WO2016194917A1

WO2016194917A1 - Adhesive for temporary fixing, adhesive film, adhesive supporting body, laminate and kit

Info

Publication number: WO2016194917A1
Application number: PCT/JP2016/066089
Authority: WO
Inventors: 悠岩井; 義貴加持
Original assignee: 富士フイルム株式会社
Priority date: 2015-06-01
Filing date: 2016-06-01
Publication date: 2016-12-08
Also published as: KR102045770B1; TW201643230A; JP6588094B2; JPWO2016194917A1; TWI732764B; KR20170139609A

Abstract

Provided are: an adhesive for temporary fixing, which has excellent releasability at room temperature, while having excellent bondability; and an adhesive film, an adhesive supporting body, a laminate and a kit, each of which uses this adhesive for temporary fixing. An adhesive for temporary fixing, which contains: a compound that is in a liquid state at 25°C and contains a silicon atom; and an elastomer X that contains a repeating unit derived from styrene at a ratio of from 50% by mass to 95% by mass (inclusive) relative to all the repeating units.

Description

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

The present invention relates to a temporary fixing adhesive, an adhesive film, an adhesive support, a laminate, and a kit. More specifically, the present invention relates to a temporary fixing adhesive, an adhesive film, an adhesive support, a laminate, and a kit that can be preferably used for manufacturing a semiconductor device or the like.

In a manufacturing process of a semiconductor device such as an IC (Integrated Circuit) or an LSI (Large Scale Integrated Circuit), a large number of IC chips are formed on a device wafer and separated into pieces by dicing.
With the need for further miniaturization and higher performance of electronic equipment, further miniaturization and higher integration are required for IC chips mounted on electronic equipment. High integration is approaching its limit.

As an electrical connection method from an integrated circuit in an IC chip to an external terminal of the IC chip, a wire bonding method has been widely known. However, in recent years, in order to reduce the size of an IC chip, a device wafer is used. A method is known in which a through-hole is provided in the semiconductor device and a metal plug as an external terminal is connected to an integrated circuit so as to pass through the through-hole (so-called silicon through electrode (TSV) forming method). However, only the method of forming the through silicon vias cannot sufficiently meet the above-described needs for higher integration of the recent IC chip.

In view of the above, a technique for improving the degree of integration per unit area of a device wafer by multilayering an integrated circuit in an IC chip is known. However, since the multilayered integrated circuit increases the thickness of the IC chip, it is necessary to reduce the thickness of the members constituting the IC chip. For example, the thinning of the device wafer is being considered as a thinning of such a member, which not only leads to the miniaturization of the IC chip, but also saves the process of manufacturing the through hole of the device wafer in the production of the silicon through electrode. Because it is possible, it is considered promising. In addition, thinning of semiconductor devices such as power devices and image sensors has been attempted from the viewpoint of improving the degree of integration and improving the degree of freedom of the device structure.

A device wafer having a thickness of about 700 to 900 μm is widely known, but in recent years, for the purpose of reducing the size of an IC chip or the like, the thickness of the device wafer can be reduced to 200 μm or less. Has been tried.
However, since a device wafer having a thickness of 200 μm or less is very thin and a semiconductor device manufacturing member based on the device wafer is very thin, such a member may be further processed, or When the member is simply moved, it is difficult to support the member stably and without damage.

In order to solve the above-mentioned problems, the device wafer and the support body before thinning provided with devices on the surface are temporarily bonded with a temporary fixing adhesive, and the back surface of the device wafer is ground and thinned, A technique for peeling the support is known.
For example, Patent Document 1 discloses an adhesive composition having a polystyrene-based elastomer and a surface modifier.
Patent Document 2 discloses a temporary fixing material containing a cycloolefin 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 adhesion between a device wafer and a support substrate, and a material containing fluorine atoms and / or silicon atoms is used for the release layer.

US 2014/0178701 A1 JP 2013-241568 A Japanese Patent Laying-Open No. 2015-065401

However, as a result of investigation by the present inventor, the adhesive composition described in Patent Document 1 and the temporary fixing material described in Patent Document 2 peel the device wafer from the support at room temperature after thinning the device wafer. I found it difficult. Further, usually, when trying to improve the peelability, the adhesiveness tends to be inferior.
The present invention is intended to solve such a problem, is excellent in peelability at room temperature, and has a temporary adhesive that is excellent in adhesiveness, and the above temporary adhesive. An object is to provide an adhesive film, an adhesive support, a laminate, and a kit.

As a result of intensive studies by the present inventors under the above-mentioned problems, by blending a styrene-based elastomer having a large proportion of repeating units derived from styrene with a liquid at 25 ° C. and containing a silicon atom, It has been found that the above problems can be solved, and the present invention has been completed.
Specifically, the above problem has been solved by the following means <1>, preferably by the following means <2> to <25>.
<1> Contains a compound containing silicon atoms and an elastomer X containing a repeating unit derived from styrene in a proportion of 50% by mass or more and 95% by mass or less in all repeating units, which is liquid at 25 ° C. Temporary adhesive.
<2> The temporary fixing adhesive according to <1>, wherein the compound containing the silicon atom has a 10% thermal mass reduction temperature of 250 ° C. or higher which is increased from 25 ° C. at 20 ° C./min.
<3> The temporary adhesive according to <1> or <2>, wherein the elastomer X has a hardness measured by a type A durometer according to the method of JIS K6253 of 80 or more.
<4> The temporary fixing adhesive according to any one of <1> to <3>, further comprising an elastomer Y containing a repeating unit derived from styrene in a proportion of 10% by mass or more and less than 50% by mass in all repeating units. Agent.
<5> The temporary fixing adhesive according to <4>, wherein the mass ratio of the elastomer X to the elastomer Y is 5:95 to 95: 5.
<6> At least one of the elastomers included in the temporary fixing adhesive has a 5% thermal mass reduction temperature of 250 ° C. or higher, increased from 25 ° C. at 20 ° C./min, <1> to <5 > The temporary fixing adhesive in any one of>.
<7> The temporary fixing adhesive according to any one of <1> to <6>, wherein the amount of unsaturated double bonds of at least one of the elastomers included in the temporary fixing adhesive is 7 mmol / g or less .
<8> The temporary fixing adhesive according to any one of <1> to <7>, wherein at least one of the elastomers included in the temporary fixing adhesive is a hydrogenated product.
<9> The temporary fixing adhesive according to any one of <1> to <8>, wherein at least one of the elastomers included in the temporary fixing adhesive is a block copolymer.
<10> The temporary fixing according to any one of <1> to <9>, wherein at least one of the elastomers included in the temporary fixing adhesive is a block copolymer derived from styrene at one or both ends. adhesive.
<11> Any one of <1> to <10>, wherein the content of the compound containing silicon atoms is 0.01% by mass or more and less than 2.5% by mass with respect to the total amount of the elastomer in the temporary fixing adhesive Temporary tack adhesive according to crab
<12> The temporary fixing according to any one of <1> to <11>, wherein the compound containing a silicon atom is selected from dimethylpolysiloxane, methylphenylpolysiloxane, diphenylpolysiloxane, and polyether-modified polysiloxane adhesive.
<13> The temporary fixing adhesive according to any one of <1> to <12>, further comprising at least one of an antioxidant and a solvent.
<14> The temporary fixing adhesive according to any one of <1> to <13>, wherein the temporary fixing adhesive is a temporary fixing adhesive for manufacturing a semiconductor device.
<15> An adhesive film having an adhesive layer made of the temporary fixing adhesive according to any one of <1> to <14>.
<16> An adhesive support comprising an adhesive layer comprising the temporary fixing adhesive according to any one of <1> to <14>, and a support.
<17> A laminate comprising a support, an adhesive layer comprising the temporary fixing adhesive according to 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 base material is located on the surface of the adhesive layer opposite to the support.
<19> A second adhesive in which the support, the adhesive layer, and the base material are laminated in the order described above, and the composition of the adhesive layer is different between the support and the adhesive layer. The laminate according to <17>, having a layer.
<20> A second adhesive layer in which the support, the adhesive layer, and the base material are laminated in the order described above, and the composition of the adhesive layer is different between the adhesive layer and the base material. The laminate according to <17>, comprising:
<21> The second adhesive layer according to <19> or <20>, wherein the second adhesive layer includes an elastomer X containing a repeating unit derived from styrene in a ratio of 50% by mass to 95% by mass in all repeating units. Laminated body.
<22> Any one of <19> to <21>, wherein the second adhesive layer includes an elastomer Y containing a repeating unit derived from styrene in a proportion of 10% by mass or more and less than 50% by mass in all repeating units. The laminated body as described in.
<23> The content of the compound that is liquid at 25 ° C. and contains silicon atoms in the second adhesive layer is liquid at 25 ° C. contained in the adhesive layer, and includes silicon atoms. The laminate according to any one of <19> to <22>, which is 10 mass% or less of the content of the compound to be contained.
<24> The laminate according to any one of <17> to <23>, wherein the substrate is a device wafer.
<25> A temporary fixing adhesive according to any one of <1> to <14>, and an elastomer X containing a repeating unit derived from styrene in a proportion of 50% by mass or more and 95% by mass or less in all repeating units. And a kit having a second adhesive having a composition different from that of the temporary adhesive.

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

It is the schematic which shows one Embodiment of the laminated body of this invention. It is the schematic which shows other embodiment of the laminated body of this invention. It is the schematic of 1st embodiment which shows the manufacturing method of a semiconductor device. It is the schematic of 2nd embodiment which shows the manufacturing method of a semiconductor device. It is the schematic of 3rd embodiment which shows the manufacturing method of a semiconductor device. It is a schematic sectional drawing explaining cancellation | release of the temporary adhesion state of the conventional adhesive support body and a device wafer.

Hereinafter, the contents of the present invention will be described in detail. In the present specification, “to” is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value.
In the description of the group (atomic group) in this specification, the description which does not describe substitution and non-substitution includes what does not have a substituent and what has a substituent. For example, the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
“Actinic light” or “radiation” in the present specification means, for example, those including visible light, ultraviolet rays, far ultraviolet rays, electron beams, X-rays and the like.
In this specification, “light” means actinic rays or radiation.
In this specification, “exposure” means not only exposure using a mercury lamp, ultraviolet rays, far ultraviolet rays typified by excimer laser, X-ray, EUV light (Extreme Ultra-Violet), etc. Also includes drawing using a particle beam such as a beam and an ion beam.
In the present specification, “(meth) acrylate” represents acrylate and methacrylate, “(meth) acryl” represents acryl and methacryl, and “(meth) acryloyl” represents acryloyl and methacryloyl.
In this specification, a weight average molecular weight and a number average molecular weight are defined as a polystyrene conversion value in gel permeation chromatography (GPC) measurement. In this specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are, for example, HLC-8220 (manufactured by Tosoh Corporation), and TSKgel Super AWM-H (manufactured by Tosoh Corporation, 6) as a column. 0.0 mm (inner diameter) × 15.0 cm) can be obtained by using a 10 mmol / L lithium bromide NMP (N-methylpyrrolidinone) solution as an eluent.
In the present specification, the “lipophilic group” means a functional group that does not contain a hydrophilic group. Further, the “hydrophilic group” means a functional group showing affinity with water.
In the embodiments described below, the members and the like described in the drawings already referred to are denoted by the same or corresponding reference numerals in the drawings, and the description is simplified or omitted.

<Temporary adhesive>
The temporary fixing adhesive of the present invention is a liquid at 25 ° C. and contains a silicon atom-containing compound (hereinafter sometimes referred to as “silicon-based liquid compound”) and a repeating unit derived from styrene as all repeating units. And elastomer X contained in a proportion of 50% by mass or more and 95% by mass or less.
According to the temporary fixing adhesive of the present invention, when performing mechanical or chemical treatment on a substrate such as a device wafer, the substrate can be stably temporarily bonded, and temporary bonding to the substrate can be performed. An adhesive layer that can be easily released can be formed.
Since the temporary fixing adhesive of the present invention contains the above-described silicon-based liquid compound, the silicon-based liquid compound is likely to be unevenly distributed 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. it can. Therefore, even if the amount of the silicon-based liquid compound is relatively small with respect to the solid content of the temporary fixing adhesive, an adhesive layer having excellent peelability with respect to the substrate and the support can be formed.
Moreover, since the elastomer X which contains the repeating unit derived from styrene in the ratio of 50 mass% or more and 95 mass% or less in all the repeating units is included, it is derived from the elastomer X in a part or all of the adhesive layer made of the temporary fixing adhesive. A hard region is formed and the peelability is improved.
The temporary fixing adhesive of the present invention can be particularly preferably used as a temporary fixing adhesive for manufacturing a semiconductor device.
Hereinafter, the temporary fixing adhesive of the present invention will be specifically described.

<< Silicon-based liquid compound >>
The temporary fixing adhesive of the present invention contains a silicon-based liquid compound.
In the present invention, the liquid state means a compound having fluidity at 25 ° C. and having a viscosity of 1 to 100,000 mPa · s at 25 ° C., for example. The viscosity of the silicon-based liquid compound at 25 ° C. is more preferably 10 to 20,000 mPa · s, and still more preferably 100 to 15,000 mPa · s. When the viscosity of the silicon-based liquid compound is within the above range, the silicon-based liquid compound is more likely to be unevenly distributed in the surface layer of the adhesive layer, which is preferable.

In the present invention, the silicon-based liquid compound can be preferably used in any form of oligomer or polymer. Moreover, the mixture of an oligomer and a polymer may be sufficient. Such a mixture may further contain a monomer. The silicon-based liquid compound may be a monomer.
The silicon-based liquid compound is preferably an oligomer, a polymer, or a mixture thereof from the viewpoint of heat resistance and the like.
As the oligomer and polymer, for example, an addition polymer, a polycondensate, an addition condensate and the like can be used without particular limitation, but a polycondensate is particularly preferable.
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 denature during the treatment of the base material used for temporary adhesion. For example, a compound that can exist in a liquid state even after heating at 250 ° C. or higher or treating the substrate with various chemical solutions is preferable. As a specific example, the viscosity at 25 ° C. is 1 to 100,000 mPa · s after heating to 250 ° C. under a temperature rising condition of 10 ° C./min from a state of 25 ° C. It is preferably 10 to 20,000 mPa · s, more preferably 100 to 15,000 mPa · s.
The silicon-based liquid compound having such characteristics is preferably a non-thermosetting compound having no reactive group. The reactive group here refers to all groups that react by heating at 250 ° C., and examples thereof include a polymerizable group and a hydrolyzable group. Specifically, a (meth) acryl group, an epoxy group, an isocyanato group, etc. are mentioned, for example.
Further, the silicon-based liquid compound preferably has a 10% thermal mass decrease temperature of 250 ° C. or higher, more preferably 280 ° C. or higher, which is heated from 25 ° C. at 20 ° C./min. Moreover, although an upper limit does not have limitation in particular, For example, 1000 degrees C or less is preferable and 800 degrees C or less is more preferable. According to this aspect, it is easy to form an adhesive layer having excellent heat resistance. In addition, mass decreasing temperature is a value measured on the said temperature rising conditions in nitrogen stream by the thermogravimetry apparatus (TGA).

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, and aromatic groups.

The alkyl group preferably has 1 to 30 carbon atoms, more preferably 1 to 10 carbon atoms, and still more preferably 1 to 3 carbon atoms. Specific examples of alkyl groups include, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tetradecyl, octadecyl, isopropyl Group, isobutyl group, sec-butyl group, tert-butyl group, 1-ethylpentyl group, 2-ethylhexyl group.
The alkyl group may have a substituent. Examples of the substituent include a halogen atom, an alkoxy group, and an aromatic group. Examples of the halogen atom include a chlorine atom, a fluorine atom, a bromine atom, and an iodine atom, and a fluorine atom is preferable.
The alkoxy group preferably has 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and still more preferably 1 to 10 carbon atoms. The alkoxy group is preferably linear or branched.
The aromatic group may be monocyclic or polycyclic. The carbon number of the aromatic group is preferably 6 to 20, more preferably 6 to 14, and particularly preferably 6 to 10.

The cycloalkyl group may be monocyclic or polycyclic. The cycloalkyl group preferably has 3 to 30 carbon atoms, more preferably 4 to 30 carbon atoms, still more preferably 6 to 30 carbon atoms, and particularly preferably 6 to 20 carbon atoms. Examples of the monocyclic cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group. Examples of the polycyclic cycloalkyl group include adamantyl group, norbornyl group, bornyl group, camphenyl group, decahydronaphthyl group, tricyclodecanyl group, tetracyclodecanyl group, camphoroyl group, dicyclohexyl group and pinenyl group. Can be mentioned.
The cycloalkyl group may have the substituent described above.

The aromatic group may be monocyclic or polycyclic. The carbon number of the aromatic group is preferably 6 to 20, more preferably 6 to 14, and particularly preferably 6 to 10. It is preferable that the aromatic group does not contain a hetero atom (for example, a nitrogen atom, an oxygen atom, a sulfur atom, etc.) in the elements constituting the ring. Specific examples of the aromatic group include benzene ring, naphthalene ring, pentalene ring, indene ring, azulene ring, heptalene ring, indecene ring, perylene ring, pentacene ring, acenaphthene ring, phenanthrene ring, anthracene ring, naphthacene ring, chrysene ring , Triphenylene ring, fluorene ring, biphenyl ring, pyrrole ring, furan ring, thiophene ring, imidazole ring, thiazole ring, thiazole ring, pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, indolizine ring, indole ring, benzofuran ring, Benzothiophene ring, isobenzofuran ring, quinolidine ring, quinoline ring, phthalazine ring, naphthyridine ring, quinoxaline ring, quinoxazoline ring, isoquinoline ring, carbazole ring, phenanthridine ring, acridine ring, phenanthroline ring, thia Train ring, chromene ring, xanthene ring, phenoxathiin ring, a phenothiazine ring, and include phenazine ring, a benzene ring is preferred.
The aromatic group may have the above-described substituent. As the substituent, a linear alkyl group is preferable.

The silicon-based liquid compound is preferably a compound represented by the following general formula.

R ¹ and R ² in the above general formula are each independently a linear or branched alkyl group, cycloalkyl group or aromatic group, and one of R ¹ and R ² is an organic group containing a polyether chain. It may be.
L ¹ represents —O— or a linking group containing a polyether chain.

The preferred range of the linear or branched alkyl group, cycloalkyl group or aromatic group as R ¹ and R ² in the above general formula is the linear or branched alkyl group described for the lipophilic group. And the same as the preferable range.
In the above general formula, one of R ¹ and R ² is preferably an organic group containing a polyether chain. The polyether structure in the organic group containing a polyether chain is not particularly limited as long as it has a structure having a plurality of ether bonds. For example, polyethylene glycol structure (polyethylene oxide structure), polypropylene glycol structure (polypropylene oxide structure) And polyoxyalkylene structures such as polybutylene glycol (polytetramethylene glycol) structures and polyether structures derived from multiple types of alkylene glycol (or alkylene oxide) (for example, poly (propylene glycol / ethylene glycol) structures). It is done. In addition, the addition form of each alkylene glycol in the polyether structure derived from a plurality of types of alkylene glycols may be a block type (block copolymer type) or a random type (random copolymer type). Also good.

The organic group containing the polyether chain may be an organic group consisting only of the polyether structure, or one or two or more of the polyether structure and one or two or more linking groups (one or more atoms may be bonded). It may be an organic group having a structure in which a divalent group) is linked. Examples of the linking group in the organic group containing a polyether chain include, for example, a divalent hydrocarbon group (particularly, a linear or branched alkylene group), a thioether group (—S—), an ester group (—COO—). ), An amide group (—CONH—), a carbonyl group (—CO—), a carbonate group (—OCOO—), a group in which two or more of these are bonded, and the like.

Further, the polyether chain of L ¹ in the above general formula is not particularly limited as long as it has a structure having a plurality of the ether bonds described above, but a structure having a plurality of the ether bonds described above can be preferably used. Further, the polyether chain may be an organic group consisting of only a polyether structure, or one or two or more of the above polyether structure and one or two or more linking groups (a divalent having one or more atoms). And an organic group having a structure in which the group) is linked. Examples of the linking group in the organic group containing a polyether chain include, for example, a divalent hydrocarbon group (particularly, a linear or branched alkylene group), a thioether group (—S—), an ester group (—COO—). ), An amide group (—CONH—), a carbonyl group (—CO—), a carbonate group (—OCOO—), a group in which two or more of these are bonded, and the like.

The silicon-based liquid compound in the present invention is more preferably at least one selected from dimethylpolysiloxane, methylphenylpolysiloxane, diphenylpolysiloxane, and polyether-modified polysiloxane.

Examples of silicon-based liquid compounds include JP-A-62-36663, JP-A-61-226746, JP-A-61-226745, JP-A-62-170950, JP-A-63-34540, Of the surfactants described in Kaihei 7-230165, JP-A-8-62834, JP-A-9-54432, JP-A-9-5988 and JP-A-2001-330953, those which are liquid at 25 ° C. Can be mentioned.
Commercially available products include “BYK-300”, “BYK-301 / 302”, “BYK-306”, “BYK-307”, “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-SILCLEAN3 00 ”,“ BYK-SILCLEAN3720 ”(above, manufactured by Big Chemie Japan Co., Ltd.), trade names“ AC FS 180 ”,“ AC FS 360 ”,“ AC S 20 ”(above, made by Algin Chemie), trade name“ "Polyflow KL-400X", "Polyflow KL-400HF", "Polyflow KL-401", "Polyflow KL-402", "Polyflow KL-403", "Polyflow KL-404", "Polyflow KL-700" Kyoeisha Chemical Co., Ltd.), 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-650 "," KP-651 "," KP-390 "," KP-391 "," KP-392 " (Shin-Etsu Chemical Co., Ltd.), trade names “LP-7001”, “LP-7002”, “SH28PA”, “8032 ADDIIVE”, “57 ADDIIVE”, “L-7604”, “FZ-” "2110", "FZ-2105", "67 ADDITIVE", "8618 ADDITIVE", "3 ADDITIVE", "56 ADDITIVE" (above, manufactured by Toray Dow Corning Co., Ltd.), " EGO WET 270 "(manufactured by Evonik Degussa Japan Co., Ltd.), can be used commercially available products such as" NBX-15 "(manufactured by Neos Co., Ltd.).

The content of the silicon-based liquid compound in the temporary fixing adhesive of the present invention is preferably 0.009% by mass or more and 0.01% by mass or more with respect to the total amount of elastomer contained in the temporary fixing adhesive. More preferably, 0.05% by mass or more is further preferable, 0.1% by mass or more is particularly preferable, and 0.2% by mass or more is even more preferable. The upper limit is preferably 10% by mass or less, more preferably 5% by mass or less, more preferably less than 2.5% by mass, and even more preferably 1% by mass or less. Preferably, it is 0.6% by mass or less.
If content of a silicon-type liquid compound is the said range, it is excellent by adhesiveness and peelability. In particular, the present invention is highly valuable in that the effects of the present invention can be achieved even if the amount of the temporary fixing adhesive is small.
One silicon-based liquid compound may be used alone, or two or more silicon-based liquid compounds may be used in combination. When using 2 or more types together, it is preferable that total content is the said range.

<< Elastomer >>
The temporary fix adhesive of the present invention contains an elastomer. By using an elastomer, it is possible to form an adhesive layer having excellent adhesiveness by following the fine irregularities of the support and the base material and by an appropriate anchor effect. Moreover, when peeling a support body from a base material, a support body can be peeled from a base material, without applying stress to a base material etc., and damage or peeling of the device etc. on a base material can be prevented.
In addition, in this specification, an elastomer represents the high molecular compound which shows elastic deformation. That is, when an external force is applied, the polymer compound is defined as a polymer compound that has the property of instantly deforming according to the external force and recovering the original shape in a short time when the external force is removed.

The elastomer included as an essential component in the present invention is an elastomer X containing a repeating unit derived from styrene in a proportion of 50% by mass or more and 95% by mass or less in all repeating units, and further, repeating units derived from styrene are all repeated. It is also preferable to include the elastomer Y contained in the unit at a ratio of 10% by mass or more and less than 50% by mass.
By using the elastomer X and the elastomer Y in combination, while having excellent peelability, the flatness of the polished surface of the substrate (hereinafter also referred to as flat polishing property) is good, and the warpage of the substrate after polishing is improved. Generation can be effectively suppressed. The mechanism by which such an effect is obtained can be assumed to be as follows.
That is, since the elastomer X is a relatively hard material, an adhesive layer having excellent peelability can be produced by including the elastomer X. In addition, since the elastomer Y is a relatively soft material, it is easy to form an adhesive layer having elasticity. For this reason, when manufacturing the laminated body of a base material and a support using the temporary fixing adhesive of the present invention, and polishing the base material into a thin film, even if pressure during polishing is locally applied, The adhesive layer can be easily elastically deformed to return to the original shape. As a result, excellent flat polishing properties can be obtained. Further, even if the laminated body after polishing is subjected to heat treatment and then cooled, the adhesive layer can relieve internal stress generated during cooling and effectively suppress the occurrence of warpage.
Moreover, even if the elastomer Y is blended with the elastomer X, the excellent peelability by the elastomer X is sufficiently achieved due to the presence of a region where the elastomer X is phase-separated.

Hereinafter, preferable conditions common to the elastomer X and the elastomer Y (they 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. For example, styrene-butadiene-styrene block copolymer (SBS), styrene-isoprene-styrene block copolymer (SIS), styrene-ethylene-butylene-styrene block copolymer (SEBS), styrene-butadiene-butylene-styrene. Examples thereof include copolymers (SBBS) and hydrogenated products thereof, styrene-ethylene-propylene-styrene block copolymers (SEPS), and styrene-ethylene-ethylene-propylene-styrene block copolymers.

The weight average molecular weight of the polystyrene-based elastomer is preferably from 2,000 to 200,000, more preferably from 10,000 to 200,000, and even more preferably from 50,000 to 100,000. By being in this range, the solubility of the temporary fixing adhesive in a solvent will be excellent, and the applicability will be improved. In addition, when the remaining adhesive layer is removed after peeling the substrate from the support, there is an advantage that no residue remains on the substrate or the support because of excellent solubility in a solvent.

In the present invention, examples of the polystyrene-based elastomer include block copolymers, random copolymers, and graft copolymers. Block copolymers are preferred, and one or both ends are block copolymers of styrene. Is more preferable, and it is particularly preferable that both ends are block copolymers of styrene. If both ends of the polystyrene-based elastomer are made of a styrene block copolymer (a repeating unit derived from styrene), the thermal stability tends to be further improved. This is because a repeating unit derived from styrene having high heat resistance is present at the terminal. In particular, the block part of the repeating unit derived from styrene is preferably a reactive polystyrene hard block, which tends to be more excellent in heat resistance and chemical resistance. Moreover, when these are made into a block copolymer, it is thought that phase-separation by a hard block and a soft block will be performed at 200 degreeC or more. The shape of the phase separation is considered to contribute to the suppression of the occurrence of irregularities on the substrate surface of the device wafer. In addition, such a resin is more preferable from the viewpoint of solubility in a solvent and resistance to a resist solvent.

In the present invention, the polystyrene elastomer is preferably a hydrogenated product. When the polystyrene-based elastomer is a hydrogenated product, thermal stability and storage stability are improved. Furthermore, the peelability and the cleaning / removability of the adhesive layer after peeling are improved. The hydrogenated product means a polymer having a structure in which an elastomer is hydrogenated (hydrogenated).

The polystyrene elastomer has a 5% thermal mass reduction temperature of 25 ° C. raised at 20 ° C./min, preferably 250 ° C. or higher, more preferably 300 ° C. or higher, and 350 ° C. or higher. Is more preferable, and it is especially preferable that it is 400 degreeC or more. Moreover, although an upper limit is not specifically limited, For example, 1000 degrees C or less is preferable and 800 degrees C or less is more preferable. According to this aspect, it is easy to form an adhesive layer having excellent heat resistance.
Polystyrene elastomer can be deformed up to 200% with a small external force at room temperature (20 ° C.) when the original size is 100%, and within 130% or less in a short time when the external force is removed. It preferably has a returning property.

The amount of unsaturated double bonds in the polystyrene-based elastomer is preferably less than 15 mmol / g, more preferably less than 7 mmol / g, and less than 5 mmol / g from the viewpoint of peelability after the heating step. More preferably, it is more preferably less than 0.5 mmol / g. The lower limit is not particularly defined, but can be, for example, 0.001 mmol / g or more.
In addition, the amount of unsaturated double bonds here does not include the unsaturated double bond in the benzene ring derived from styrene. The amount of unsaturated double bonds can be calculated by nuclear magnetic resonance (NMR) measurement.

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

Examples of commercially available polystyrene elastomers include Tufprene A, Tufprene 125, Tufprene 126S, Solprene T, Asaprene T-411, Asaprene T-432, Asaprene T-437, Asaprene T-438, Asaprene T-439, Tuftec H1272 Tuftec P1500, Tuftec H1052, Tuftec H1062, Tuftec M1943, Tuftec M1911, Tuftec H1041, Tuftec MP10, Tuftec M1913, Tuftec H1051, Tuftech H1053, Tuftec P2000, Tuftec H1043 (trade name, manufactured by Asahi Kasei Elastomer Co., Ltd.) AR-850C, Elastomer AR-815C, Elastomer AR-840C, Elastomer AR-830C, Elasto -AR-860C, Elastomer AR-875C, Elastomer AR-885C, Elastomer AR-SC-15, Elastomer AR-SC-0, Elastomer AR-SC-5, Elastomer AR-710, Elastomer AR-SC-65, Elastomer AR -SC-30, Elastomer AR-SC-75, Elastomer AR-SC-45, Elastomer AR-720, Elastomer AR-741, Elastomer AR-731, Elastomer AR-750, Elastomer AR-760, Elastomer AR-770, Elastomer AR-781, Elastomer AR-791, Elastomer AR-FL-75N, Elastomer AR-FL-85N, Elastomer AR-FL-60N, Elastomer AR-1050, Elastomer AR-1060 Elastomer AR-1040 (trade name, manufactured by Aron Kasei), Clayton D1111, Clayton D1113, Clayton D1114, Clayton D1117, Clayton D1119, Clayton D1124, Clayton D1126, Clayton D1161, Clayton D1162, Clayton D1163, Clayton D1164, Clayton D1165 Clayton D1183, Clayton D1193, Clayton DX406, Clayton D4141, Clayton D4150, Clayton D4153, Clayton D4158, Clayton D4271, Clayton D 4433, Clayton D 1170, Clayton D 1171, Clayton D 1173, Califlex IR0307 Flex IR 0310, Califlex IR 0401, Clayton D0242, Clayton D1101, Clayton D1102, Clayton D1116, Clayton D1118, Clayton D1133, Clayton D1152,

Clayton D1153, Clayton D1155, Clayton D1184, Clayton D1186, Clayton D1189, Clayton D1191, Clayton DX1192, Clayton DX405, Clayton DX410, Clayton DX414, Clayton DX415, Clayton A1535, Clayton FG1904, Clayton FG1904 G Clayton G1641, Clayton G1642, Clayton G1643, Clayton G1645, Clayton G1633, Clayton G1650, Clayton G1651, Clayton G1652, Clayton G1654, Clayton G1657, Clayton G1660, Clayton G1726, Clayton G1701, Iton G1702, Clayton G1730, Clayton G1750, Clayton G1765, Clayton G4609, Clayton G4610 (above, trade name, manufactured by Kraton), TR2000, TR2001, TR2003, TR2250, TR2500, TR2601, TR2630, TR2787, TR2827, TR1086, TR1600, SIS5002, SIS5200, SIS5250, SIS5405, SIS5505, Dynalon 6100P, Dynalon 4600P, Dynalon 6200P, Dynalon 4630P, Dynalon 8601P, Dynalon 8630P, Dynalon 8600P, Dynalon 8903P, Dynalon 13201P, Dynalon 1321P, Dynalon 1321P Ron 9901P (trade name, manufactured by JSR Corporation), Denka STR series (trade name, manufactured by Denki Kagaku Kogyo Co., Ltd.), Quintac 3520, Quintac 3433N, Quintac 3421, Quintac 3620, Quintac 3450 , Quintac 3460 (above, trade name, manufactured by Zeon Corporation), TPE-SB series (above, trade name, manufactured by Sumitomo Chemical Co., Ltd.), Lavalon series (trade name, manufactured by Mitsubishi Chemical Corporation), Septon 1001, Septon, 8004, septon 4033, septon 2104, septon 8007, septon 2007, septon 2004, septon 2063, septon HG252, septon 8076, septon 2002, septon 1020, septon 8104, septon 2005, septon 2006, septon 4055, septe 4044, Septon 4077, Septon 4099, Septon 8006, Septon V9461, Septon V9475, Septon V9827, Hibler 7311, Hibler 7125, Hibler 5127, Hibler 5125 (above, trade name, manufactured by Kuraray), Sumiflex (trade name, Sumitomo Bakelite) (Manufactured by Riken Vinyl Industry Co., Ltd.) and the like.

Next, a preferable range specific to “elastomer X” will be described.
Elastomer X is an elastomer containing a repeating unit derived from styrene in a proportion of 50% by mass to 95% by mass in all repeating units, and the content of the repeating unit derived from styrene exceeds 50% by mass and is 95% by mass. % Or more, more than 50% by weight, more preferably 90% by weight or less, more preferably more than 50% by weight and 80% by weight or less, particularly preferably 55 to 75% by weight, even more preferably 56 to 70% by weight. .
The hardness of the elastomer X is preferably 83 or greater, more preferably 85 or greater, and even more preferably 90 or greater. The upper limit value is not particularly defined, but is 99 or less, for example. The hardness is a value measured with a type A durometer according to the method of JIS (Japanese Industrial Standard) K6253.

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

In the present invention, an elastomer other than the elastomer X and the elastomer Y may be blended. Other elastomers that can be used include polyester elastomers, polyolefin elastomers, polyurethane elastomers, polyamide elastomers, polyacryl elastomers, silicone elastomers, polyimide elastomers, rubber-modified epoxy resins, and the like.

The total amount of elastomer X, elastomer Y and other elastomers in the temporary fixing adhesive of the present invention is preferably 50.00 to 99.99% by mass relative to the mass of the temporary fixing adhesive excluding the solvent. 00 to 99.99 mass% is more preferable, and 88.00 to 99.99 mass% is particularly preferable. If the content of the elastomer is in the above range, it is more excellent in adhesiveness and peelability.
In addition, the elastomer X, the elastomer Y, and the other elastomer in the temporary fixing adhesive of the present invention may be a plurality of combinations.

Of the elastomer content contained in the temporary adhesive of the present invention, the total amount of elastomer X and elastomer Y preferably accounts for 90% by mass or more, more preferably 95% by mass or more, 98 It is particularly preferable to occupy at least mass%.
When the elastomer Y is blended, the mass ratio of the elastomer X to the elastomer Y is preferably elastomer X: elastomer Y = 5: 95 to 95: 5, more preferably 20:80 to 90:10, and 40:60. ~ 85: 15 is particularly preferred. If it is the said range, curvature suppression and peelability will be obtained more effectively.

<< Antioxidant >>
The temporary tacking adhesive of the present invention may contain an antioxidant from the viewpoint of preventing low molecular weight and gelation of the elastomer due to oxidation during heating. As the antioxidant, a phenol-based antioxidant, a sulfur-based antioxidant, a phosphorus-based antioxidant, a quinone-based antioxidant, an amine-based antioxidant, and the like can be used.
Examples of phenolic antioxidants include para-methoxyphenol, 2,6-di-tert-butyl-4-methylphenol, “Irganox 1010”, “Irganox 1330”, “Irganox 3114”, “Irganox 1035” manufactured by BASF Corporation, Examples thereof include “Sumilizer MDP-S” and “Sumilizer GA-80” manufactured by Sumitomo Chemical Co., Ltd.
Examples of the sulfur-based antioxidant include 3,3′-thiodipropionate distearyl, “Sumilizer TPM”, “Sumilizer TPS”, “Sumilizer TP-D” manufactured by Sumitomo Chemical Co., Ltd., and the like.
Examples of phosphorus antioxidants include tris (2,4-di-tert-butylphenyl) phosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, and poly (dipropylene glycol) phenyl. Examples thereof include phosphite, diphenylisodecyl phosphite, 2-ethylhexyl diphenyl phosphite, triphenyl phosphite, “Irgafos 168” and “Irgafos 38” manufactured by BASF Corporation.
Examples of the quinone antioxidant include para-benzoquinone and 2-tert-butyl-1,4-benzoquinone.
Examples of amine-based antioxidants include dimethylaniline and phenothiazine.
Among the above-mentioned antioxidants, Irganox 1010,

Irganox

1330, 3,3′-thiodipropionate distearyl and Sumilizer TP-D are preferable, Irganox 1010 and Irganox 1330 are more preferable, and Irganox 1010 is particularly preferable.
Further, among the above antioxidants, it is preferable to use a phenol-based antioxidant and a sulfur-based antioxidant or a phosphorus-based antioxidant in combination, and a phenol-based antioxidant and a sulfur-based antioxidant are used in combination. It is particularly preferred. In particular, when a polystyrene-based elastomer is used as the elastomer, it is preferable to use a phenol-based antioxidant and a sulfur-based antioxidant in combination. By using such a combination, it can be expected that the deterioration of the elastomer due to the oxidation reaction can be efficiently suppressed. When a phenolic antioxidant and a sulfurous antioxidant are used in combination, the mass ratio of the phenolic antioxidant to the sulfurous antioxidant is: phenolic antioxidant: sulfurous antioxidant = 95: 5 to 5:95 is preferable, and 25:75 to 75:25 is more preferable.
As the combination of antioxidants, Irganox 1010 and Sumilizer TP-D, Irganox 1330 and Sumilizer TP-D, and Sumilizer GA-80 and Sumilizer TP-D are preferable, Irganox 1010 and Sumilizer TP-D, 13g More preferred are Irganox 1010 and Sumilizer TP-D.

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

In the case where the temporary adhesive has an antioxidant, the content of the antioxidant is preferably 0.001 to 20.0% by mass with respect to the total solid content of the temporary adhesive, and 0.005 to 10. 0 mass% is more preferable.
Only one type of antioxidant may be used, or two or more types may be used. When there are two or more antioxidants, the total is preferably in the above range.

<< Solvent >>
The temporary fixing adhesive of the present invention preferably contains a solvent. In particular, when the adhesive layer is formed by applying the temporary adhesive of the present invention, it is preferable to add a solvent. Any 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, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, alkyl oxyacetate (examples) : Methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate (for example, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate)), 3-oxypropionic acid alkyl esters (example: 3 -Methyl oxypropionate, ethyl 3-oxypropionate, etc. (eg, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate)), 2-oxy Alkyl propionate Stealth (eg, methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, etc. (eg, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, Methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), methyl 2-oxy-2-methylpropionate and ethyl 2-oxy-2-methylpropionate (eg methyl 2-methoxy-2-methylpropionate) Ethyl 2-ethoxy-2-methylpropionate), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, 1-methoxy- Esters such as 2-propyl acetate
Diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol Ethers such as monoethyl ether acetate and propylene glycol monopropyl ether acetate;
Ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone, N-methyl-2-pyrrolidone, γ-butyrolactone;
Toluene, xylene, anisole, mesitylene, ethylbenzene, propylbenzene, cumene, n-butylbenzene, sec-butylbenzene, isobutylbenzene, tert-butylbenzene, amylbenzene, isoamylbenzene, (2,2-dimethylpropyl) benzene, 1 -Phenylhexane, 1-phenylheptane, 1-phenyloctane, 1-phenylnonane, 1-phenyldecane, cyclopropylbenzene, cyclohexylbenzene, 2-ethyltoluene, 1,2-diethylbenzene, o-cymene, indane, 1 , 2,3,4-tetrahydronaphthalene, 3-ethyltoluene, m-cymene, 1,3-diisopropylbenzene, 4-ethyltoluene, 1,4-diethylbenzene, p-cymene, 1,4-diisopropylbenzene, -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, Aromatic hydrocarbons such as 1,2,3,5-tetramethylbenzene, 1,2,4,5-tetramethylbenzene, pentamethylbenzene;
Preferable examples include hydrocarbons such as limonene, p-menthane, nonane, decane, dodecane and decalin.
Among these, mesitylene, tert-butylbenzene, 1,2,4-trimethylbenzene, p-menthane, γ-butyrolactone, anisole, methyl 3-ethoxypropionate, 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 are preferred, and mesitylene is more preferred.

These solvents are preferably mixed in two or more types from the viewpoint of improving the properties of the coated surface. In this case, particularly preferably, mesitylene, tert-butylbenzene, 1,2,4-trimethylbenzene, p-menthane, γ-butyrolactone, anisole, methyl 3-ethoxypropionate, 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 It is a mixed solution comprised by the above.

When the temporary fixing adhesive contains a solvent, the content of the temporary fixing adhesive is preferably such that the total solid concentration of the temporary fixing adhesive is 5 to 80% by mass from the viewpoint of applicability. Is more preferably from 50 to 50% by weight, particularly preferably from 15 to 40% by weight.
One type of solvent may be sufficient and 2 or more types may be sufficient as it. When there are two or more solvents, the total is preferably in the above range.
As will be described later, when the temporary adhesive of the present invention is used for an adhesive film or an adhesive layer of an adhesive support, the solvent content is preferably 1% by mass or less, and 0.1% by mass or less. More preferably, it is particularly preferable not to contain.

<< Radically polymerizable compound >>
The temporary fixing adhesive of the present invention preferably contains a radically polymerizable compound. By using a temporary fixing adhesive containing a radical polymerizable compound, it is easy to suppress fluid deformation of the adhesive layer during heating. For this reason, for example, in the case of heat-treating the laminate 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. Moreover, since the adhesive layer with hardness can be formed, even if a pressure is locally applied at the time of grinding | polishing of a base material, an adhesive layer cannot change easily and flat polishing property is excellent.

In the present invention, the radical polymerizable compound is a compound having a radical polymerizable group, and a known radical polymerizable compound that can be polymerized by a radical can be used. Such compounds are widely known in the art, and can be used without particular limitation in the present invention. These may be any of chemical forms such as monomers, prepolymers, oligomers or mixtures thereof and multimers thereof. As the radically polymerizable compound, the description in paragraphs 00099 to 080 of JP-A-2015-087611 can be referred to, and the contents thereof are incorporated in the present specification.

Examples of the radical polymerizable compound include urethane acrylates as described in JP-B-48-41708, JP-A-51-37193, JP-B-2-32293, and JP-B-2-16765. Also suitable are urethane compounds having an ethylene oxide skeleton as described in JP-B-58-49860, JP-B-56-17654, JP-B-62-39417, and JP-B-62-39418. Further, as radically polymerizable compounds, addition polymerization having an amino structure or a sulfide structure in the molecule described in JP-A-63-277653, JP-A-63-260909, and JP-A-1-105238 is described. Monomers can also be used.

Commercially available radical polymerizable compounds include urethane oligomers UAS-10, UAB-140 (manufactured by Sanyo Kokusaku Pulp Co., Ltd.), NK ester M-40G, NK ester 4G, NK ester A-9300, NK ester M-9300, NK Ester A-TMMT, NK ester A-DPH, NK ester A-BPE-4, UA-7200 (manufactured by Shin-Nakamura Chemical), DPHA-40H (manufactured by Nippon Kayaku), UA-306H, UA-306T, UA -306I, AH-600, T-600, AI-600 (manufactured by Kyoeisha Chemical Co., Ltd.), Blemmer PME400 (manufactured by NOF Corporation), and the like.

In the present invention, the radically polymerizable compound preferably has at least one of the partial structures represented by the following (P-1) to (P-4) from the viewpoint of heat resistance. More preferably, it has a partial structure represented. * In the formula is a connecting hand.

Specific examples of the radical polymerizable compound having the above partial structure include, for example, trimethylolpropane tri (meth) acrylate, isocyanuric acid ethylene oxide-modified di (meth) acrylate, isocyanuric acid ethylene oxide-modified tri (meth) acrylate, and isocyanuric acid. Triallyl, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dimethylolpropane tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tetramethylolmethanetetra ( (Meth) acrylates and the like, and in the present invention, these radically polymerizable compounds can be particularly preferably used.

In the temporary fixing adhesive of the present invention, the content in the case of adding a radical polymerizable compound is the mass of the temporary fixing adhesive excluding the solvent from the viewpoint of good adhesiveness, flat polishing property, peelability, and warpage suppression. The content is preferably 1 to 50% by mass, more preferably 1 to 30% by mass, and still more preferably 5 to 30% by mass. A radically polymerizable compound may be used alone or in combination of two or more.
In the temporary fixing adhesive of the present invention, the mass ratio of the elastomer and the radical polymerizable compound when the radical polymerizable compound is added is preferably elastomer: radical polymerizable compound = 98: 2 to 10:90, 95 : 5 to 30:70 is more preferable, and 90:10 to 50:50 is particularly preferable. When the mass ratio of the elastomer and the radical polymerizable compound is in the above range, an adhesive layer excellent in adhesiveness, flat polishing property, peelability and warpage suppression can be formed.

<< polymer compound >>
The temporary tacking adhesive of the present invention has a polymer compound other than the above-described silicon-based liquid compound and elastomer as necessary in order to adjust applicability, adhesiveness, releasability, heat resistance, and the like. May be. Here, the coating property means the uniformity of the film thickness after coating and the film forming property 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 the polymer compound include, for example, hydrocarbon resins, novolac resins, phenol resins, epoxy resins, melamine resins, urea resins, unsaturated polyester resins, alkyd resins, polyimide resins, polyvinyl chloride resins, and polyvinyl acetate resins. , Teflon (registered trademark), polyamide resin, polyacetal resin, polycarbonate resin, polyphenylene ether resin, polybutylene terephthalate resin, polyethylene terephthalate resin, polyphenylene sulfide resin, polysulfone resin, polyethersulfone resin, polyarylate resin, polyetheretherketone resin And polyamideimide resin. Among these, hydrocarbon resins, novolak resins, and polyimide resins are preferable, and hydrocarbon resins are more preferable. You may use a high molecular compound in combination of 2 or more type as needed.

Any hydrocarbon resin can be used.
The hydrocarbon resin basically means a resin consisting of only carbon atoms and hydrogen atoms, but if the basic skeleton is a hydrocarbon resin, it may contain other atoms as side chains. That is, when a functional group other than a hydrocarbon group is directly bonded to the main chain, such as an acrylic resin, a polyvinyl alcohol resin, a polyvinyl acetal resin, or a polyvinyl pyrrolidone resin, in addition to a hydrocarbon resin consisting of only carbon atoms and hydrogen atoms. Are also included in the hydrocarbon resin in the present invention. In this case, the content of the repeating unit in which the hydrocarbon group is directly bonded to the main chain is 30 mol% or more based on the entire repeating unit of the resin. Preferably there is.
Examples of the hydrocarbon resin meeting the above conditions include terpene resin, terpene phenol resin, modified terpene resin, hydrogenated terpene resin, hydrogenated terpene phenol resin, rosin, rosin ester, hydrogenated rosin, hydrogenated rosin ester, and polymerized rosin. Polymerized rosin ester, modified rosin, rosin modified phenolic 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. Can be mentioned.
The hydrocarbon resin is preferably a terpene resin, rosin, petroleum resin, hydrogenated rosin, or polymerized rosin, and more preferably a terpene resin or rosin.

From the viewpoint of improving coatability, releasability and heat resistance, it is preferable to contain a polymer compound having a non-three-dimensional crosslinked structure having fluorine atoms. The non-three-dimensional crosslinked structure means that the compound does not contain a crosslinked structure or the ratio of the crosslinked structure forming the three-dimensional crosslinked structure to the total crosslinked structure in the compound is 5% or less. % Or less is preferable. As the polymer compound having a non-three-dimensional crosslinked structure having a fluorine atom, a polymer composed of one or more fluorine-containing monofunctional monomers can be preferably used. More specifically, it is selected from tetrafluoroethylene, hexafluoropropene, tetrafluoroethylene oxide, hexafluoropropene oxide, perfluoroalkyl vinyl ether, chlorotrifluoroethylene, vinylidene fluoride, and perfluoroalkyl group-containing (meth) acrylic acid ester. Homopolymers of one or more fluorine-containing monofunctional monomers or copolymers of these monomers, copolymers of one or more fluorine-containing monofunctional monomers with ethylene, fluorine-containing monofunctional monomers And at least one fluorine-containing resin selected from a copolymer of one or more of these and chlorotrifluoroethylene.

The polymer compound having a non-three-dimensional crosslinked structure having a fluorine atom is preferably a perfluoroalkyl group-containing (meth) acrylic resin that can be synthesized from a perfluoroalkyl group-containing (meth) acrylic acid ester.
Specifically, the perfluoroalkyl group-containing (meth) acrylic acid ester is preferably a compound represented by the following formula (101).

Formula (101)

In 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 combinations thereof. To express. 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 group represented by R ¹⁰¹ , R ¹⁰² , R ¹⁰³ are preferably alkyl groups having 1 to 8 carbon atoms, such as a methyl group, an ethyl group, a propyl group, Examples include octyl group, isopropyl group, tert-butyl group, isopentyl group, 2-ethylhexyl group, 2-methylhexyl group, cyclopentyl group and the like. Examples of the aryl group are preferably aryl groups having 6 to 12 carbon atoms, and examples thereof include a phenyl group, a 1-naphthyl group, and a 2-naphthyl group. 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 combinations thereof. The divalent aliphatic group is preferably a chain structure rather than a cyclic structure, and more preferably a straight chain structure than a branched chain structure. The number of carbon atoms in the divalent aliphatic group is preferably 1-20, more preferably 1-15, still more preferably 1-12, and even more preferably 1-10. 1 to 8 is even more preferable, and 1 to 4 is particularly preferable.
Examples of the divalent aromatic group include a phenylene group, a substituted phenylene group, a naphthalene group, and a substituted naphthalene group, and a phenylene group is preferable.
Y ¹⁰¹ is preferably an aliphatic group having a divalent linear structure.

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 more preferably 1 to Fifteen fluorine-containing alkyl groups are particularly preferred. This fluorine-containing alkyl group is a straight chain {for example, —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. }, A branched structure {eg, —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 and the like} and an alicyclic structure (preferably a 5-membered or 6-membered ring such as a perfluorocyclohexyl group, a perfluorocyclopentyl group, or an alkyl group substituted with these). An ether bond (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.) may have. Further, it may be a perfluoroalkyl group.

Specifically, the perfluoroalkyl group-containing (meth) acrylic resin has a repeating unit represented by the following formula (102).
Formula (102)

In general formula (102), R ¹⁰¹ , R ¹⁰² , R ¹⁰³ , Y ¹⁰¹ , and Rf have the same meanings as those in general formula (101), and preferred embodiments are also the same.

In the perfluoroalkyl group-containing (meth) acrylic resin, a copolymer component can be selected in addition to the perfluoroalkyl group-containing (meth) acrylic acid ester from the viewpoint of peelability. Examples of the radical polymerizable compound capable of forming a copolymer component include acrylic acid esters, methacrylic acid esters, N, N-2 substituted acrylamides, N, N-2 substituted methacrylamides, styrenes, and acrylonitriles. And radical polymerizable compounds selected from methacrylonitriles and the like.

More specifically, for example, acrylic esters (eg, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate) such as alkyl acrylate (the alkyl group preferably has 1 to 20 carbon atoms). Amyl acrylate, ethyl hexyl acrylate, octyl acrylate, tert-octyl acrylate, chloroethyl acrylate, 2,2-dimethylhydroxypropyl acrylate, 5-hydroxypentyl acrylate, trimethylolpropane monoacrylate, pentaerythritol monoacrylate, Glycidyl acrylate, benzyl acrylate, methoxybenzyl acrylate, furfuryl acrylate, tetrahydrofurfuryl acrylate, etc.), aryl acrylates (eg phenyl Methacrylic acid esters (eg, methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, amyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate). , Benzyl methacrylate, chlorobenzyl methacrylate, octyl methacrylate, 4-hydroxybutyl methacrylate, 5-hydroxypentyl methacrylate, 2,2-dimethyl-3-hydroxypropyl methacrylate, trimethylolpropane monomethacrylate, pentaerythritol monomethacrylate, glycidyl methacrylate, full Furyl methacrylate, tetrahydrofurfuryl meta Relates, etc.), aryl methacrylates (eg, phenyl methacrylate, cresyl methacrylate, naphthyl methacrylate, etc.), styrenes such as styrene, alkyl styrene (eg, methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, diethyl styrene, isopropyl styrene, butyl) Styrene, hexyl styrene, cyclohexyl styrene, decyl styrene, benzyl styrene, chloromethyl styrene, trifluoromethyl styrene, ethoxymethyl styrene, acetoxymethyl styrene, etc.), alkoxy styrene (for example, methoxy styrene, 4-methoxy-3-methyl styrene, Dimethoxystyrene), halogen styrene (eg, chlorostyrene, dichlorostyrene, trichlorostyrene) Tetrachlorostyrene, pentachlorostyrene, bromostyrene, dibromostyrene, iodostyrene, fluorostyrene, trifluorostyrene, 2-bromo-4-trifluoromethylstyrene, 4-fluoro-3-trifluoromethylstyrene, etc.) Radical polymerizable compounds containing acrylonitrile, methacrylonitrile acrylic acid, carboxylic acid (acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, para-carboxylstyrene, and metal salts of these acid groups, (Meth) acrylic acid ester having a hydrocarbon group having 1 to 24 carbon atoms is preferable from the viewpoint of releasability, such as methyl (meth) acrylate, butyl, 2- Ethylhexyl, lauryl, steer Le, include such glycidyl ester, 2-ethylhexyl, lauryl, higher alcohol (meth) acrylate stearyl, especially acrylate.

A commercially available polymer compound having a non-three-dimensional crosslinked structure having a fluorine atom may be used. For example, Teflon (registered trademark) (DuPont), Tefzel (DuPont), Fullon (Asahi Glass), Halar (SolvaySolexis), Heiler (SolvaySolexis), Lumiflon (Asahi Glass), Afras (Asahi Glass), Cytop (Asahi Glass Co., Ltd.), Cefral Soft (Central Glass Co., Ltd.), Cefral Coat (Central Glass Co., Ltd.), Dionine (3M Co.), and other fluororesins, Vuitton (DuPont Co., Ltd.), Kalrez (DuPont Co., Ltd.) Various fluoro oils, including perfluoropolyether oils such as fluoro rubber, Krytox (DuPont), Fomblin (Daitotech), Demnam (Daikin Industries), etc., and Die Free FB series (Daikin) Kogyo Co., Ltd.), MegaFuck series (DIC), etc. Examples thereof include nitrogen-containing release agents.

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

When the temporary fixing adhesive of the present invention contains a polymer compound other than the above-described silicon-based liquid compound and elastomer, the content thereof is 0.01 to 60 with respect to the total solid content of the temporary fixing adhesive. The content is preferably mass%, more preferably 0.05 to 50 mass%, and still more preferably 0.1 to 30 mass%.

<< Surfactant >>
The temporary fixing adhesive of the present invention may contain a surfactant. The surfactant here does not contain a silicon-based liquid compound.
As the surfactant, any of anionic, cationic, nonionic, or amphoteric surfactants can be used, but a preferred surfactant is a nonionic surfactant.
Preferable examples of nonionic surfactants include polyoxyethylene higher alkyl ethers, polyoxyethylene higher alkyl phenyl ethers, higher fatty acid diesters of polyoxyethylene glycol, and fluorine surfactants.
As specific examples of the surfactant, the description in paragraphs 0173 to 0177 of JP-A-2015-065401 can be referred to, and the contents thereof are incorporated in the present specification.
The content of the surfactant in the temporary fixing adhesive is preferably 0.001 to 5% by mass, more preferably 0.005 to 1% by mass, based on the total solid content of the temporary fixing adhesive, from the viewpoint of applicability. 0.01 to 0.5% by mass is particularly preferable. Only one surfactant may be used, or two or more surfactants may be used. When there are two or more surfactants, the total is preferably in the above range.

<< Fluorine-based liquid compound >>
From the viewpoint of improving applicability or releasability, the temporary fixing adhesive of the present invention preferably contains a fluorinated liquid compound.
Here, the liquid compound means a compound having fluidity at 25 ° C. and having a viscosity of 1 to 100,000 mPa · s at 25 ° C., for example.
The viscosity of the fluorinated liquid compound at 25 ° C. is more preferably, for example, 10 to 20,000 mPa · s, and further preferably 100 to 15,000 mPa · s. When the viscosity of the fluorinated liquid compound is within the above range, the fluorinated liquid compound tends to be unevenly distributed in the surface layer of the adhesive layer.

The fluorinated liquid compound can be preferably used in any form of oligomer or polymer. Moreover, the mixture of an oligomer and a polymer may be sufficient. Such a mixture may further comprise a monomer. Further, the fluorinated liquid compound may be a monomer.
The fluorine-based liquid compound is preferably an oligomer, a polymer, or a mixture thereof from the viewpoint of heat resistance and the like.
Examples of the oligomer and polymer include a radical polymer, a cationic polymer, and an anionic polymer, and any of them can be preferably used. A vinyl polymer is particularly preferred.
The weight average molecular weight of the fluorinated 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 fluorinated liquid compound is preferably a compound that is not denatured during the treatment of the substrate used for temporary adhesion. For example, a compound that can exist in a liquid state even after heating at 250 ° C. or higher or treating the substrate with various chemical solutions is preferable. As a specific example, the viscosity at 25 ° C. is 1 to 100,000 mPa · s after heating to 250 ° C. under a temperature rising condition of 10 ° C./min from a state of 25 ° C. It is preferably 10 to 20,000 mPa · s, more preferably 100 to 15,000 mPa · s.
The fluorinated liquid compound having such characteristics is preferably a non-thermosetting compound having no reactive group. The reactive group here refers to all groups that react by heating at 250 ° C., and examples thereof include a polymerizable group and a hydrolyzable group. Specifically, a (meth) acryl group, an epoxy group, an isocyanato group, etc. are mentioned, for example.
Further, in the fluorinated liquid compound, the 10% thermal mass reduction temperature raised from 25 ° C. at 20 ° C./min is preferably 250 ° C. or more, and more preferably 280 ° C. or more. Moreover, although an upper limit does not have limitation in particular, For example, 1000 degrees C or less is preferable and 800 degrees C or less is more preferable. According to this aspect, it is easy to form an adhesive layer having excellent heat resistance. In addition, mass decreasing temperature is a value measured on the said temperature rising conditions in nitrogen stream by the thermogravimetry apparatus (TGA).

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

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

The cycloalkyl group may be monocyclic or polycyclic. The cycloalkyl group preferably has 3 to 30 carbon atoms, more preferably 4 to 30 carbon atoms, still more preferably 6 to 30 carbon atoms, and most preferably 6 to 20 carbon atoms. Examples of the monocyclic cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group. Examples of the polycyclic cycloalkyl group include adamantyl group, norbornyl group, bornyl group, camphenyl group, decahydronaphthyl group, tricyclodecanyl group, tetracyclodecanyl group, camphoroyl group, dicyclohexyl group and pinenyl group. Can be mentioned.
The cycloalkyl group may have the substituent described above.

The aromatic group may be monocyclic or polycyclic. The carbon number of the aromatic group is preferably 6 to 20, more preferably 6 to 14, and most preferably 6 to 10. It is preferable that the aromatic group does not contain a hetero atom (for example, a nitrogen atom, an oxygen atom, a sulfur atom, etc.) in the elements constituting the ring. Specific examples of the aromatic group include benzene ring, naphthalene ring, pentalene ring, indene ring, azulene ring, heptalene ring, indecene ring, perylene ring, pentacene ring, acetaphthalene ring, phenanthrene ring, anthracene ring, naphthacene ring, chrysene ring , Triphenylene ring, fluorene ring, biphenyl ring, pyrrole ring, furan ring, thiophene ring, imidazole ring, thiazole ring, thiazole ring, pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, indolizine ring, indole ring, benzofuran ring, Benzothiophene ring, isobenzofuran ring, quinolidine ring, quinoline ring, phthalazine ring, naphthyridine ring, quinoxaline ring, quinoxazoline ring, isoquinoline ring, carbazole ring, phenanthridine ring, acridine ring, phenanthroline ring, Ntoren ring, chromene ring, xanthene ring, phenoxathiin ring, a phenothiazine ring, and a phenazine ring.
The aromatic group may have the above-described substituent.

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

As the fluorine group, a known fluorine group can be used. Examples thereof include a fluorine-containing alkyl group and a fluorine-containing alkylene group. Of the fluorine groups, those that function as lipophilic groups are included in the lipophilic groups.
The carbon number of the fluorine-containing alkyl group is preferably 1 to 30, more preferably 1 to 20, and more preferably 1 to 15. The fluorine-containing alkyl group may be linear, branched or cyclic. Moreover, you may have an ether bond. 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 to 30, more preferably 2 to 20, and more preferably 2 to 15. The fluorine-containing alkylene group may be linear, branched or cyclic. Moreover, you may have an ether bond. The fluorine-containing alkylene group may be a perfluoroalkylene group in which all of the hydrogen atoms are substituted with fluorine atoms.

The fluorine-containing liquid compound preferably has a fluorine atom content of 1 to 90% by mass, more preferably 2 to 80% by mass, and still more preferably 5 to 70% by mass. When the fluorine content is in the above range, the peelability is excellent.
The content of fluorine atoms is defined as “{(number of fluorine atoms in one molecule × mass of fluorine atoms) / mass of all atoms in one molecule} × 100”.

A commercially available product can be used as the fluorinated liquid compound. For example, F-251, F-281, F-477, F-553, F-554, F-555, 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 710F, 710FM, 710FS, 730FL, and 730LM are preferred.

In the temporary fixing adhesive of the present invention, when a fluorinated liquid compound is used, its content is preferably 0.01 to 10% by mass relative to the mass of the temporary fixing adhesive excluding the solvent. More preferably, the content is 0.02 to 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. If content of a fluorine-type liquid compound is the said range, it is excellent in adhesiveness and peelability. One type of fluorine-based liquid compound may be used alone, or two or more types may be used in combination. When using 2 or more types together, it is preferable that total content is the said range.

<< Other ingredients >>
The temporary fixing adhesive in the present invention is within the range that does not impair the effects of the present invention, and various additives, for example, plasticizers, curing agents, catalysts other than the above, fillers, adhesion promoters, ultraviolet absorbers, if necessary. Agents, anti-aggregation agents, elastomers and other polymer compounds can be blended. When blending these additives, the blending amount is preferably 3% by mass or less, more preferably 1% by mass or less, based on the total solid content of the temporary fixing adhesive. The lower limit when blending is preferably 0.0001% by mass or more. Further, the total amount of these additives is preferably 10% by mass or less, more preferably 3% by mass or less, based on the total solid content of the temporary adhesive. The lower limit of the total blending amount when blending these components is preferably 0.0001% by mass or more.

The temporary fixing adhesive in 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, even more preferably 10 ppt or less, and substantially not contained (below the detection limit of the measuring apparatus). Are particularly preferred.
Examples of a method for removing impurities such as metals from the temporary fixing adhesive include filtration using a filter. The filter pore diameter is preferably 10 nm or less, more preferably 5 nm or less, and still more preferably 3 nm or less. The filter material is preferably a polytetrafluoroethylene, polyethylene, or nylon filter. You may use the filter previously wash | cleaned with the organic solvent. In the filter filtration step, a plurality of types of filters may be connected in series or in parallel. When using a plurality of types of filters, filters having different hole diameters and / or materials may be used in combination. Moreover, the adhesive may be filtered a plurality of times, and the step of filtering a plurality of times may be a circulation filtration step.
Moreover, as a method of reducing impurities such as metals contained in the temporary fixing adhesive, a raw material having a low metal content is selected as a raw material constituting the temporary fixing adhesive. Examples of the method include filtering and performing distillation under conditions where the inside of the apparatus is lined with polytetrafluoroethylene or the like and contamination is suppressed as much as possible. The preferable conditions for filter filtration performed on the raw materials constituting the temporary fixing adhesive are the same as those described above.
In addition to filter filtration, impurities may be removed using an adsorbent, or filter filtration and adsorbent may be used in combination. As the adsorbent, known adsorbents can be used. For example, inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon can be used.

<Preparation of temporary adhesive>
The temporary fixing adhesive of the present invention can be prepared by mixing the above-described 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 may be performed in multiple stages or repeated many times. Moreover, the filtered liquid can also be refiltered.
Any filter can be used without particular limitation as long as it has been conventionally used for filtration. For example, fluororesins such as polytetrafluoroethylene (PTFE), polyamide resins such as nylon-6 and nylon-6,6, polyolefin resins such as polyethylene and polypropylene (PP) (polyolefin resins with high density and ultra high molecular weight) And a filter using a material such as). Among these materials, polypropylene (including high density polypropylene) and nylon are preferable.
The pore size of the filter is suitably about 0.003 to 5.0 μm, for example. By setting it within this range, it becomes possible to reliably remove fine foreign matters such as impurities and aggregates contained in the composition while suppressing filtration clogging.
When using filters, different filters may be combined. At that time, the filtering by the first filter may be performed only once or may be performed twice or more. When filtering two or more times by combining different filters, it is preferable that the second and subsequent hole diameters are the same or smaller than the first filtering hole diameter. Moreover, you may combine the 1st filter of a different hole diameter within the range mentioned above. The pore diameter here can refer to the nominal value of the filter manufacturer. As a commercially available filter, for example, it can be selected from various filters provided by Nippon Pole Co., Ltd., Advantech Toyo Co., Ltd., Japan Entegris Co., Ltd. (formerly Japan Microlith Co., Ltd.) or KITZ Micro Filter Co., Ltd. .

<Use of temporary adhesive>
The temporary fix adhesive of the present invention can form an adhesive layer excellent in adhesiveness and peelability. For this reason, for example, when mechanical or chemical treatment is performed on the device wafer, the device wafer and the support can be stably temporarily bonded together, and the temporary bonding to the device wafer can be easily released. The temporary fixing adhesive of the present invention can be suitably used as a temporary fixing adhesive for manufacturing a semiconductor device.

<Adhesive film>
Next, the adhesive film of the present invention will be described.
The adhesive film of the present invention has an adhesive layer made of the temporary adhesive of the present invention.
In the adhesive film of the present invention, the silicon-based liquid compound is unevenly distributed in the surface layer of the adhesive layer. For this reason, it is excellent in peelability. In addition, since the adhesive layer contains an elastomer, excellent adhesiveness can be obtained by following the fine irregularities of the support and the substrate and by an appropriate anchor effect. For this reason, both adhesiveness and peelability can be achieved.
In the adhesive layer of the adhesive film of the present invention, the concentration of the silicon-based liquid compound exceeds 5% in the thickness direction and the region in the range of 5% of the thickness of the adhesive layer from either surface of the adhesive layer. It is preferable that the difference in the region in the range of 50%.
The concentration of the silicon-based liquid compound in the adhesive layer can be determined by combining, for example, a method of performing X-ray photoelectron spectroscopy (ESCA) measurement while performing etching, or oblique cutting and time-of-flight secondary ion mass spectrometry (TOF-SIMS) measurement. It can be measured by the 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 contained. The solvent content of the adhesive film can be measured by a gas chromatography method.

In the adhesive film of the present invention, the average thickness of the adhesive layer is not particularly limited, but is preferably 0.1 to 500 μm, more preferably 0.1 to 200 μm, still more preferably 10 to 200 μm, and 50 Particularly preferred is ~ 200 μm. When the average thickness of the adhesive layer is in the above range, it is easy to obtain an adhesive film having excellent flatness. In the present invention, the average thickness of the adhesive layer is defined as the average value of five points measured 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. An example of the other layer is a release layer.
The average thickness of the release layer is preferably 0.001 to 1 μm, and more preferably 0.01 to 0.5 μm. If it is the said range, while an adhesive film has moderate adhesive force and adhesiveness with a base material or a support body is good, an adhesive film can be easily peeled from a base material or a support body. In the present invention, the average thickness of the release layer is defined as the average value of five points measured by ellipsometry. The release layer preferably contains a compound containing a fluorine atom. Details of the release layer can be referred to the descriptions in paragraphs 0068 to 0145 of JP-A-2014-066385, and the contents thereof are incorporated in the present specification.
Moreover, the adhesive film of this invention is good also as a structure which does not have a mold release layer. This is because the adhesive layer itself made of the temporary adhesive in the present invention has peelability.

The adhesive film of this invention is good also as a "adhesive film with a release film" by sticking a release film on the single side | surface or both surfaces of an adhesive layer. According to this aspect, a long adhesive film is roll shape. It is possible to prevent troubles that the surface of the adhesive layer is scratched or sticks during storage when it is rolled up.
The release film can be peeled off when used. For example, in the case where the release film is bonded on both sides, by peeling off the release film on one side, laminating the adhesive surface to a substrate or support, and then peeling off the remaining release film, The sheet surface can be kept as clean as possible.

<Method for producing adhesive film>
The adhesive film of the present invention can be produced by a conventionally 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 realizes fluidity by heating and melting the raw material composition, and forming this melt into a sheet using an extrusion molding apparatus or an injection molding apparatus, and cooling it to form a film (sheet) Is the way to get.
In the extrusion molding method, a roll-like long film can be obtained. Although it is difficult to obtain a long film by the injection molding method, high film thickness accuracy can be obtained. Other additives can also be added by mixing, melting and stirring. A release film may be bonded to one side or both sides of the film to form an “adhesive film with a release film”.
The solution casting method realizes fluidity by dissolving the raw material composition with a solvent, and coats this solution on a support such as a film, drum or band to form a sheet, and then the film (sheet) ). To apply, apply the solution by extruding the solution with pressure from the slit-shaped opening, transferring the solution with a gravure or an aronics roller, and scanning while discharging the solution from a spray or dispenser. Examples include coating methods, dip coating by storing the solution in a tank and passing it through a film, drum or band, and coating by scraping the solution with a wire bar. . Other additives can also be added by using a solution that is dissolved, mixed and stirred. A single film (sheet) can be obtained by coating the solution on the support, then drying to form a solid sheet, and then mechanically peeling the sheet from the support. In order to easily peel off, a release layer may be applied on the support in advance by applying a release layer, immersion treatment, gas treatment, electromagnetic wave irradiation treatment, plasma irradiation treatment, or the like. Or it is good also as an "adhesive film with a release film", leaving a film as it is, without peeling off from a support body, and the sheet | seat adhere | attached on the film support body. By performing these treatments continuously, a roll-like long film can be obtained. Alternatively, a release film may be bonded to both sides of the adhesive film to form a “sheet with a double-sided release film”.

<Adhesive support>
Next, the adhesive support of the present invention will be described.
The adhesive support body of this invention has a support body and the contact bonding layer which consists of a temporary fix | bonding adhesive of this invention. The adhesive layer preferably includes the elastomer X and the elastomer Y described above as the elastomer.
The average thickness of the adhesive layer varies depending on the application, but is preferably, for example, 0.1 to 500 μm.
The adhesive layer is applied to the support surface by applying the temporary adhesive of the present invention using a spin coating method, a spray method, a roller coating method, a flow coating method, a doctor coating method, a dipping method, or the like, and is dried (baked). Can be formed. Drying is performed, for example, at 60 to 150 ° C. for 10 seconds to 2 minutes. The average thickness of the adhesive layer in this case is not particularly limited, but is preferably 1 to 100 μm, and more preferably 1 to 10 μm.
The adhesive layer can also be formed by laminating the above-described adhesive film of the present invention on a support. By forming an adhesive layer using an adhesive film, an adhesive layer can be formed even with materials such as elastomers that are poorly soluble in solvents, so an adhesive layer with excellent heat resistance and chemical resistance is formed. Cheap. In addition, a thick adhesive layer having a thickness of 10 μm or more can be made flat without thickness unevenness. The average thickness of the adhesive layer in this case is not particularly limited, but is preferably 0.1 to 200 μm, more preferably 10 to 200 μm, and particularly preferably 50 to 200 μm.
To form an adhesive layer on a support using an adhesive film, for example, set the adhesive film on a vacuum laminator, place the adhesive film on the support with this device, and support the adhesive film and the support under vacuum. And a method of fixing (laminating) an adhesive film to a support by bringing the body into contact with each other and pressing with a roller or the like. Moreover, you may cut the adhesive film (adhesion layer) fixed to the support body in desired shapes, such as circular shape, for example.

In the adhesive support of the present invention, the adhesive layer has a region where the concentration of the silicon-based liquid compound is 5% in the thickness direction of the adhesive layer from the surface on the opposite side of the support. It is preferable to be higher than the region in the range of more than 5% and 50% in the thickness direction of the adhesive layer from the surface. According to this aspect, the peelability is improved when the adhesive support is temporarily bonded to a substrate such as a device wafer and then peeled from the device wafer. Furthermore, the adhesive layer can be easily removed from the surface of the substrate or device wafer by a method such as mechanical peeling.
The concentration of the silicon-based liquid compound ranges from 5% in the thickness direction of the adhesive layer from the surface on the opposite side of the support to more than 5% in the thickness direction of the adhesive layer from the surface on the opposite side of the support. It is preferably more than 10% by mass and more preferably more than 30% by mass than the region in the range of 50%.

In the adhesive support of the present invention, the support (also referred to as a carrier support) is not particularly limited, and examples thereof include a silicon substrate, a glass substrate, a metal substrate, and a compound semiconductor substrate. In particular, in view of the point that it is difficult to contaminate a silicon substrate typically used as a substrate of a semiconductor device and the point that an electrostatic chuck widely used in the manufacturing process of a semiconductor device can be used, it is a silicon substrate. preferable.
The thickness of the support is not particularly limited, but 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 release layer having a 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 has a material containing fluorine atoms and / or silicon atoms. The fluorine content of the release layer is preferably 30 to 80% by mass, more preferably 40 to 76% by mass, and particularly preferably 60 to 75% by mass.
As the material for the release layer, the same material as the release layer that may be formed on the surface layer of the adhesive film described above can be used.

<Laminated body>
Next, the laminated body of this invention is demonstrated. The laminate of the present invention has a support, an adhesive layer made of the temporary fixing adhesive of the present invention, and a substrate.
Hereinafter, preferred embodiments of the laminate of the present invention will be described with reference to FIGS. Needless to say, embodiments of the laminate of the present invention are not limited to these embodiments. 1 and 2, reference numeral 1 denotes a base material, 2 denotes a support, and 3, 3A and 3B denote adhesive layers.

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 substrate 1 is on the surface opposite to the support of the adhesive layer 3. It is the mode which is located. Thus, it is preferable that the adhesive layer 3 is provided between the base material and the support, and the adhesive layer 3 is in contact with the base material and the support in terms of improving the throughput of forming the laminate. That is, in the laminate, an embodiment in which the above-described release layer is not included between the base material and the support, and only the adhesive layer is exemplified.
In the first embodiment, the peel strength A between the support and the adhesive layer made of the temporary adhesive of the present invention, and the peel strength B of the adhesive layer made of the temporary adhesive of the present invention and the substrate are as follows: It is preferable to satisfy the following formulas (1) and (2).
A <B Formula (1)
B ≦ 4N / cm ・・・・ Formula (2)
When the peel strength A and the peel strength B satisfy the relationship of the above formula (1), when peeling the support from the base material, the peel strength A and the peel strength B peel from the interface between the support and the adhesive layer made of the temporary fixing adhesive of the present invention can do.
And when peeling strength B satisfy | fills the relationship of said Formula (2), an adhesive layer can be easily peeled from the base-material surface with a film form. That is, the adhesive layer can be easily peeled off by mechanical peeling.
The peel strength B is preferably 3 N / cm or less, and more preferably 2 N / cm or less.
The peel strength in the present invention is a value obtained by measuring the strength when pulled up in the 90 ° direction. 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.

For the laminate of the present invention, when the support is peeled from the base material, the adhesive layer made of the temporary adhesive of the present invention is peeled from the interface between the base material and the adhesive layer, In the range of 50% or more of the area of the peeled surface, the residue of the silicon-based liquid compound is adhered, or the adhesive layer is peeled from the interface between the support and the adhesive layer, and the adhesive layer of the support In the range of 50% or more of the area of the peeled surface, the residue of the silicon-based liquid compound is preferably attached. Moreover, it is preferable that the residue derived from an elastomer does not adhere in the range of 50% or more of the area of the peeling surface, and more preferably does not adhere in a range of 99% or more.
Residues of silicon-based liquid compounds and elastomer-derived residues can be observed by visual observation, optical microscope, scanning electron microscope, X-ray photoelectron spectroscopy, etc. In the present invention, the peeled surface is measured by X-ray photoelectron spectroscopy. Shall be.
In the present specification, “residue of silicon-based liquid compound” is a silicon-based liquid compound component of the adhesive layer, and “residue derived from elastomer” means an elastomer component of the adhesive layer.

The laminate of the present invention can be produced by thermocompression bonding the surface of the adhesive support of the present invention described above on which the adhesive layer is formed and the substrate. The pressure bonding conditions are preferably, for example, a temperature of 100 to 200 ° C., a pressure of 0.01 to 1 MPa, and a time of 1 to 15 minutes.

2nd embodiment of the laminated body of this invention is an aspect shown in FIG. 2, Comprising: The support body 2, adhesive layer 3A, and the base material 1 are laminated | stacked in the said order, and the support body 2 and In this embodiment, a second adhesive layer 3B having a composition different from that of the adhesive layer 3A is provided between the adhesive layers 3A. In the present 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 with each other on the surface.
By using two or more adhesive layers as in the second embodiment, there is an advantage that the support and the base material can be easily bonded together (with no voids). In particular, the embedding property can be improved more effectively by providing the adhesive layer 3B on the support 2 side and providing the second adhesive layer 3A on the substrate 1 side and bonding them together.

In the third embodiment of the laminate of the present invention, the support 2, the adhesive layer 3 </ b> A, and the substrate 1 are laminated in the above order, and the adhesive layer is between the adhesive layer 3 </ b> A and the substrate. In this embodiment, the second adhesive layer has a different composition. In the present 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 substrate are preferably in contact with each other on the surface.

Next, the second adhesive layer in the second and third embodiments 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 made of the temporary adhesive of the present invention. Therefore, the second adhesive layer 3B may also be an adhesive layer made of the same components as the temporary fixing adhesive of the present invention. However, in this case, the adhesive layer 3A and the adhesive layer 3B have different compositions.
In the present invention, it is preferable that the second adhesive layer contains an elastomer X containing a repeating unit derived from styrene in a proportion 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 the compound that is liquid at 25 ° C. and contains silicon atoms contained in the adhesive layer It is preferable that it is 10 mass% or less of content of. By adopting such a second adhesive layer, it becomes easier to adjust the peeling interface.
For example, in the base material (device wafer) / second adhesive layer / adhesive layer / support (carrier) comprising the temporary fixing adhesive of the present invention, it is necessary for peeling between the base material and the second adhesive layer. If the force is larger than the force necessary to peel between the adhesive layer made of the temporary adhesive of the present invention and the support, the adhesive layer made of the temporary adhesive of the present invention will Can be peeled off. By adopting such a configuration, peeling becomes easier.
Moreover, it is preferable that the 2nd contact bonding layer in this invention contains the elastomer Y which contains the repeating unit derived from styrene in the ratio of 10 mass% or more and less than 50 mass% in all the repeating units. By setting it as such a structure, the curvature of a wafer can be suppressed effectively.
In the second adhesive layer, the elastomer X and the elastomer Y, and the blending ratio thereof are synonymous with those described in the temporary fixing adhesive of the present invention, and the preferred ranges are also the same. Moreover, you may mix | blend various additives etc. which were described in the place of the temporary fix | bonding adhesive agent of this invention also with a 2nd contact bonding layer.

The fourth embodiment of the laminate of the present invention is an aspect having other layers in the first to third embodiments. Examples of other layers include layers called release layers, release layers, or separation layers. As the release layer, for example, the description in paragraphs 0025 to 0055 of JP 2014-212292 A can be referred to, and the contents thereof are incorporated in the present specification. As the separation layer, the description in paragraphs 0069 to 0124 of International Publication No. WO2013 / 064417 can be referred to, and the contents thereof are incorporated in the present specification.

A device wafer is preferably used as the substrate. A known device wafer can be used without limitation, and examples thereof include a silicon substrate and a compound semiconductor substrate. Specific examples of the compound semiconductor substrate include a SiC substrate, a SiGe substrate, a ZnS substrate, a ZnSe substrate, a GaAs substrate, an InP substrate, and a GaN substrate.
A mechanical structure or a circuit may be formed on the surface of the device wafer. Examples of device wafers on which mechanical structures and circuits are formed include MEMS (Micro Electro Mechanical Systems), power devices, image sensors, micro sensors, light emitting diodes (LEDs), optical devices, interposers, embedded devices, and micro devices. Etc.
The device wafer preferably has a structure such as a metal bump. According to the present invention, it is possible to stably temporarily bond even a device wafer having such a structure on the surface, and to easily release the temporary adhesion to the device wafer. The height of the structure is not particularly limited, but is preferably 1 to 150 μm, for example, and more preferably 5 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. For example, 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 thinning by mechanical or chemical treatment is preferably less than 500 μm, more preferably 400 μm or less, and even more preferably 300 μm or less. For example, the lower limit is preferably 1 μm or more, and more preferably 5 μm or more.

In the laminate of the present invention, the support (carrier support) is synonymous with the support described in the adhesive support described above, and the preferred range is also the same.
Alternatively, the adhesive layer 3A may be provided on the base material, and the adhesive layer 3B may be provided on the support to be bonded. In this case, the adhesive layer 3A and the adhesive layer 3B may be the same or different. If they are different, change the type of compound containing silicon atoms, or change the type and amount of other additives such as compounds containing lipophilic groups and fluorine atoms. And the peeling selectivity at the interface between the support and the peeling force can be adjusted as appropriate.
Moreover, it can also manufacture by arrange | positioning the adhesive sheet of this invention mentioned above between a support body and a base material, and thermocompression-bonding.

In the laminate of the present invention, the adhesive layer of the present invention is formed on one of the support and the substrate using the temporary adhesive of the present invention, and the temporary adhesive of the present invention is formed on the other of the support and the substrate. Alternatively, the adhesive layer can be formed by using the other temporary fixing adhesive described above, and the surfaces on which the support layer and the adhesive layer of the base material are formed can be thermocompression-bonded. According to this method, since the adhesive layers are bonded together, the support and the substrate can be bonded together with good embedding properties.

Furthermore, in the laminate of the present invention, the adhesive layer 3 </ b> A and the adhesive layer 3 </ b> B are each one of the support and the base material using the temporary adhesive of the present invention and the other temporary adhesive described above. It can also be produced by forming an adhesive layer including at least one layer, placing the other of the support and the substrate on the adhesive layer, and thermocompression-bonding the support and the substrate.

<Method for Manufacturing Semiconductor Device>
<< First Embodiment >>
Hereinafter, an embodiment of a method of manufacturing a semiconductor device that has undergone a process of manufacturing a stacked body will be described with reference to FIG. In addition, this invention is not limited to the following embodiment.
3A to 3E are schematic cross-sectional views (FIGS. 3A and 3B) for explaining the temporary bonding between the support and the device wafer, respectively, and the device wafer temporarily bonded to the support. The thinned state (FIG. 3C), the support and the device wafer are peeled off (FIG. 3D), and the state after the adhesive layer is removed from the device wafer (FIG. 3E). It is a schematic sectional drawing.

In this embodiment, as shown in FIG. 3A, first, an adhesive support 100 in which an adhesive layer 11 is provided on a support 12 is prepared.
It is preferable that the adhesive layer 11 is an embodiment that does not substantially contain a solvent.
The device wafer 60 (base material) is formed by providing a plurality of device chips 62 on a surface 61 a of a silicon substrate 61.
The thickness of the silicon substrate 61 is preferably 200 to 1200 μm, for example. The device chip 62 is preferably a metal structure, for example, and the height is preferably 10 to 100 μm.
In the process of forming the adhesive layer 11, a step of cleaning the support 12 or the back surface of the device wafer 60 with a solvent may be provided. Specifically, by removing the residue of the adhesive layer adhering to the end surface and the back surface of the support 12 and the device wafer 60 using a solvent that dissolves the adhesive layer, the contamination of the apparatus can be prevented and the thickness can be reduced. The TTV (Total Thickness Variation) of the device wafer can be reduced. As the solvent used in the step of cleaning the support 12 or the back surface of the device wafer 60 with a solvent, the solvent contained in the above-described temporary fixing adhesive can be used.

Next, as shown in FIG. 3B, the adhesive support 100 and the device wafer 60 are pressure-bonded, and the support 12 and the device wafer 60 are temporarily bonded.
The adhesive layer 11 preferably completely covers the device chip 62, and preferably satisfies the relationship of “X + 100 ≧ Y> X” when the height of the device chip is X μm and the thickness of the adhesive layer is Y μm.
The fact that the adhesive layer 11 completely covers the device chip 62 is effective when it is desired to further reduce the TTV (Total Thickness Variation) of the thin device wafer (that is, when the flatness of the thin device wafer is to be further improved). It is.
That is, when the device wafer is thinned, the plurality of device chips 62 are protected by the adhesive layer 11, so that it is possible to almost eliminate the uneven shape on the contact surface with the support 12. Therefore, even if the thickness is reduced in such a supported state, the possibility that the shape derived from the plurality of device chips 62 is transferred to the back surface 61b1 of the thin device wafer is reduced, and as a result, the thin device finally obtained The TTV of the wafer can be further reduced.

Next, as shown in FIG. 3C, the back surface 61b of the silicon substrate 61 is subjected to mechanical or chemical treatment (though not particularly limited, for example, thinning treatment such as grinding or chemical mechanical polishing (CMP)). , Chemical vapor deposition (CVD), physical vapor deposition (PVD) and other high-temperature / vacuum treatments, treatments using chemicals such as organic solvents, acidic treatment solutions and basic treatment solutions, plating treatments, actinic rays 3) to reduce the thickness of the silicon substrate 61 (for example, the average thickness is preferably less than 500 μm, preferably 1 to 200 μm). More preferably, a thin device wafer 60a is obtained.
After thinning the device wafer, it may be possible to provide a step of cleaning the adhesive layer that protrudes outside the area of the substrate surface of the device wafer with a solvent at a stage before performing the treatment under high temperature and vacuum. Specifically, after thinning the device wafer, the protruding adhesive layer is removed using a solvent that dissolves the adhesive layer, whereby the treatment under high temperature and vacuum is directly applied to the adhesive layer. Deformation and alteration of the adhesive layer can be prevented. As the solvent used in the step of washing the adhesive layer protruding outside the area of the substrate surface of the device 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 device wafer is D μm, and the diameter of the film surface of the adhesive layer is T μm, (C-200) ≧ T ≧ D It is more preferable to satisfy. Furthermore, the diameter of the substrate surface of the support is _C μm, the diameter of the substrate surface of the device wafer is _D μm, the diameter of the film surface in contact with the support of the adhesive layer is T _C μm, and the device wafer of the adhesive layer is When the diameter of the film surface on the side in contact is T _D μm, it is preferable that (C-200) ≧ T _C > T _D ≧ D. By setting it as such a structure, a deformation | transformation and a quality change of the contact bonding layer by the process under high temperature and a vacuum being directly performed to a contact bonding layer can be suppressed more.
The area of the film surface of the adhesive layer refers to the area when viewed from the direction perpendicular to the support, and the film surface is not considered uneven. The same applies to the substrate surface of the device wafer. That is, the substrate surface of the device wafer referred to here is, for example, a surface corresponding to the surface 61a in FIG. The same applies to the diameter of the adhesive layer such as the film surface.
Further, regarding the diameter T of the film surface of the adhesive layer, the diameter of the film surface on the side in contact with the support of the adhesive layer is T _C μm, and the diameter of the film surface on the side of the adhesive layer in contact with the device wafer is T _D When 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 device wafer refer to the diameter of the surface in contact with the adhesive layer.
In addition, although it is prescribed | regulated as a "diameter" about a support body etc., it is not essential that a support body etc. are circular (perfect circle) in a mathematical meaning, and what is necessary is just circular. If it is not a perfect circle, the diameter when converted to a perfect circle of the same area is taken as the diameter.
Further, as a mechanical or chemical treatment, a through hole (not shown) penetrating the silicon substrate is formed from the back surface 61b1 of the thin device wafer 60a after the thinning process, and a silicon through electrode ( A process of forming (not shown) may be performed.
Heat treatment may be performed after the support 12 and the device wafer 60 are temporarily bonded to each other and then peeled off. As an example of the heat treatment, heat treatment may be performed in a mechanical or chemical treatment.
The maximum temperature achieved in the heat treatment is preferably 80 to 400 ° C, more preferably 130 ° C to 400 ° C, and still more preferably 180 ° C to 350 ° C. The highest temperature achieved in the heat treatment is preferably lower than the decomposition temperature of the adhesive layer. The heat treatment is preferably performed for 30 seconds to 30 minutes at the highest temperature, and more preferably for 1 minute to 10 minutes at the highest temperature.

Next, as shown in FIG. 3D, the support 12 is detached from the thin device wafer 60a. The method of detachment is not particularly limited, but it is preferable that the separation is performed by pulling up from the end of the thin device wafer 60a in a direction perpendicular to the thin device wafer 60a without any treatment. At this time, the peeling interface is preferably peeled off at the interface between the support 12 and the adhesive layer 11. In this case, the peel strength A at the interface between the support 12 and the adhesive layer 11 and the peel strength B between the device wafer surface 61a and the adhesive layer 11 preferably satisfy the following expressions.
A <B Formula (1)

Further, the adhesive layer 11 is brought into contact with a stripping solution described later, and then, if necessary, the thin device wafer 60a is slid with respect to the support 12 and then the end of the thin device wafer 60a is applied to the device wafer. It can also be peeled off by pulling up in the vertical direction.

<Release solution>
Hereinafter, the stripping solution will be described in detail.
As the stripping solution, water and a solvent (organic solvent) can be used.
Moreover, as a peeling liquid, the organic solvent which melt | dissolves the contact bonding layer 11 is preferable. Examples of the organic solvent include aliphatic hydrocarbons (hexane, heptane, isoper E, H, G (manufactured by Esso Chemical Co., Ltd.), limonene, para-menthane, nonane, decane, dodecane, decalin, etc.), aromatic Hydrocarbons (toluene, xylene, anisole, mesitylene, ethylbenzene, propylbenzene, cumene, n-butylbenzene, sec-butylbenzene, isobutylbenzene, tert-butylbenzene, amylbenzene, isoamylbenzene, (2,2-dimethylpropyl ) Benzene, 1-phenylhexane, 1-phenylheptane, 1-phenyloctane, 1-phenylnonane, 1-phenyldecane, cyclopropylbenzene, cyclohexylbenzene, 2-ethyltoluene, 1,2-diethylbenzene, ortho-cymene , Indan 1,2,3,4-tetrahydronaphthalene, 3-ethyltoluene, meta-cymene, 1,3-diisopropylbenzene, 4-ethyltoluene, 1,4-diethylbenzene, para-cymene, 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-ortho-xylene 1,2,4-triethylbenzene, 1,3,5-triethylbenzene, 1,3,5-triisopropylbenzene, 5-tert-butyl-meta-xylene, 3,5-di-tert-butyltoluene, 1,2,3,5-tetramethylbenzene, 1,2,4,5-tetramethylbenzene, pentamethylbenzene Zen, etc.), halogenated hydrocarbons (methylene dichloride, ethylene dichloride, trichlorethylene, monochlorobenzene, etc.), polar solvents. Particularly polar solvents include alcohols (methanol, ethanol, propanol, isopropanol, 1-butanol, 1-pentanol, 1-hexanol, 1-heptanol, 1-octanol, 2-octanol, 2-ethyl-1-hexanol, 1-nonanol, 1-decanol, benzyl alcohol, ethylene glycol monomethyl ether, 2-ethoxyethanol, diethylene glycol monoethyl ether, diethylene glycol monohexyl ether, triethylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether, polyethylene glycol Monomethyl ether, polypropylene glycol, tetraethylene glycol, ethylene glycol monobutyl Ether, ethylene glycol monobenzyl ether, ethylene glycol monophenyl ether, propylene glycol monophenyl ether, methylphenyl carbinol, n-amyl alcohol, methyl amyl alcohol, etc.), ketones (acetone, methyl ethyl ketone, ethyl butyl ketone, 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 levulinate, etc.) (Triethyl phosphate, tricresyl phosphate, N-phenylethanolamine, N-phenyl Le diethanolamine, N- methyldiethanolamine, N- ethyldiethanolamine, 4- (2-hydroxyethyl) morpholine, N, N- dimethylacetamide, N- methylpyrrolidone and the like) and the like.

Furthermore, from the viewpoint of peelability, the stripping solution may contain an alkali, an acid, and a surfactant. When these components are blended, the blending amount is preferably 0.1 to 5.0% by mass of the stripping solution.
Further, from the viewpoint of peelability, a form in which two or more organic solvents and water, two or more alkalis, an acid, and a surfactant are mixed is also preferable.

Examples of the alkali include tribasic sodium phosphate, tribasic potassium phosphate, tribasic ammonium phosphate, dibasic sodium phosphate, dibasic potassium phosphate, dibasic ammonium phosphate, sodium carbonate, potassium carbonate, and ammonium carbonate. , Inorganic alkali agents such as sodium bicarbonate, potassium bicarbonate, ammonium bicarbonate, sodium borate, potassium borate, ammonium borate, sodium hydroxide, ammonium hydroxide, potassium hydroxide and lithium hydroxide, monomethylamine, Dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine, triisopropylamine, n-butylamine, monoethanolamine, diethanolamine, triethanol Min, monoisopropanolamine, diisopropanolamine, ethyleneimine, ethylenediamine, pyridine, may be used an organic alkali agent such as tetramethylammonium hydroxide. These alkali agents can be used alone or in combination of two or more.

Acids include inorganic acids such as hydrogen halides, sulfuric acid, nitric acid, phosphoric acid, boric acid, methanesulfonic acid, ethanesulfonic acid, benzenesulfonic acid, para-toluenesulfonic acid, trifluoromethanesulfonic acid, acetic acid, citric acid Organic acids such as formic acid, gluconic acid, lactic acid, oxalic acid and tartaric acid can be used.

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

Examples of the anionic surfactant include, but are not limited to, fatty acid salts, abietic acid salts, hydroxyalkane sulfonic acid salts, alkane sulfonic acid salts, dialkyl sulfosuccinic acid salts, linear alkyl benzene sulfonic acid salts, branched alkyl benzene sulfonic acid salts, Alkylnaphthalene sulfonates, alkyl diphenyl ether (di) sulfonates, alkylphenoxy polyoxyethylene alkyl sulfonates, polyoxyethylene alkyl sulfophenyl ether salts, N-alkyl-N-oleyl taurine sodium, N-alkyl sulfosuccinic acid Monoamide disodium salts, petroleum sulfonates, sulfated castor oil, sulfated beef oil, sulfate esters of fatty acid alkyl esters, alkyl sulfate esters, polio Siethylene alkyl ether sulfates, fatty acid monoglyceride sulfates, polyoxyethylene alkylphenyl ether sulfates, polyoxyethylene styryl phenyl ether sulfates, alkyl phosphates, polyoxyethylene alkyl ether phosphates, polyoxy Examples thereof include ethylene alkylphenyl ether phosphoric acid ester salts, partial saponification products of styrene-maleic anhydride copolymer, partial saponification products of olefin-maleic anhydride copolymer, and naphthalene sulfonate formalin condensates. Of these, alkylbenzene sulfonates, alkylnaphthalene sulfonates, and alkyl diphenyl ether (di) sulfonates are particularly preferably used.

The cationic surfactant is not particularly limited, and conventionally known cationic surfactants can be used. Examples thereof include alkylamine salts, quaternary ammonium salts, alkyl imidazolinium salts, polyoxyethylene alkylamine salts, and polyethylene polyamine derivatives.

The nonionic surfactant is not particularly limited, but is a polyethylene glycol type higher alcohol ethylene oxide adduct, alkylphenol ethylene oxide adduct, alkyl naphthol ethylene oxide adduct, phenol ethylene oxide adduct, naphthol ethylene oxide adduct, fatty acid. Ethylene oxide adduct, polyhydric alcohol fatty acid ester ethylene oxide adduct, higher alkylamine ethylene oxide adduct, fatty acid amide ethylene oxide adduct, fat and oil ethylene oxide adduct, polypropylene glycol ethylene oxide adduct, dimethylsiloxane-ethylene oxide block Copolymer, dimethylsiloxane- (propylene oxide-ethylene oxide) block copolymer , Fatty acid esters of polyhydric alcohol type glycerol, fatty acid esters of pentaerythritol, fatty acid esters of sorbitol and sorbitan, fatty acid esters of sucrose, alkyl ethers of polyhydric alcohols, fatty acid amides of alkanolamines. Among these, those having an aromatic ring and an ethylene oxide chain are preferable, and an alkyl-substituted or unsubstituted phenol ethylene oxide adduct or an alkyl-substituted or unsubstituted naphthol ethylene oxide adduct is more preferable.

Zwitterionic surfactants include, but are not limited to, amine oxides such as alkyldimethylamine oxide, betaines such as alkylbetaines, and amino acids such as sodium alkylamino fatty acids. In particular, alkyldimethylamine oxide which may have a substituent, alkylcarboxybetaine which may have a substituent, and alkylsulfobetaine which may have a substituent are preferably used. Specifically, the compound represented by the formula (2) in paragraph [0256] of JP-A-2008-203359, the formula (I) and the formula (II) in paragraph [0028] of JP-A-2008-276166 are disclosed. ), A compound represented by the formula (VI), and compounds represented by paragraph numbers [0022] to [0029] of JP-A-2009-47927 can be used.

Further, if necessary, the stripping solution can contain additives such as an antifoaming agent and a hard water softening agent.

Then, as shown in FIG. 3E, the thin device wafer can be obtained by removing the adhesive layer 11 from the thin device wafer 60a.
The method for removing the adhesive layer 11 includes, for example, a method of peeling and removing (mechanical peeling) the adhesive layer in the form of a film, a method of peeling and removing the adhesive layer after swelling with a peeling liquid, and spraying the peeling liquid onto the adhesive layer. Examples thereof include a method for destructive removal, a method for dissolving and removing the adhesive layer by dissolving it in a peeling solution, and a method for removing the adhesive layer by decomposition and vaporization by irradiation with actinic rays and radiation or heating. A method of peeling and removing the adhesive layer in the form of a film and a method of dissolving and removing the adhesive layer in an aqueous solution or an organic solvent can be preferably used. As an organic solvent, the organic solvent demonstrated with the stripping solution mentioned above can be used. From the viewpoint of reducing the amount of solvent used, it is preferable to remove the film as it is. Further, from the viewpoint of reducing damage on the surface of the device wafer, dissolution and removal are preferable.
In order to remove the film as it is, the peel strength B between the device wafer surface 61a and the adhesive layer 11 preferably satisfies the following formula (2).
B ≦ 4N / cm ・・・・ Formula (2)

Assuming that the peel strength at the interface between the support 12 and the adhesive layer 11 is A and the peel strength B between the device wafer surface 61a and the adhesive layer 11, both the above-described equations (1) and (2) are satisfied. When peeling from the thin device wafer 60a, the edge of the thin device wafer 60a can be pulled up in a direction perpendicular to the device wafer without any treatment, and the adhesive layer 11 on the device wafer surface 61a can be peeled off. Can be removed in the form of a film.
After the support 12 is detached from the thin device wafer 60a, various known processes are performed on the thin device wafer 60a as necessary to manufacture a semiconductor device having the thin device wafer 60a.

Further, when the adhesive layer is attached to the support, the support can be regenerated by removing the adhesive layer. As a method of removing the adhesive layer, peeling in the form of a film, a method of physically removing by brush, ultrasonic waves, ice particles, aerosol spraying, a method of dissolving and removing by dissolving in an aqueous solution or an organic solvent, A chemical removal method such as a method of decomposing or vaporizing by irradiation with actinic rays, radiation, or heat can be mentioned, and conventionally known cleaning methods can be used depending on the support.
For example, when a silicon substrate is used as the support, a conventionally known silicon wafer cleaning method can be used. For example, examples of the aqueous solution or organic solvent that can be used for chemical removal include strong acids, strong bases, strong oxidants, and mixtures thereof. Specifically, sulfuric acid, hydrochloric acid, hydrofluoric acid, nitric acid, organic acids Acids such as tetramethylammonium, ammonia, organic bases, oxidizing agents such as hydrogen peroxide, or a mixture of ammonia and hydrogen peroxide, a mixture of hydrochloric acid and hydrogen peroxide, sulfuric acid and hydrogen peroxide Examples thereof include a mixture, a mixture of hydrofluoric acid and hydrogen peroxide, a mixture of hydrofluoric acid and ammonium fluoride.

From the viewpoint of adhesiveness when the regenerated support is used, it is preferable to use a support cleaning liquid.
The support cleaning liquid preferably contains an acid (strong acid) having a pKa of less than 0 and hydrogen peroxide. The acid having a pKa of less than 0 is selected from inorganic acids such as hydrogen iodide, perchloric acid, hydrogen bromide, hydrogen chloride, nitric acid and sulfuric acid, or organic acids such as alkylsulfonic acid and arylsulfonic acid. From the viewpoint of detergency of the adhesive layer on the support, an inorganic acid is preferable, and sulfuric acid is particularly preferable.

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 to 100: 1 in terms of mass ratio. ˜10: 1 is more preferred, and 3: 1 to 5: 1 is particularly preferred.

<< Second Embodiment >>
A second embodiment of a semiconductor manufacturing method that has undergone a process for manufacturing a laminated body will be described with reference to FIG. The same portions as those in the first embodiment described above are denoted by the same reference numerals and the description thereof is omitted.
4A to 4E are schematic cross-sectional views (FIGS. 4A and 4B) for explaining the temporary bonding between the support and the device wafer, and the device wafer temporarily bonded to the support. The thinned state (FIG. 4C), the support and the device wafer are peeled off (FIG. 4D), and the state after the adhesive layer is removed from the device wafer (FIG. 4E). It is a schematic sectional drawing.
As shown in FIG. 4A, this embodiment is different from the first embodiment in that an adhesive layer is formed on the surface 61a of the device wafer.
When the adhesive layer 11a is provided on the surface 61a of the device wafer 60, the adhesive layer 11a is formed by applying (preferably applying) a temporary fixing adhesive to the surface 61a of the device wafer 60 and then drying (baking). be able to. Drying can be performed, for example, at 60 to 150 ° C. for 10 seconds to 2 minutes.
Next, as shown in FIG. 4B, the support 12 and the device wafer 60 are pressure-bonded, and the support 12 and the device wafer 60 are temporarily bonded. Next, as shown in FIG. 4C, the back surface 61b of the silicon substrate 61 is subjected to mechanical or chemical treatment to reduce the thickness of the silicon substrate 61, thereby obtaining a thin device wafer 60a. Next, as shown in FIG. 4D, the support 12 is detached from the thin device wafer 60a. Then, as shown in FIG. 4E, the adhesive layer 11 is removed from the thin device wafer 60a.

<< Third Embodiment >>
A third embodiment of a semiconductor manufacturing method that has undergone a process for manufacturing a laminated body will be described with reference to FIG. The same portions as those in the first embodiment described above are denoted by the same reference numerals and the description thereof is omitted.
5A to 5E are schematic cross-sectional views (FIGS. 5A and 5B) for explaining the temporary bonding between the support and the device wafer, respectively, and the device wafer temporarily bonded to the support. The thinned state (FIG. 5C), the support and the device wafer are peeled off (FIG. 5D), and the state after the adhesive layer is removed from the device wafer (FIG. 5E). It is a schematic sectional drawing.
In this embodiment, as shown in FIGS. 4A and 4B,

adhesive layers

11b and 11c are formed on the support 12 and the surface 61a of the device wafer, respectively. The point which manufactures a laminated body by crimping | bonding the surfaces of the formed side (temporarily adhere | attaches the support body 12 and the device wafer 60) is different from said 1st embodiment.
At least one of the adhesive layer 11b and the adhesive layer 11c can be formed using the temporary fixing adhesive of the present invention. Both the adhesive layer 11b and the adhesive layer 11c can also be formed using the temporary fixing adhesive of the present invention. Only one adhesive layer uses the temporary fixing adhesive of the present invention, and the other adhesive layer is the above-described adhesive layer. It can also be formed using the temporary fixing adhesive B. It is preferable that the adhesive layer 11b is formed using the above-described temporary fixing adhesive B, and the adhesive layer 11c is formed using the temporary fixing adhesive of the present invention.
Further, each of the

adhesive layers

11b and 11c may be composed of only one layer, or may be a laminate formed by laminating two or more adhesive layers. That is, each adhesive layer can be formed by repeatedly applying two or more types of temporary adhesives.
After the support 12 and the device wafer 60 are temporarily bonded, the back surface 61b of the silicon substrate 61 is then subjected to mechanical or chemical treatment as shown in FIG. The thin device wafer 60a is obtained. Next, as shown in FIG. 5D, the support 12 is detached from the thin device wafer 60a. Then, as shown in FIG. 5E, the adhesive layer 11d is removed from the thin device wafer 60a.

<< Conventional Embodiment >>
Next, a conventional embodiment will be described.
FIG. 6 is a schematic cross-sectional view for explaining the release of the temporarily bonded state between the conventional adhesive support and the device wafer.
In the conventional embodiment, as shown in FIG. 6, as an adhesive support, an adhesive support in which an adhesive layer 11a formed of a conventional temporary fixing adhesive is provided on a support 12 is provided. 100a, otherwise, the adhesive support 100a and the device wafer are temporarily bonded in the same manner as described with reference to FIG. 3, and the silicon substrate is thinned on the device wafer. Similar to the above-described procedure, the thin device wafer 60a is peeled off from the adhesive support 100a.

However, according to the conventional temporary fixing adhesive, it is difficult to easily release the temporary support to the device wafer without temporarily supporting the device wafer with a high adhesive force and damaging the device wafer. For example, in order to ensure sufficient temporary bonding between the device wafer and the support, if a highly adhesive adhesive is used among conventional temporary adhesives, the temporary bonding between the device wafer and the support tends to be too strong. It becomes. Therefore, in order to release the temporary bonding that is too strong, for example, as shown in FIG. 6, a tape (for example, dicing tape) 70 is attached to the back surface of the thin device wafer 60a, and the thin device wafer 60a is bonded from the adhesive support 100a. In the case of peeling off, the structure chip 63 is detached from the device chip 62 provided with the structure 63 and the device chip 62 is likely to be damaged.
On the other hand, if a low temporary adhesive adhesive is used, the temporary support for the device wafer can be easily released, but the temporary attachment between the device wafer and the support is too weak in the first place. A problem that the wafer cannot be reliably supported by the support tends to occur.

On the other hand, the laminate of the present invention exhibits sufficient adhesiveness and can easily release the temporary adhesion between the device wafer 60 and the support. That is, according to the laminated body of the present invention, the device wafer 60 can be temporarily bonded with high adhesive force, and the temporary bonding to the thin device wafer 60a can be easily released without damaging the thin device wafer 60a.

The method for manufacturing a semiconductor device of the present invention is not limited to the above-described embodiment, and appropriate modifications and improvements can be made.
In the above-described embodiment, the adhesive layer has a single layer structure, but the adhesive layer may have a multilayer structure.
In the above-described embodiment, a silicon substrate is used as the device wafer. However, the present invention is not limited to this, and any device that can be subjected to mechanical or chemical processing in the method of manufacturing a semiconductor device is not limited thereto. It may be a processing member. For example, a compound semiconductor substrate can also be mentioned, and specific examples of the compound semiconductor substrate include a SiC substrate, a SiGe substrate, a ZnS substrate, a ZnSe substrate, a GaAs substrate, an InP substrate, and a GaN substrate.
In the above-described embodiments, the device wafer (silicon substrate) is mechanically or chemically treated as a device wafer thinning process and a through silicon via formation process, but is not limited thereto. Any processing required in the method of manufacturing a semiconductor device is included.
In addition, the shape, size, number, arrangement location, and the like of the device chip in the device wafer exemplified in the above-described embodiment are arbitrary and are not limited.

<Kit>
Next, the kit of the present invention will be described.
The kit of the present invention includes the first temporary fixing adhesive of the present invention described above and an elastomer X containing a repeating unit derived from styrene in a proportion of 50% by mass or more and 95% by mass or less in all repeating units, and It has the 2nd adhesive agent from which a composition differs from the said 1st temporary fix | stop adhesive. The second adhesive preferably contains an elastomer X containing a repeating unit derived from styrene in a proportion of 50% by mass or more and 95% by mass or less in all repeating units. Further, in the second adhesive, the content of the compound that is liquid at 25 ° C. and that contains silicon atoms is contained in the first temporary adhesive, and is liquid at 25 ° C. It is preferable that it is 10 mass% or less of content of the compound containing an atom. Moreover, it is preferable that the 2nd adhesive agent in this invention contains the elastomer Y which contains the repeating unit derived from styrene in the ratio of 10 mass% or more and less than 50 mass% in all the repeating units. With such a configuration, the warpage of the wafer can be more effectively suppressed.
In the second adhesive, the elastomer X and the elastomer Y, and the blending ratio thereof are synonymous with those described for the temporary adhesive of the present invention, and the preferred ranges are also the same. Moreover, you may mix | blend the various additives etc. which were described in the place of the temporary fix | adhesive adhesive agent of this invention with the 2nd adhesive agent. These blending amounts and the like are also preferably in the range described in the temporary fixing adhesive of the present invention.
It is preferable that the kit of this invention has a base material and a support body further. As a base material and a support body, the base material and support body which were demonstrated by the laminated body mentioned above are mentioned, These can be used.
By further including a base material and a support, a laminate having the first adhesive layer made of the temporary fixing adhesive of the present invention and the above-described second adhesive layer is provided between the base material and the support. Can be manufactured.

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples unless it exceeds the gist thereof. Unless otherwise specified, “part” and “%” are based on mass.
Propylene glycol-1-methyl ether acetate is referred to as “PGMEA”.

In this example, the following materials were used.
[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 (manufactured by Shin-Etsu Chemical Co., Ltd.)
(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) BYK333 (by Big Chemie)
(A-10) Polyflow KL-700 (manufactured by Kyoeisha Chemical Co., Ltd.)
(A-11) TEGO WET 270 (Evonik Degussa Japan Co., Ltd.)
(A-12) SH28PA (Toray Dow Corning Co., Ltd.)
(A-13) NBX-15 (manufactured by Neos Corporation)
(Ra-1) KR220L (solid silicone resin, manufactured by Shin-Etsu Chemical Co., Ltd.)
(Ra-2) 1-dodecene (hydrocarbon oil, manufactured by Tokyo Chemical Industry Co., Ltd.)
The viscosities at 25 ° C. of (a-1) to (a-13) were in the range of 10 to 20,000 mPa · s.

[B component]
(B-1): Septon 2104 (hydrogenated polystyrene elastomer, styrene content = 65 mass%, unsaturated double bond content = less than 0.5 mmol / g, 5% thermal mass reduction temperature = 400 ° C. or higher and lower than 450 ° C. Mw = 50,000 to less than 100,000, hardness (type A durometer) = 98, manufactured by Kuraray Co., Ltd.)
(B-2): 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 ° C. More than 450 ° C, Mw = 50,000 to less than 100,000, Hardness (Type A durometer) = 90 or more, manufactured by Asahi Kasei Corporation
(B-3): Septon 8104 (hydrogenated polystyrene 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 durometer) = 98, manufactured by Kuraray Co., Ltd.)
(B-4): Kraton A1535 (hydrogenated polystyrene elastomer, styrene content = 58 mass%, unsaturated double bond content = less than 0.5 mmol / g, 5% thermal mass reduction temperature = 400 ° C. or more and less than 450 ° C. , Hardness (Type A durometer) = 83, manufactured by Clayton)

(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 to less than 100,000, hardness (type A durometer) = 80, manufactured by Kuraray Co., Ltd.)
(B-6): Septon 4033 (hydrogenated polystyrene elastomer, styrene content = 30 mass%, unsaturated double bond content = less than 0.5 mmol / g, 5% thermal mass reduction temperature = 400 ° C. or more and less than 400 ° C. , Hardness (Type A durometer) = 76, manufactured by Kuraray Co., Ltd.)
(B-7): Kraton G1650 (hydrogenated polystyrene elastomer, styrene content = 30% by mass, unsaturated double bond content = less than 0.5 mmol / g, 5% thermal mass reduction temperature = 400 ° C. or higher and lower than 450 ° C. , Hardness (Type A durometer) = 70, manufactured by Clayton)
(B-8): Septon 8004 (hydrogenated polystyrene elastomer, styrene content = 31 mass%, unsaturated double bond content = less than 0.5 mmol / g, 5% thermal mass reduction temperature = 400 ° C. or higher and lower than 450 ° C. Mw = 50,000 to less than 100,000, hardness (type A durometer) = 80, manufactured by Kuraray Co., Ltd.)
(B-9): Septon 8007 (hydrogenated polystyrene elastomer, styrene content = 30 mass%, unsaturated double bond content = less than 0.5 mmol / g, 5% thermal mass reduction temperature = 400 ° C. or higher and lower than 450 ° C. , Mw = 50,000 to 100,000, hardness (type A durometer) = 77, manufactured by Kuraray Co., Ltd.)
(B-10): SIS5200P (non-hydrogenated polystyrene elastomer, styrene content = 15 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 350 ° C. <° C., Mw = 100,000 to less than 200,000, manufactured by JSR Corporation)

(Rb-1): RB810 (polybutadiene elastomer, unsaturated double bond content 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 Corporation Made)
(Rb-2): ZEONEX 480R (Nippon Zeon cycloolefin polymer)
(Rb-3): Durimide (registered trademark) 284 (polyimide made by FUJIFILM)
(Rb-4): PCZ300 (Mitsubishi Gas Chemical Polycarbonate)
(Rb-5): Hytrel 7247 (polyester elastomer, 5% thermal mass reduction temperature = 383 ° C., hardness (type A durometer) = 90 or more, manufactured by Toray DuPont)
(Rb-6): 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 decrease temperature is a temperature at which 5% of the mass at the start of measurement is reduced under the condition that the temperature is increased from 25 ° C. at 20 ° C./min in a nitrogen stream by a thermogravimetric measuring device (TGA). Is a measured value.

[Test Example 1]
<Formation of Adhesive Support 1>
The adhesive layer forming coating solution 1 is applied onto a Si wafer (support wafer) having a diameter of 100 mm and a thickness of 525 μm by spin coating, followed by baking at 110 ° C. for 1 minute and further by baking at 190 ° C. for 4 minutes. An adhesive support 1 having a layer was prepared.

<Composition of Coating Solution 1 for Adhesive Layer Formation>
-A component: The A component of Table 1 is the mass part shown in Table 1.-B component: The B component of Table 1 is the mass part shown in Table 1.-Irganox 1010 (manufactured by BASF Corp.): 0 .9 parts by mass-Sumilizer TP-D (manufactured by Sumitomo Chemical Co., Ltd.): 0.9 part by mass-Solvent:

<Preparation of test piece>
A surface of the adhesive support 1 on which the adhesive layer is formed and a device surface of a Si wafer (device wafer) with a bump made of Cu having a diameter of 100 mm, a thickness of 525 μm, and a height of 10 μm are subjected to 190 ° C. under vacuum. The test piece was manufactured by pressure bonding for 3 minutes at a pressure of 0.11 MPa.

<Adhesiveness>
Using a tensile tester (Imada Digital Force Gauge, Model: ZP-50N), the tensile strength of the test piece was measured in a direction along the surface of the adhesive layer under the condition of 250 mm / min. Evaluation was made according to the following criteria.
A: Adhesive force of 50N or more B: Adhesive force of 10N or more and less than 50N C: Adhesive force of less than 10N

<Peelability>
The test piece was set together with a dicing frame in the center of the dicing tape mounter, and the dicing tape was arranged from above. Under vacuum, the test piece and the dicing tape were fixed with a roller, the dicing tape was cut on a dicing frame, and the test piece was mounted on the dicing tape.
Under 25 ° C., the test piece was pulled in the direction perpendicular to the surface of the adhesive layer (90 ° direction) under the condition of 50 mm / min, and the peelability was evaluated according to the following criteria. In addition, after heating the prepared test piece at 250 ° C. for 30 minutes, the test piece was pulled at 25 ° C. in the vertical direction of the adhesive layer under the condition of 50 mm / min, and the peelability after the thermal process was confirmed. The evaluation was based on the following criteria. In addition, the presence or absence of the damage of Si wafer was confirmed visually.
A: The maximum peeling force was less than 12N, and peeling was possible.
B: It was able to peel off with the largest peeling force being 12N or more and less than 16N.
C: Separation was possible when the maximum peeling force was 16N or more and less than 20N.
D: Separation was possible when the maximum peeling force was 20N or more and less than 25N.
E: The maximum peeling force was 25 N / cm or more or the Si wafer was damaged.

<Removability (dissolution removal)>
After completion of the peelability test, the adhesive layer-attached Si wafer (device wafer) is set on a spin coater with the adhesive layer facing up, and the same solvent as the solvent for the adhesive layer forming coating solution shown in Table 1 below is used as a cleaning solvent. And sprayed for 5 minutes. Furthermore, only Comparative Examples 5, 6, and 7 in which mesitylene was not used for spraying for 5 minutes were rinsed by spraying isopropyl alcohol (IPA) while rotating the Si wafer. Further, spin drying was performed. Thereafter, the appearance was observed and the presence or absence of the remaining adhesive layer was checked visually and by X-ray photoelectron spectroscopy with the amount of carbon atoms on the surface of the Si wafer, and evaluated according to the following criteria.

<< Measurement Method of X-ray Photoelectron Spectroscopy >>
The measurement apparatus uses PHI Quantera SXM (manufactured by ULVAC-PHI), irradiates the substrate surface of the wafer 1400 μm × 700 μm with 25 W of monochromatic AlKα ray, and detects it at an extraction angle of 45 °. The abundance ratio (atm%) of carbon atoms was measured. The measurement temperature was 25 ° C. and the measurement pressure was 10 ⁻⁸ Pa or less.
The area of the substrate surface of the wafer refers to the area of the surface of the substrate when it is assumed that there is no uneven portion even when the surface of the substrate surface is uneven.
Evaluation was made according to the following evaluation categories.
A: As a result of ESCA measurement, the abundance ratio of carbon atoms was less than 1%.
B: As a result of ESCA measurement, the abundance ratio of carbon atoms was 1% or more and less than 3%.
C: As a result of ESCA measurement, the abundance ratio of carbon atoms was 3% or more.

<Removability (film removal)>
At 25 ° C., the Si wafer with an adhesive layer (device wafer) after the peelability test is fixed so as not to move, and a peeling tape (manufactured by Lintec Corporation) is attached to the adhesive layer on the Si wafer with an adhesive layer. Then, the peeling tape was pulled in the direction perpendicular to the adhesive layer, and the adhesive layer was pulled up at a speed of 50 mm / min in the 90 ° direction to peel the adhesive layer from the device surface of the Si wafer (device wafer) into a film. Thereafter, the appearance was observed, the presence or absence of a peeling residue of the adhesive layer remaining on the Si wafer was visually checked, and evaluated according to the following criteria.
A: With a peel strength of 4 N / cm or less, the adhesive layer can be removed in the form of a film without breaking, and no peeling residue of the adhesive layer is observed.
B: With a peel strength exceeding 4 N / cm, the adhesive layer can be removed in a film form without breaking, and no peel residue of the adhesive layer is observed.
C: Not applicable to any of the above A and B (breakage during peeling)

<Wafer warpage>
After polishing the surface of the device wafer that is not in contact with the adhesive layer of the prepared test piece until the thickness of the device wafer reaches 35 μm, the surface is raised using FLX-2320 manufactured by KLA-Tencor. The temperature rate and the cooling rate were set to 10 ° C./min, heated from room temperature to 200 ° C., then cooled to 25 ° C., and the Bow value (warping magnitude) was measured.
A: Bow value is 40 μm or less B: Bow value exceeds 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

As apparent from the above results, when the temporary adhesive of the present invention was used, the adhesiveness and the room temperature peelability were good. Furthermore, the peelability after heating and the removability of the adhesive layer were good, and the warpage of the wafer was suppressed.
Further, in the example in which the above-described elastomer X and elastomer Y were used in combination as the elastomer, the warpage of the wafer was more effectively suppressed.

[Test Example 2]
<Formation of Adhesive Support 2>
The adhesive layer forming coating solution 2 is spin-coated on a Si wafer (support wafer) having 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. The adhesive support body 2 which has a layer was produced.
Further, the coating solution 3 for forming the adhesive layer was spin coated on a Si wafer (device wafer) with a bump made of Cu having a diameter of 100 mm, a thickness of 525 μm, and a height of 10 μm, and then baked at 110 ° C. for 1 minute. The adhesive base material which has an adhesive layer was produced by baking at 190 degreeC for 4 minutes.

<Composition of

coating liquids

2 and 3 for forming an adhesive layer>
-A component: The A component described in Table 2 is the mass part shown in Table 2.-B component: The B component described in Table 2 is the mass part shown in Table 2.-Irganox 1010 (manufactured by BASF Corp.): 0 .9 parts by mass. Sumilizer TP-D (manufactured by Sumitomo Chemical Co., Ltd.): 0.9 parts by mass. Mesitylene: 30 parts by mass.

<Preparation of test piece>
The surface of the adhesive support 2 on which the adhesive layer is formed and the surface of the adhesive base material on which the adhesive layer is formed are pressure-bonded under a vacuum at 190 ° C. and a pressure of 0.11 MPa for 3 minutes, A test piece was prepared.

<Adhesiveness>
The adhesiveness was evaluated by the same method and standard as the adhesiveness evaluation in Test Example 1.
<Embeddability>
Adhesive layer after bonding the test piece using C-SAM (ultrasonic microscope) (including the interface between the adhesive layers, the bonding surface between the bonding layer and the substrate, and the bonding surface between the bonding layer and the support) The presence or absence of voids was confirmed.
A: No void was generated.
B: 1 to 5 small voids having a diameter of 10 μm or less can be confirmed, but there is no actual harm
C: More than 5 small voids having a diameter of 10 μm or less can be confirmed, but there is no actual harm.
D: Ten or more voids having a diameter of more than 10 μm are generated, which is actually harmful.
<Peelability>
The peelability was evaluated by the same method and standard as the peelability evaluation in Test Example 1.
<Removability (dissolution removal)>
The removability (dissolution removal) was evaluated by the same method and standard as the removability (dissolution removal) in Test Example 1.
<Removability (film removal)>
The removability (film removal) was evaluated by the same method and standard as the removability (film removal) in Test Example 1.
<Wafer warpage>
Wafer warpage was evaluated by the same method and standard as the wafer warpage in Test Example 1.

As apparent from the above results, when the temporary adhesive of the present invention was used, the adhesiveness and the room temperature peelability were good. Furthermore, the peelability after heating and the removability of the adhesive layer were good.
Further, in the example in which the above-described elastomer X and elastomer Y were used in combination as the elastomer, the warpage of the wafer was more effectively suppressed.
In addition, when applied to both the support side and the device side (Examples 34 to 41), the embedding property was good.

[Test Example 3]
<Method for producing adhesive film>
The adhesive film forming compositions of Examples 42 to 50 and Comparative Examples 12 to 15 and 18 to 21 were coated on a release polyethylene terephthalate (PET) film having a thickness of 75 μm with a wire bar at a speed of 1 m / min. By drying at 140 ° C. for 10 minutes, an adhesive film having a film thickness of 100 μm was produced.
The adhesive film forming compositions of Comparative Examples 16 and 17 were melted and stirred at 300 ° C. for 5 minutes, and extruded from a slit having a width of 100 μm to produce an adhesive film (extruded sheet).

(Composition of the composition for forming an adhesive film)
-A component: The A component of Table 3 is the mass part shown in Table 3.-B component: The B component of Table 3 is the mass part shown in Table 3.-Solvent: The solvent of Table 3 is the table. 3 parts by mass

<Preparation of test piece>
A surface of the adhesive support 2 on which the adhesive layer was formed and a Si wafer having a diameter of 100 mm were pressure-bonded under a vacuum at 190 ° C. and a pressure of 0.11 MPa for 3 minutes to prepare a test piece.

<Adhesiveness>
The adhesiveness was evaluated by the same method and standard as the adhesiveness evaluation in Test Example 1.
<Peelability>
The peelability was evaluated by the same method and standard as the peelability evaluation in Test Example 1.
<Removability (dissolution removal)>
After completion of the peelability test, the Si wafer with an adhesive layer was set on a spin coater with the adhesive layer facing upward, and sprayed onto the wafer for 5 minutes using the solvents described in Table 3 below as the cleaning solvent. Further, spin drying was performed. Thereafter, the appearance was observed to visually check the presence or absence of the remaining adhesive layer, and evaluated according to the following criteria.
A: Remaining adhesive layer is not observed B: Remaining adhesive layer is observed <Removability (film removal)>
The removability (film removal) was evaluated by the same method and standard as the removability (film removal) in Test Example 1.
<Wafer warpage>
Wafer warpage was evaluated by the same method and standard as the wafer warpage in Test Example 1.

1: base material 2:

supports

3, 3A, 3B, 11, 11a to 11d: adhesive layer 12: support 60: device wafer 60a: thin device wafer 61: silicon substrate 61a: front surface 61b :, 61b1: back surface 62: Device chip 63:

structure

100, 100a: adhesive support

Claims

A compound that is liquid at 25 ° C. and contains silicon atoms;
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,
Temporary tack adhesive containing.
The temporary fixing adhesive according to claim 1, wherein the compound containing silicon atoms has a 10% thermal mass reduction temperature of 250 ° C or higher when the temperature is increased from 25 ° C at 20 ° C / min.
The temporary fixing adhesive according to claim 1 or 2, wherein the elastomer X has a hardness measured by a type A durometer according to the method of JIS K6253 of 83 or more.
The temporary fixing adhesive according to any one of claims 1 to 3, further comprising an elastomer Y containing a repeating unit derived from styrene in a proportion of 10% by mass or more and less than 50% by mass in all repeating units.
The temporary adhesive according to claim 4, wherein the mass ratio of the elastomer X and the elastomer Y is 5:95 to 95: 5.
The 5% thermal mass reduction temperature at which at least one of the elastomers contained in the temporary adhesive is heated from 25 ° C. at 20 ° C./min is 250 ° C. or higher. Temporary fixing adhesive according to item.
The temporary fixing adhesive according to any one of claims 1 to 6, wherein an amount of unsaturated double bonds of at least one of the elastomers contained in the temporary fixing adhesive is 7 mmol / g or less.
The temporary fixing adhesive according to any one of claims 1 to 7, wherein at least one of the elastomers contained in the temporary fixing adhesive is a hydrogenated product.
The temporary fixing adhesive according to any one of claims 1 to 8, wherein at least one of the elastomers contained in the temporary fixing adhesive is a block copolymer.
The temporary fixing adhesive according to any one of claims 1 to 9, wherein at least one of the elastomers contained in the temporary fixing adhesive is a block copolymer derived from styrene at one end or both ends.
The content of the compound containing silicon atoms is 0.01% by mass or more and less than 2.5% by mass with respect to the total amount of elastomer in the temporary fixing adhesive. Temporary adhesive.
The temporary fixing adhesive according to any one of claims 1 to 11, wherein the compound containing a silicon atom is selected from dimethylpolysiloxane, methylphenylpolysiloxane, diphenylpolysiloxane, and polyether-modified polysiloxane.
The temporary adhesive according to any one of claims 1 to 12, further comprising at least one of an antioxidant and a solvent.
The temporary adhesive according to any one of claims 1 to 13, wherein the temporary adhesive is a temporary adhesive for manufacturing a semiconductor device.
An adhesive film having an adhesive layer made of the temporary fixing adhesive according to any one of claims 1 to 14.
An adhesive support comprising an adhesive layer comprising the temporary fixing adhesive according to any one of claims 1 to 14 and a support.
A laminate comprising a support, an adhesive layer comprising the temporary fixing adhesive according to any one of claims 1 to 14, and a substrate.
The laminate according to claim 17, wherein the adhesive layer is located on a surface of the support, and the base material is located on a surface of the adhesive layer opposite to the support.
The support, the adhesive layer, and the base material are laminated in the order described above, and a second adhesive layer having a composition different from that of the adhesive layer is provided between the support and the adhesive layer. The laminate according to claim 17.
The support, the adhesive layer, and the base material are laminated in the order described above, and a second adhesive layer having a composition different from that of the adhesive layer is provided between the adhesive layer and the base material. The laminate according to claim 17.
21. The laminate according to claim 19 or 20, wherein the second adhesive layer contains an elastomer X containing a repeating unit derived from styrene in a proportion of 50% by mass or more and 95% by mass or less in all repeating units.
The second adhesive layer according to any one of claims 19 to 21, wherein the second adhesive layer includes an elastomer Y containing a repeating unit derived from styrene in a proportion of 10% by mass or more and less than 50% by mass in all repeating units. Laminated body.
The content of the compound that is liquid at 25 ° C. and contains silicon atoms in the second adhesive layer is the compound that is liquid at 25 ° C. and contains silicon atoms contained in the adhesive layer The laminate according to any one of claims 19 to 22, which is 10 mass% or less of the content of.
The laminate according to any one of claims 17 to 23, wherein the substrate is a device wafer.
A temporary fixing adhesive according to any one of claims 1 to 14 and an elastomer X containing a repeating unit derived from styrene in a proportion of 50% by mass or more and 95% by mass or less in all repeating units, and A kit having a second adhesive having a composition different from that of the temporary fixing adhesive.