa of less than 0 can be selected from inorganic acids such as hydrogen iodide, perchloric acid, hydrogen bromide, hydrogen chloride, nitric acid, and sulfuric acid, or organic acids such as alkyl sulfonic acid and aryl sulfonic acid. From the viewpoint of the cleaning properties of the adhesive layer on the support, an inorganic acid is preferred, and sulfuric acid is particularly preferred.

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

<<Second Embodiment>> Referring to FIGS. 4(A) to 4(E), a second embodiment of a semiconductor manufacturing method that has passed through the steps of manufacturing a laminate will be described. The same reference numerals are given to the same parts as in the first embodiment, and the description thereof is omitted. 4(A) to 4(E) are schematic cross-sectional views (FIG. 4(A), FIG. 4(B)) for explaining the temporary connection of the support and the device wafer, respectively, showing the temporary connection to the support The thinned element wafer state (Figure 4(C)), the state where the support and the element wafer are peeled off (Figure 4(D)), the state after the adhesive layer is removed from the element wafer (Figure 4(E) )) is a schematic cross-sectional view. In this embodiment, as shown in FIG. 4(A), the point that the adhesive layer is formed on the surface 61 a of the element wafer is different from the first embodiment. In the case where the adhesive layer 11a is provided on the surface 61a of the element wafer 60, it can be formed by applying (preferably coating) a temporary adhesive on the surface 61a of the element wafer 60 and then drying (baking). . Drying can be performed, for example, at 60°C to 150°C for 10 seconds to 2 minutes. Then, as shown in FIG. 4(B), the support 12 and the element wafer 60 are press-contacted to temporarily bond the support 12 and the element wafer 60. Then, as shown in FIG. 4(C), the back surface 61b of the silicon substrate 61 is mechanically or chemically processed to reduce the thickness of the silicon substrate 61 to obtain a thin device wafer 60a. Then, as shown in FIG. 4(D), the support 12 is detached from the thin element wafer 60a. Furthermore, as shown in FIG. 4(E), the adhesive layer 11 can be removed from the thin element wafer 60a.

<<Third Embodiment>> Referring to FIGS. 5(A) to 5(E), a third embodiment of a semiconductor manufacturing method that has passed through the steps of manufacturing a laminate will be described. The same reference numerals are given to the same parts as in the first embodiment, and the description thereof is omitted. Figures 5(A) to 5(E) are schematic cross-sectional views (Figures 5(A) and 5(B)) for explaining the temporary attachment of the support and the element wafer, respectively, showing the temporary attachment to the support The thinned state of the element wafer (Figure 5(C)), the state where the support and the element wafer are peeled off (Figure 5(D)), the state after the adhesive layer is removed from the element wafer (Figure 5(E) )) is a schematic cross-sectional view. In this embodiment, as shown in FIG. 5(A) and FIG. 5(B), the adhesive layer 11b and the adhesive layer 11c are formed on the support 12 and the surface 61a of the device wafer, respectively, and the support and the device wafer The circular surfaces on the side where the adhesive layer is formed are press-bonded to each other to manufacture a laminated body (temporary bonding of the support 12 and the element wafer 60) is different from the above-mentioned first embodiment. At least one of the adhesive layer 11b and the adhesive layer 11c can be formed using the temporary adhesive of the present invention. The temporary adhesive of the present invention may be used to form both the adhesive layer 11b and the adhesive layer 11c, or only one of the adhesive layers may be formed using the temporary adhesive of the present invention, and the other adhesive layer may be formed using the temporary adhesive. Preferably, the temporary adhesive is used to form the adhesive layer 11b, and the temporary adhesive of the present invention is used to form the adhesive layer 11c. In addition, each of the adhesive layer 11b and the adhesive layer 11c may include only one layer, or may be a laminate in which two or more adhesive layers are laminated. That is, each adhesive layer may be formed by overlaying two or more temporary adhesives. After the support 12 and the element wafer 60 are temporarily attached, then, as shown in FIG. 5(C), the back surface 61b of the silicon substrate 61 is mechanically or chemically treated to make the thickness of the silicon substrate 61 thinner. A thin element wafer 60a is obtained. Then, as shown in FIG. 5(D), the support 12 is detached from the thin element wafer 60a. Furthermore, as shown in FIG. 5(E), the adhesive layer 11d can be removed from the thin element wafer 60a.

<<Previous embodiment>> Next, the previous embodiment will be described. 6 is a schematic cross-sectional view for explaining the release of the temporary bonding state between the conventional adhesive support and the element wafer. In the previous embodiment, as shown in FIG. 6, an adhesive support 100a in which an adhesive layer 11a formed of a previous temporary adhesive is provided on the support 12 is used as an adhesive support. In the same manner as the procedure described with reference to FIGS. 3(A) to 3(E), the adhesive support 100a is temporarily attached to the device wafer, and the silicon substrate in the device wafer is thinned. In the same procedure, the thin element wafer 60a is peeled from the adhesive support 100a.

However, if the previous temporary adhesive is used, the device wafer is temporarily supported by a high adhesive force, and it is difficult to easily release the temporary support of the device wafer without causing damage to the device wafer. For example, if a temporary adhesive with high adhesiveness among the conventional temporary adhesives is used in order to make sufficient temporary bonding between the element wafer and the support, the temporary adhesive between the element wafer and the support tends to be too strong. Therefore, in order to relieve this excessively strong temporary bonding, for example, as shown in FIG. 6, an adhesive tape (for example, a dicing tape) 70 is attached to the back surface of the thin element wafer 60a, and the thin element wafer 60a is peeled off from the self-adhesive support 100a. In this case, a problem is likely to occur that the structure 63 is detached from the element wafer 62 on which the structure 63 is provided, and the element wafer 62 is damaged. On the other hand, if a temporary adhesive with low adhesiveness among the conventional temporary adhesives is used, the temporary support of the device wafer can be easily released, but after all, the temporary adhesion between the device wafer and the support is too weak, which is easy There is a problem that the device wafer cannot be reliably supported by the support.

In contrast, the laminate of the present invention can exhibit sufficient adhesiveness, and the temporary adhesion between the element wafer 60 and the support can be easily released. That is, if the laminated body of the present invention is used, the element wafer 60 can be temporarily bonded with high adhesive force, and the temporary adhesion to the thin element wafer 60a can be easily released without damaging the thin element wafer 60a.

The manufacturing method of the semiconductor device of the present invention is not limited to the above-mentioned embodiment, and may be appropriately modified, improved, and the like. In addition, in the above-mentioned embodiment, the adhesive layer may have a single-layer structure, and the adhesive layer may also have a multi-layer structure. In addition, in the above-mentioned embodiment, as the element wafer, there is a silicon substrate, but it is not limited to this, and it may be any member to be processed that can be subjected to mechanical or chemical processing in the manufacturing method of a semiconductor device. . For example, compound semiconductor substrates can also be cited. Specific examples of compound semiconductor substrates include SiC substrates, SiGe substrates, ZnS substrates, ZnSe substrates, GaAs substrates, InP substrates, and GaN substrates. Furthermore, in the above-mentioned embodiment, as the mechanical or chemical treatment of the element wafer (silicon substrate), the thinning of the element wafer and the formation of silicon through-electrodes may be mentioned, but it is not limited to this These may also include any processing required in the method of manufacturing a semiconductor device. In addition, the shape, size, number, arrangement position, etc. of the element wafers in the element wafers exemplified in the above-mentioned embodiment are arbitrary and not limited.

<Set> Next, the set of the present invention will be described. The set of the present invention has: the temporary adhesive of the present invention; and a second adhesive including the elasticity of containing repeating units derived from styrene in a ratio of 50% by mass to 95% by mass in all repeating units Body X, and has a different composition from the temporary adhesive. The second adhesive preferably contains elastomer X containing styrene-derived repeating units in a ratio of 50% by mass or more and 95% by mass or less in all repeating units. Furthermore, in the second adhesive, the content of the compound that is liquid at 25° C. and contains silicon atoms is preferably 10% of the content of the compound that is liquid at 25° C. and contains silicon atoms contained in the temporary adhesive. Less than mass%. In addition, the second adhesive in the present invention preferably includes elastomer Y containing styrene-derived repeating units in a ratio of 10% by mass or more and less than 50% by mass in all repeating units. With such a configuration, the warpage of the wafer can be more effectively suppressed. The elastomer X and the elastomer Y in the second adhesive agent, and the blending ratio thereof have the same meanings as those described in the temporary adhesive agent of the present invention, and the preferred ranges are also the same. In addition, various additives and the like described in the temporary adhesive of the present invention may be blended in the second adhesive. These compounding amounts and the like are also preferably within the range described in the temporary adhesive of the present invention. The kit of the present invention preferably further has a substrate and a support. As the base material and the support, the base material and the support described in the above-mentioned laminate can be mentioned, and these base materials and the support can be used. By further having a substrate and a support, a laminate having the first adhesive layer containing the temporary adhesive of the present invention and the second adhesive layer between the substrate and the support can be produced. [Example]

Hereinafter, the present invention will be further described in detail with examples. As long as the gist of the present invention is not exceeded, the present invention is not limited to the following examples. In addition, unless otherwise specified, "parts" and "%" are quality standards. In addition, propylene glycol-1-methyl ether acetate is described as "PGMEA".

The following materials were used in this example. [Component A] (a-1) KP-323 (manufactured by Shin-Etsu Chemical Co., Ltd.) (a-2) KP-326 (manufactured by Shin-Etsu Chemical Co., Ltd.) (a-3) KP-341 (Shin-Etsu Chemical Co., Ltd.) Manufacturing) (a-4) KP-360A (manufactured by Shin-Etsu Chemical Co., Ltd.) (a-5) KP-361 (manufactured by Shin-Etsu Chemical Co., Ltd.) (a-6) KP-354 (manufactured by Shin-Etsu Chemical Co., Ltd.) (A-7) KP-356 (manufactured by Shin-Etsu Chemical Co., Ltd.) (a-8) KP-358 (manufactured by Shin-Etsu Chemical Co., Ltd.) (a-9) BYK 333 (BYK- (Manufactured by Chemie) (a-10) Polyflow KL-700 (manufactured by Kyoeisha Chemical Co., Ltd.) (a-11) TEGO WET 270 (Japan Evonik (Manufactured by Evonik Degussa Japan (share)) (a-12) SH28PA (manufactured by Toray Dow Corning (share)) (a-13) NBX-15 (NEOS (share)) Manufacturing) (Ra-1) KR220L (silicone resin solid, manufactured by Shin-Etsu Chemical Co., Ltd.) (Ra-2) 1-Dodecene (hydrocarbon-based oil, manufactured by Tokyo Chemical Industry Co., Ltd.) (a-1)～ (A-13) The viscosity at 25°C is in the range of 10 mPa·s to 20,000 mPa·s.

[Component B] (b-1): Septon 2104 (hydrogenated polystyrene elastomer, styrene content = 65% by mass, unsaturated double bond content = less than 0.5 mmol/g, 5% heat Mass reduction temperature = 400°C or more and less than 450°C, Mw = 50,000 or more and less than 100,000, hardness (Type A hardness tester) = 98, manufactured by Kuraray (stock)) (b-2): TAFF Tyco (Tuftec) P2000 (hydrogenated polystyrene elastomer, styrene content = 67% by mass, unsaturated double bond content = 0.5 mmol/g or more and less than 5 mmol/g, 5% thermal mass reduction temperature = 400 ℃ or more and less than 450℃, Mw=50,000 or more and less than 100,000, hardness (Type A hardness tester)=90 or more, manufactured by Asahi Kasei Co., Ltd.) (b-3): Septon 8104 (hydrogenated polymer Styrene elastomer, styrene content = 60% by mass, unsaturated double bond content = less than 0.5 mmol/g, 5% thermal mass reduction temperature = 350°C or more and less than 400°C, hardness (Type A hardness meter) = 98. Kuraray (Stock) Manufacturing) (b-4): Kraton A1535 (hydrogenated polystyrene elastomer, styrene content = 58% by mass, unsaturated double bond content = less than 0.5 mmol/g, 5% thermal mass reduction temperature = above 400°C and less than 450°C, hardness (Type A hardness tester) = 83, manufactured by Kraton Company)

(B-5): Septon 2002 (Hydrogenated polystyrene elastomer, styrene content = 30% by mass, unsaturated double bond content = less than 0.5 mmol/g, 5% thermal mass reduction temperature = 350°C or more and less than 400°C, Mw=50,000 or more and less than 100,000, hardness (Type A hardness tester)=80, manufactured by Kuraray (stock)) (b-6): Septon 4033 (Hydrogenated polystyrene elastomer, styrene content = 30% by mass, unsaturated double bond content = less than 0.5 mmol/g, 5% thermal mass reduction temperature = more than 400°C and less than 450°C, hardness (Type A Hardness tester = 76, manufactured by Kuraray (stock) (b-7): Kraton G1650 (hydrogenated polystyrene elastomer, styrene content = 30% by mass, unsaturated double bond Quantity = less than 0.5 mmol/g, 5% thermal mass reduction temperature = above 400°C and less than 450°C, hardness (Type A hardness tester) = 70, manufactured by Kraton company) (b-8): Septon (Septon) 8004 (Hydrogenated polystyrene elastomer, styrene content = 31% by mass, unsaturated double bond content = less than 0.5 mmol/g, 5% thermal mass reduction temperature = more than 400°C and less than 450°C, Mw = 50,000 or more and less than 100,000, hardness (Type A durometer) = 80, manufactured by Kuraray (stock) (b-9): Septon 8007 (hydrogenated polystyrene elastomer) , Styrene content = 30% by mass, unsaturated double bond content = less than 0.5 mmol/g, 5% thermal mass reduction temperature = 400 ℃ or more and less than 450 ℃, Mw = 50,000 or more and less than 100,000, hardness (A Type Hardness Tester) = 77, Kuraray (Stock) Manufacturing) (b-10): SIS5200P (non-hydrogenated polystyrene elastomer, styrene content = 15% by mass, unsaturated double bond content = 5 mmol/g or more and less than 15 mmol/g, 5% thermal mass reduction temperature=250°C or more and less than 350°C, Mw=100,000 or more and less than 200,000, manufactured by JSR (shares))

(Rb-1): RB810 (polybutadiene elastomer, unsaturated double bond content of 15 mmol/g or more, 5% thermal mass reduction temperature = 100°C or more and less than 250°C, Mw=200,000 or more and less than 300,000. JSR (Stock) Manufacturing) (Rb-2): ZEONEX 480R (Cycloolefin polymer manufactured by ZEON) (Rb-3): Durimide (Registered trademark) 284 (polyimide manufactured by Fujifilm) (Rb-4): PCZ300 (polycarbonate manufactured by Mitsubishi Gas Chemical Corporation) (Rb-5): Hytrel 7247 ( Polyester elastomer, 5% thermal mass reduction temperature = 383°C, hardness (Type A durometer) = 90 or more, manufactured by Du Pont-Toray (Rb-6): Prima Louis ( Primalloy) CP300 (polyester elastomer, 5% thermal mass reduction temperature = 399°C, hardness (Type A durometer) = 90 or more, manufactured by Mitsubishi Chemical Corporation)

The amount of unsaturated double bonds is a value calculated by NMR measurement. The 5% thermal mass reduction temperature is a value obtained by measuring the temperature at which the mass is reduced by 5% at the start of the measurement under the condition of increasing the temperature at 20°C/min from 25°C under a nitrogen flow using a thermogravimetry device (TGA).

[Test Example 1] <Formation of Adhesive Support 1> The coating solution 1 for forming an adhesive layer was spin-coated on a Si wafer (support wafer) with a diameter of 100 mm and a thickness of 525 μm, and then Baked at 110°C for 1 minute, and further baked at 190°C for 4 minutes, thereby producing an adhesive support 1 having an adhesive layer.

<Composition of Coating Liquid 1 for Adhesive Layer Formation> · A component: A component described in Table 1, and a mass part shown in Table 1 · B component: a B component described in Table 1, which is shown in Table 1 Yi Lu Nuosi parts by mass · (Irganox) 1010 (BASF (BASF) (shares) Ltd.): 0.9 parts by mass Sumi Leiser (Sumilizer) TP-D (manufactured by Sumitomo chemical (shares) Ltd.): 0.9 parts by mass solvent : Solvents listed in Table 1, parts by mass shown in Table 1

<Preparation of the test piece> Under vacuum, the surface of the adhesive support 1 on the side where the adhesive layer is formed, and a tape with a diameter of 100 mm, a thickness of 525 μm, and a height of 10 μm were applied to the adhesive support 1 at a pressure of 190°C and 0.11 MPa. The device surface of the Si wafer (device wafer) made of Cu bumps was crimped for 3 minutes to produce a test piece.

<Adhesion> Use a tensile testing machine (digital force gauge manufactured by IMADA (stock), type: ZP-50N), and stretch at 250 mm/min in the direction along the surface of the adhesive layer In the measurement, the shear adhesive force of the test piece was evaluated based on the following criteria. A: Adhesive force of 50 N or more B: Adhesive force of 10 N or more and less than 50 N C: Adhesive force of less than 10 N

<Releasability> Place the test piece together with the dicing frame in the center of the dicing tape mounting machine, and arrange the dicing tape from above. Under vacuum, the test piece and the dicing tape are fixed by a roller, the dicing tape is cut on the dicing frame, and the test piece is installed on the dicing tape. The test piece was stretched in a direction (90° direction) perpendicular to the surface of the adhesive layer under a condition of 50 mm/min at 25° C., and the peelability was evaluated based on the following criteria. In addition, after heating the produced test piece at 250°C for 30 minutes, the test piece was stretched in the direction perpendicular to the adhesive layer under the condition of 50 mm/min at 25°C to confirm the peelability after the thermal process. The evaluation is based on the following criteria. Furthermore, it was visually confirmed whether the Si wafer was damaged. A: The maximum peeling force is less than 12 N, and it is peelable. B: The maximum peeling force is 12 N or more and less than 16 N, which is peelable. C: The maximum peeling force is 16 N or more and less than 20 N, which is peelable. D: The maximum peeling force is 20 N or more and less than 25 N, and it is peelable. E: The maximum peeling force is 25 N or more or the Si wafer is broken.

<Removability (dissolution removal)> After the peeling test, the Si wafer with an adhesive layer (component wafer) was placed on the spin coater with the adhesive layer facing up, and the following table 1 was used. Then, the same solvent as the solvent of the coating liquid for layer formation was used as a cleaning solvent, and spraying was performed for 5 minutes. Furthermore, only in Comparative Example 5, Comparative Example 6, and Comparative Example 7 in which mesitylene was not used for spraying for 5 minutes, the rinsing was performed by spraying isopropanol (IPA) while rotating the Si wafer . Furthermore, spin drying is performed. After that, the appearance was observed, the presence or absence of the remaining adhesive layer was visually inspected, and the carbon atom content of the Si wafer surface was inspected by X-ray photoelectron spectroscopy, and the evaluation was performed based on the following criteria.

＜＜Measurement method of X-ray photoelectron spectroscopy＞＞ The measuring device uses PHI Quantera SXM (manufactured by ULVAC-PHI) to irradiate the substrate surface of the wafer with an analysis area of 1400 μm´700 μm 25 W monochromatic AlKα rays are detected at an emission angle of 45° to measure the abundance ratio (atm%) of carbon atoms. The measurement temperature is 25°C, and the measurement pressure is 10 ^-8 Pa or less. In addition, the area of the substrate surface of the wafer, when there are irregularities on the surface of the substrate surface, also refers to the area of the surface of the substrate assuming that the irregularities are not present. Evaluation is performed according to the following evaluation categories. A: The result of ESCA measurement is that the abundance ratio of carbon atoms is less than 1%. B: As a result of the ESCA measurement, the abundance ratio of carbon atoms is 1% or more and less than 3%. C: As a result of ESCA measurement, the abundance ratio of carbon atoms is 3% or more.

<Removability (film removal)> At 25°C, the Si wafer (component wafer) with the adhesive layer after the peelability test is fixed so that it cannot move, and the peeling tape (Lintec) Co., Ltd.) The adhesive layer is attached to the Si wafer with the adhesive layer, and the peeling tape is stretched in a direction perpendicular to the adhesive layer, and the adhesive layer is moved to the 90° direction at a speed of 50 mm/min. Pull up, and peel off the adhesive layer in a film form from the device surface of the Si wafer (device wafer). After that, the appearance was observed and the presence or absence of peeling residues of the adhesive layer remaining on the Si wafer was visually inspected, and the evaluation was performed according to the following criteria. A: The adhesive layer can be removed in a film form with a peel strength of 4 N/cm or less without breaking, and no peeling residue of the adhesive layer is confirmed. B: The adhesive layer can be removed in a film form with a peel strength exceeding 4 N/cm without breaking, and no peeling residue of the adhesive layer is confirmed. C: It does not meet either of the above-mentioned A and B (fracture occurred during peeling).

<Wafer warpage> The surface of the component wafer of the produced test piece that is not in contact with the adhesive layer is polished until the thickness of the component wafer becomes 35 μm, and then manufactured by KLA-Tencor For FLX-2320, set the heating rate and cooling rate to 10°C/min. After heating from room temperature to 200°C, it is cooled to 25°C, and the Bow value (the magnitude of warpage) is measured. A: Bow value is 40 μm or less B: Bow value is more than 40 μm and less than 80 μm C: Bow value is 80 μm or more and less than 200 μm D: Bow value is 200 μm or more

[Table 1]

From the above results, it is clear that when the temporary adhesive of the present invention is used, the adhesiveness and room temperature peeling properties are good. Furthermore, the releasability after heating and the removability of the adhesive layer are good, and the warpage of the wafer is suppressed. In addition, the warpage of the wafer of the example in which the elastic body X and the elastic body Y are used as the elastic body is more effectively suppressed.

[Experimental Example 2] <Formation of Adhesive Support 2> The coating liquid 2 for forming an adhesive layer was spin-coated on a Si wafer (support wafer) with a diameter of 100 mm and a thickness of 525 μm. Baked at 110°C for 1 minute, and further baked at 190°C for 4 minutes, thereby fabricating an adhesive support 2 having an adhesive layer. In addition, the coating solution 3 for forming an adhesive layer was spin-coated on a Si wafer (element wafer) with Cu bumps with a diameter of 100 mm, a thickness of 525 μm, and a height of 10 μm, and then heated at 110°C. Bake for 1 minute, and further bake at 190°C for 4 minutes, thereby fabricating an adhesive substrate with an adhesive layer.

<Composition of Adhesive Layer Formation Coating Liquid 2 and Adhesive Layer Formation Coating Liquid 3> · A component: A component described in Table 2, a mass part shown in Table 2 · B component: A component described in Table 2 Component B, quality as shown in Table 2, Irganox 1010 (Summer Chemical) (Summer Chemical) (Sumizumi) (BASF) (manufactured by BASF): )Manufacturing: Quality: 30 copies of toluene: 0.9 quality copies

<Preparation of the test piece> Under vacuum, pressure bonding was performed on the surface of the adhesive support 2 on the side where the adhesive layer was formed and the surface of the adhesive base material where the adhesive layer was formed at 190°C and 0.11 MPa for 3 minutes. , And make a test piece.

<Adhesiveness> The adhesiveness was evaluated by the same method and criteria as the adhesiveness evaluation in Test Example 1. <Embedding property> Using C-SAM (ultrasonic microscope) on the test piece, confirm the bonding layer (including the interface between the bonding layers, the bonding surface between the bonding layer and the substrate, and the bonding surface between the bonding layer and the support ) Is there any gap in it. A: No voids are generated. B: One or more and five or less small voids with a diameter of 10 μm or less can be confirmed, but there is no actual damage. C: More than five and less than ten small voids with a diameter of 10 μm or less can be confirmed, but there is no actual damage. D: Ten or more voids with a diameter exceeding 10 μm are generated, and there is actual damage. <Peelability> The peelability was evaluated by the same method and criteria as the peelability evaluation in Test Example 1. <Removability (dissolution removal)> The removal performance (dissolution removal) was evaluated by the same method and criteria as the removal performance (dissolution removal) in Test Example 1. <Removability (film removal)> The removability (film removal) was evaluated by the same method and criteria as the removability (film removal) in Test Example 1. <Wafer warpage> The wafer warpage was evaluated by the same method and criteria as the wafer warpage in Test Example 1.

[Table 2]

From the above results, it is clear that when the temporary adhesive of the present invention is used, the adhesiveness and room temperature peeling properties are good. Furthermore, the releasability after heating and the removability of the adhesive layer are good. In addition, the warpage of the wafer of the example in which the elastic body X and the elastic body Y are used as the elastic body is more effectively suppressed. In addition, when applied to both the support side and the element side (Example 34 to Example 41), the embedding property was good.

[Experimental example 3] <Method for producing adhesive film> Example 42 to Example 50, Comparative Example 12 to Comparative Example 15, and Comparative Example 18 to Comparative Example 21 were adhered with a wire rod at a speed of 1 m/min The film-forming composition was coated on a 75 μm-thick release polyethylene terephthalate (PET) film, and dried at 140°C for 10 minutes to produce a 100 μm-thick adhesive membrane. The adhesive film forming composition of Comparative Example 16 and Comparative Example 17 was melted and stirred at 300° C. for 5 minutes, and then extruded from a slit having a width of 100 μm to produce an adhesive film (extruded sheet).

(Composition of the composition for film formation) · A component: A component described in Table 3, a part by mass shown in Table 3 · B component: a B component described in Table 3, a part by mass shown in Table 3 ·Solvent: Solvents listed in Table 3, parts by mass shown in Table 3

<Preparation of the test piece> The surface of the adhesive support 2 on the side where the adhesive layer is formed and the Si wafer with a diameter of 100 mm were crimped under vacuum at 190°C and 0.11 MPa for 3 minutes to produce Test piece.

<Adhesiveness> The adhesiveness was evaluated by the same method and criteria as the adhesiveness evaluation in Test Example 1. <Peelability> The peelability was evaluated by the same method and criteria as the peelability evaluation in Test Example 1. <Removability (dissolution removal)> After the peeling test, the Si wafer with the adhesive layer is placed on the spin coater with the adhesive layer facing up, and the solvent described in Table 3 below is used as the cleaning solvent, and Spray the wafer for 5 minutes. Furthermore, spin drying is performed. After that, the appearance was observed and the presence or absence of the remaining adhesive layer was checked visually, and the evaluation was performed according to the following criteria. A: Remaining of the adhesive layer is not confirmed B: Remains of the adhesive layer is confirmed <Removability (membrane removal)> The removability (membrane removal) was evaluated by the same method and criteria as the removability (membrane removal) in Test Example 1 . <Wafer warpage> The wafer warpage was evaluated by the same method and criteria as the wafer warpage in Test Example 1.

[table 3]

From the above results, it is clear that when the temporary adhesive of the present invention is used, the adhesiveness and room temperature peeling properties are good. Furthermore, the releasability after heating and the removability of the adhesive layer are good, and the warpage of the wafer is suppressed. In addition, the warpage of the wafer of the example in which the elastic body X and the elastic body Y are used as the elastic body is more effectively suppressed.

1‧‧‧Substrate 2.12‧‧‧Support 3. 3A, 3B, 11, 11a～11d‧‧‧Continuous layer 60‧‧‧Component Wafer 60a‧‧‧Thin component wafer 61‧‧‧Silicon substrate 61a‧‧‧surface 61b, 61b1‧‧‧Back 62‧‧‧Component chip 63‧‧‧Structure 70‧‧‧Tape 100, 100a‧‧‧Adhesive support

Fig. 1 is a schematic view showing an embodiment of the laminate of the present invention. Fig. 2 is a schematic view showing another embodiment of the laminate of the present invention. 3(A) to 3(E) are schematic diagrams showing a first embodiment of a method of manufacturing a semiconductor device. 4(A) to 4(E) are schematic diagrams showing a second embodiment of the method of manufacturing a semiconductor device. 5(A) to 5(E) are schematic diagrams showing a third embodiment of the method of manufacturing a semiconductor device. 6 is a schematic cross-sectional view for explaining the release of the temporary bonding state between the conventional adhesive support and the element wafer.

60a: Thin component wafer

61: Silicon substrate

61a: surface

61b1: back

62: Component wafer

Claims (22)

A temporary adhesive, which contains: a compound that is liquid at 25°C and contains silicon atoms; and an elastomer containing a styrene-derived compound in a proportion of 50% by mass or more and 95% by mass or less in all repeating units The elastomer X of the repeating unit has a hardness of 83 or more based on the method of Japanese Industrial Standard K6253 and measured with a type A durometer, relative to the total amount of elastomer in the temporary adhesive The content of the silicon atom-containing compound is 0.2% by mass or more and less than 2.5% by mass, and the content of the elastomer in the temporary adhesive is 50.00% by mass to 99.99 relative to the mass of the temporary adhesive excluding the solvent % By mass, the amount of unsaturated double bonds of at least one of the elastomers contained in the temporary adhesive is less than 15 mmol/g, and at least one of the elastomers contained in the temporary adhesive is set at 20°C/min from 25°C The 5% thermal mass reduction temperature of the heating is 250°C or higher, and the compound containing silicon atoms is a compound represented by the following formula:

In the formula, R ¹ and R ² each independently represent a linear or branched alkyl group, a cycloalkyl group, an aromatic group or an organic group containing a polyether chain, and L ¹ represents -O- or a linking group containing a polyether chain . The temporary adhesive as described in item 1 of the scope of patent application, wherein the silicon atom-containing compound has a 10% thermal mass reduction temperature from 25°C at 20°C/min of 250°C or higher. The temporary adhesive as described in item 1 or item 2 of the scope of patent application, which further includes elastomer Y containing styrene-derived repeating units in a ratio of 10% by mass or more and less than 50% by mass in all repeating units . The temporary adhesive as described in item 3 of the scope of patent application, wherein the mass ratio of the elastomer X to the elastomer Y is 5:95 to 95:5. The temporary adhesive as described in item 1 or item 2 of the scope of patent application, wherein the amount of unsaturated double bonds of at least one elastomer contained in the temporary adhesive is 7 mmol/g or less. The temporary adhesive according to item 1 or item 2 of the scope of the patent application, wherein at least one of the elastomers contained in the temporary adhesive is a hydride. The temporary adhesive according to item 1 or 2 of the scope of patent application, wherein at least one of the elastomers contained in the temporary adhesive is a block copolymer. The temporary adhesive agent according to the first or second item of the scope of the patent application, wherein at least one of the elastomers contained in the temporary adhesive agent is a block copolymer derived from styrene at one end or both ends. Such as the temporary adhesive described in item 1 or item 2 of the scope of patent application, The silicon atom-containing compound is selected from dimethyl polysiloxane, methyl phenyl polysiloxane, diphenyl polysiloxane and polyether modified polysiloxane. The temporary adhesive as described in item 1 or item 2 of the scope of the patent application further includes at least one of an antioxidant and a solvent. The temporary adhesive as described in item 1 or item 2 of the scope of patent application, wherein the temporary adhesive is a temporary adhesive for semiconductor device manufacturing. An adhesive film comprising: an adhesive layer containing the temporary adhesive according to any one of items 1 to 11 in the scope of the patent application. An adhesive support having an adhesive layer containing the temporary adhesive described in any one of the scope of the patent application to any one of items 1 to 11, and a support. A laminate having a support, an adhesive layer containing the temporary adhesive described in any one of items 1 to 11 in the scope of patent application, and a base material. The laminate according to claim 14, wherein the adhesive layer is located on the surface of the support, and the substrate is located on the surface of the adhesive layer on the opposite side of the support. The laminate according to claim 14, wherein the support, the adhesive layer, and the base material are layered in the order described, and between the support and the adhesive layer The second adhesive layer having a different composition. The laminated body according to claim 14, wherein the support, the adhesive layer, and the base material are laminated in the stated order, and there is and between the adhesive layer and the base material. The second adhesive layer having a different composition. The laminate according to claim 16, wherein the second adhesive layer includes an elastomer X containing repeating units derived from styrene in a ratio of 50% by mass or more and 95% by mass or less in all repeating units . The laminate according to claim 16, wherein the second adhesive layer includes elastomer Y containing styrene-derived repeating units in a ratio of 10% by mass or more and less than 50% by mass in all repeating units . The laminate according to claim 16, wherein the content of the compound that is liquid at 25°C and contains silicon atoms in the second adhesive layer is the amount contained in the adhesive layer at 25°C It is 10% by mass or less of the content of the compound containing silicon atoms in a liquid state. The laminated body according to the 14th patent application, wherein the substrate is a device wafer. An adhesive kit comprising: a temporary adhesive as described in any one of items 1 to 11 in the scope of the patent application; and a second adhesive containing 50% by mass or more and 95% by mass in all repeating units The ratio of mass% or less contains elastomer X derived from a repeating unit of styrene, and is different from the composition of the temporary adhesive.

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