KR20170139609A - A temporary fixing adhesive, an adhesive film, an adhesive support, a laminate and a kit - Google Patents

Abstract

An adhesive film, an adhesive support, a laminate, and a kit using the temporary fixing adhesive excellent in peeling property at room temperature and excellent in adhesion and the temporary fixing adhesive are provided.
Is a temporarily fixed adhesive comprising a elastomer X which is liquid at 25 占 폚 and contains a silicon atom-containing compound and a repeating unit derived from styrene in a proportion of 50% by mass or more and 95% by mass or less in the total repeating units.

Description

A temporary fixing adhesive, an adhesive film, an adhesive support, a laminate and a kit

The present invention relates to a temporary fixing adhesive, an adhesive film, an adhesive support, a laminate and a kit. More particularly, the present invention relates to a temporary fixing adhesive, an adhesive film, an adhesive support, a laminate, and a kit which can be suitably used for manufacturing semiconductor devices and the like.

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

Further miniaturization and high integration of IC chips mounted on electronic devices are required due to the demand for further miniaturization and high performance of electronic devices, but the integration of integrated circuits in the plane direction of device wafers is approaching the limit.

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

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

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

However, a device wafer having a thickness of 200 占 퐉 or less is very thin, and a semiconductor device manufacturing member made of such a substrate is extremely thin. Therefore, when such a member is subjected to additional processing, or when such a member is simply moved, It is difficult to stably support the member without damaging it.

In order to solve the above problems, there is known a technique of peeling a back surface of a device wafer after thinning the back surface of a device wafer by adhering a device wafer and a supporting member, which are provided with a device on a surface thereof, with a temporary fixing adhesive.

For example, Patent Document 1 discloses an adhesive composition comprising a polystyrene-based elastomer and a surface modifier.

Patent Document 2 discloses a waxy composition containing a cycloolefin-based polymer and a compound having a structure such as a dialkyl silicone structure and a polyoxyalkylene structure.

Patent Document 3 discloses that a material containing fluorine atoms and / or silicon atoms is used for the release layer by using a release layer and a protective layer when the device wafer and the support substrate are adhered.

Patent Document 1: U.S. Patent Publication No. 2014 / 0178701A1 Patent Document 2: JP-A-2013-241568 Patent Document 3: JP-A-2015-065401

However, the inventors of the present invention have found that it is difficult to peel off the device wafer and the support at room temperature after the adhesive composition disclosed in Patent Document 1 and the temporary fixing furnace described in Patent Document 2 are made thinner. In general, if it is attempted to improve the peelability, the adhesive property tends to be poor.

It is an object of the present invention to solve these problems, and an object of the present invention is to provide a temporary fixing adhesive excellent in releasability at room temperature and excellent in adhesion, and an adhesive film, an adhesive support, And to provide a kit.

Under the above-mentioned problems, the present inventors have intensively studied and, as a result, have found that a styrene-based elastomer having a large proportion of repeating units derived from styrene can be compounded with a compound containing a silicon atom, The present invention has been accomplished on the basis of these findings.

More specifically, the above-mentioned problem is solved by the following means <1>, preferably by the following means <2> to <25>.

&Lt; 1 > A pressure-sensitive adhesive comprising a elastomer X containing a silicone-containing compound and a repeating unit derived from styrene at a ratio of 50 mass% to 95 mass% .

&Lt; 2 > The temporary fixing adhesive according to < 1 >, wherein the 10% thermal mass reduction temperature of the compound containing silicon atoms is raised from 25 DEG C to 20 DEG C / min.

<3> The temporary fixing adhesive according to <1> or <2>, wherein the hardness of the elastomer X measured by a Type A durometer according to the method of JIS K6253 is 80 or more.

<4> The temporary fixing adhesive according to any one of <1> to <3>, further comprising an elastomer Y containing repeating units derived from styrene in a proportion of 10% by mass or more and less than 50% .

<5> The temporary fixing adhesive according to <4>, wherein the mass ratio of the elastomer X and the elastomer Y is 5: 95 to 95: 5.

<6> The thermoplastic resin composition according to any one of <1> to <5>, wherein the 5% thermal mass reduction temperature of at least one of the elastomers contained in the temporary fixing adhesive is increased from 25 ° C. to 20 ° C./min, And the like.

<7> The temporary fixing adhesive according to any one of <1> to <6>, wherein the amount of the unsaturated double bond of at least one of the elastomers contained 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 contained in the temporary fixing adhesive is a hydrogenation product.

<9> The temporary fixing adhesive according to any one of <1> to <8>, wherein at least one of the elastomers contained in the temporary fixing adhesive is a block copolymer.

<10> The temporary fixing adhesive according to any one of <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 terminal or both terminals.

<11> The temporary fixed adhesive according to any one of <1> to <10>, wherein the content of the silicon-containing compound relative to the total amount of the elastomers in the temporary fixing adhesive is less than 0.01% by mass and less than 2.5% by mass.

<12> The temporary fixing film according to any one of <1> to <11>, wherein the silicon atom-containing compound is selected from dimethyl polysiloxane, methylphenyl polysiloxane, diphenyl polysiloxane and polyether modified polysiloxane. glue.

<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 temporarily fixing adhesive for manufacturing semiconductor devices.

<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 backing having an adhesive layer made of the temporary fixing adhesive according to any one of <1> to <14> and a support.

<17> A laminate having a support and an adhesive layer made of the temporary fixation 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 a surface of the support, and the substrate is located on a surface of the adhesive layer opposite to the support.

<19> The liquid crystal display device according to <17>, wherein the support, the adhesive layer, and the substrate are stacked in this order, and a second adhesive layer is formed between the support and the adhesive layer, Laminates.

<20> The laminate according to <17>, wherein the support, the adhesive layer and the substrate are laminated in this order, and a second adhesive layer having a composition different from that of the adhesive layer is provided between the adhesive layer and the substrate sieve.

<21> The laminate according to <19> or <20>, wherein the second adhesive layer comprises an elastomer X containing repeating units derived from styrene in a proportion of 50% by mass or more and 95% sieve.

<22> The method according to any one of <19> to <21>, wherein the second adhesive layer comprises an elastomer Y containing repeating units derived from styrene in a proportion of 10% by mass or more and less than 50% &Lt; / RTI &gt;

The content of the compound having a silicon atom in the liquid phase at 25 ° C. in the second adhesive layer is preferably 10 mass% or less of the content of the compound containing silicon atoms % Or less, based on the total weight of the layered product.

<24> The laminate according to any one of <17> to <23>, wherein the substrate is a device wafer.

<25> A tackifier as described in any one of <1> to <14>, and an elastomer X containing 50% by mass or more and 95% by mass or less of styrene- And a second adhesive different in composition from the temporary fixing adhesive.

According to the present invention, it is made possible to provide a temporarily fixed adhesive excellent in peeling property at room temperature and excellent in adhesiveness, and an adhesive film, an adhesive support, a laminate and a kit using the temporary fixing adhesive.

BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic view showing one embodiment of the laminate of the present invention. Fig.
2 is a schematic view showing another embodiment of the laminate of the present invention.
3 is a schematic view of a first embodiment showing a manufacturing method of a semiconductor device.
4 is a schematic view of a second embodiment showing a manufacturing method of a semiconductor device.
5 is a schematic view of a third embodiment showing a manufacturing method of a semiconductor device.
6 is a schematic cross-sectional view illustrating the release of the adhesion state between the conventional adhesive support and the device wafer.

Hereinafter, the contents of the present invention will be described in detail. In the present specification, "~" is used to mean that the numerical values described before and after the numerical value are included as the lower limit value and the upper limit value.

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

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

In the present specification, the term "light" means an actinic ray or radiation.

In the present specification, the term "exposure" means not only exposure using deep ultraviolet rays, X-rays, EUV light (extreme ultra-violet) typified by mercury lamps, ultraviolet rays and excimer lasers, And the drawing using the particle lines of FIG.

As used herein, "(meth) acrylate" refers to acrylate and methacrylate, "(meth) acryl" refers to acryl and methacryl, "(meth) acryloyl" And methacryloyl.

In the present specification, the weight average molecular weight and the number average molecular weight are defined as polystyrene reduced values 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 , 6.0 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 term "hydrophilic group" means a functional group not containing a hydrophilic group. The term "hydrophilic group" means a functional group exhibiting affinity with water.

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

<Fixed adhesive>

The temporary fixing adhesive of the present invention has a structure in which the compound having a liquid phase at 25 占 폚 and containing a silicon atom (hereinafter sometimes referred to as a "silicon-based liquid phase compound") and a repeating unit derived from styrene, By mass to 95% by mass or less of the elastomer X.

According to the temporary fixing adhesive of the present invention, when a substrate such as a device wafer is mechanically or chemically treated, it is possible to stably adhere the substrate and to easily adhere the substrate to the substrate An adhesive layer can be formed.

Since the temporary fixing adhesive of the present invention includes the silicon-based liquid phase compound described above, the silicon-based liquid phase compound tends to be unevenly distributed in the surface layer of the adhesive layer, and the concentration of the silicon-based liquid phase compound in the surface layer of the adhesive layer can be increased. Accordingly, the adhesive layer having an excellent releasability to the substrate or the support can be formed at least relative to the solid content of the silicon-based liquid phase compound in the solid component of the fixed adhesive.

Further, since the elastomer X containing the repeating unit derived from styrene in a proportion of not less than 50% by mass and not more than 95% by mass in the total repeating units is included, a part or all of the adhesive layer made of the temporary fixing adhesive contains a rigid Regions are 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 semiconductor device production.

Hereinafter, the temporary fixing adhesive of the present invention will be described in detail.

<< Silicon-based liquid phase compound >>

The temporary fixing adhesive of the present invention contains a silicon-based liquid phase compound.

In the present invention, the liquid phase means a compound having fluidity at 25 ° C, for example, a compound having a viscosity at 25 ° C of 1 to 100,000 mPa · s. The viscosity of the silicon-based liquid phase compound at 25 占 폚 is more preferably from 10 to 20,000 mPa 占 퐏, and still more preferably from 100 to 15,000 mPa 占 퐏. When the viscosity of the silicon-based liquid phase compound is within the above range, it is preferable that the silicon-based liquid phase compound is more likely to be localized on the surface layer of the adhesive layer.

In the present invention, the silicon-based liquid phase compound may be any of oligomer and polymer compounds. It may also be a mixture of an oligomer and a polymer. Such a mixture may further contain a monomer. The silicon-based liquid phase compound may be a monomer.

The silicon-based liquid phase compound is preferably an oligomer, a polymer and a mixture thereof from the viewpoint of heat resistance and the like.

As the oligomer and polymer, for example, an addition polymer, a polycondensation product, an addition condensation product and the like can be used without particular limitation, but polycondensation is particularly preferable.

The weight average molecular weight of the silicon-based liquid phase compound is preferably from 500 to 100,000, more preferably from 1,000 to 50,000, and still more preferably from 2,000 to 20,000.

In the present invention, the silicon-based liquid phase compound is preferably a compound which is not denatured during the treatment of a base material used for adhesion. For example, a compound which can be present as a liquid phase even after heating at 250 DEG C or higher or after treating the substrate with various chemical solutions is preferable. As a specific example, the viscosity at 25 ° C after heating from 250 ° C to 25 ° C at a temperature elevation rate of 10 ° C / min from 25 ° C is preferably from 1 to 100,000 mPa · s, more preferably from 10 to 20,000 mPa · s · S is more preferable, and 100 to 15,000 mPa · s is even more preferable.

The silicon-based liquid phase compound having such characteristics is preferably a non-thermosetting compound having no reactive group. The term reactive group as used herein refers to the whole period of the reaction in the heating at 250 ° C, and includes a polymerizable group and a hydrolyzable group. Specific examples thereof include (meth) acrylic groups, epoxy groups, and isocyanato groups.

The silicon-based liquid-phase compound preferably has a 10% thermal mass reduction temperature at 25 ° C or higher and 20 ° C / minute at 250 ° C or higher, more preferably 280 ° C or higher. The upper limit value is not particularly limited, but is preferably 1000 占 폚 or lower, for example, and more preferably 800 占 폚 or lower. According to this embodiment, it is easy to form an adhesive layer having excellent heat resistance. The mass reduction temperature is a value measured under the temperature elevation condition under a nitrogen stream by a thermogravimetric analyzer (TGA).

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

The number of carbon atoms in the alkyl group is preferably from 1 to 30, more preferably from 1 to 10, and still more preferably from 1 to 3. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a dodecyl group, a tetradecyl group, , Isobutyl group, sec-butyl group, tert-butyl group, 1-ethylpentyl group and 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 carbon number of the alkoxy group is preferably from 1 to 30, more preferably from 1 to 20, and even more preferably from 1 to 10. The alkoxy group is preferably straight-chain or branched.

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

The cycloalkyl group may be monocyclic or polycyclic. The number of carbon atoms of the cycloalkyl group is preferably from 3 to 30, more preferably from 4 to 30, still more preferably from 6 to 30, and particularly preferably from 6 to 20. 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 an adamantyl group, a norbornyl group, a vinyl group, a camphanyl group, a decahydronaphthyl group, a tricyclodecanyl group, a tetracyclodecanyl group, a camphoryl group, a dicyclohexyl group, .

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 from 6 to 20, more preferably from 6 to 14, and particularly preferably from 6 to 10. It is preferable that the aromatic group does not contain a hetero atom (for example, a nitrogen atom, an oxygen atom, a sulfur atom, etc.) in the element constituting the ring. Specific examples of the aromatic group include a benzene ring, a naphthalene ring, a pentane ring, an indene ring, an azole ring, a heptylene ring, an indene ring, a perylene ring, a pentacene ring, an acenaphthene ring, a phenanthrene ring, an anthracene ring, a naphthacene ring, A thiophene ring, an imidazole ring, an oxazole ring, a thiazole ring, a pyridine ring, a pyrazine ring, a pyrimidine ring, a pyridazin ring, an indolizine ring, A benzofuran ring, an isobenzofuran ring, a quinoline ring, a quinoline ring, a phthalazine ring, a naphthyridine ring, a quinoxaline ring, a quinoxazoline ring, an isoquinoline ring, a carbazole ring, a phenanthrene ring, A phenanthroline ring, a phenanthroline ring, a thianthrene ring, a chroman ring, a zenthene ring, a phenoxathiine ring, a phenothiazine ring, and a phenanthrene ring, and a benzene ring is preferable.

The aromatic group may have the substituent described above. As the substituent, a straight-chain alkyl group is preferable.

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

[Chemical Formula 1]

R ¹ and R ² in the above general formula are each independently a straight chain or branched alkyl group, cycloalkyl group or aromatic group, and one of R ¹ and R ² may be an organic group containing a polyether chain.

L ¹ represents -O- or a linking group containing a polyether chain.

The preferable range of the straight-chain or branched alkyl group, cycloalkyl group or aromatic group as R ¹ and R ² in the above general formula is the same as the straight-chain or branched alkyl group, cycloalkyl group or aromatic group described in the item of the above- same.

In the above general formulas, one of R ¹ and R ² is preferably an organic group containing a polyether chain. The polyether structure in the organic group including the polyether chain may be any structure having a plurality of ether bonds and is not particularly limited. Examples of the polyether structure include a polyethylene glycol structure (polyethylene oxide structure), polypropylene glycol (Polypropylene oxide) structure, a polytetylene glycol (polytetramethylene glycol) structure, a polyether structure derived from a plurality of alkylene glycol (or alkylene oxide) (for example, poly (Propylene glycol / ethylene glycol) structure) and the like. The addition form of each alkylene glycol in the polyether structure derived from plural kinds of alkylene glycol may be a block type (block copolymerization type) or a random type (random copolymerization type) .

The organic group containing the polyether chain may be an organic group composed of only the polyether structure, and one or more of the polyether structure and one or more linking groups (a bivalent group having one or more atoms) are connected Organic &lt; / RTI &gt; Examples of the linking group in the organic group containing a polyether chain include 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-), and groups in which two or more thereof are bonded.

The polyether chain of L &lt; ¹ &gt; in the above general formula is not particularly limited as long as it has a structure having a plurality of the above-described ether bonds, but a structure having a plurality of the above-described ether bonds can be preferably used. The polyether chain may be an organic group composed of only a polyether structure, an organic group having a structure in which one or more of the polyether structures and one or more linking groups (a bivalent group having at least one atom) Contributing. Examples of the linking group in the organic group containing a polyether chain include 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-), and groups in which two or more thereof are bonded.

The silicon-based liquid phase compound in the present invention is more preferably at least one selected from dimethyl polysiloxane, methylphenyl polysiloxane, diphenyl polysiloxane and polyether modified polysiloxane.

The silicon-based liquid-phase compounds are disclosed in, for example, Japanese Patent Application Laid-Open Nos. 62-36663, 61-226746, 61-226745, 62-170950, Japanese Patent Application Laid-Open No. 63-34540, Japanese Patent Application Laid-Open Nos. 7-230165, 8-62834, 9-54432, 9-5988, Among the surfactants described in each of Japanese Patent Application Laid-Open No. 2001-330953, those having a liquid phase at 25 占 폚 may be mentioned.

BYK-315, BYK-313, BYK-313, BYK-307, BYK-310, BYK- BYK-331 "," BYK-332 "," BYK-323 "," BYK-325 "," BYK- 377 "," BYK-377 "," BYK-347 "," BYK-344 "," BYK- BYK-SILCLEAN 3720 " (" BYK-SILCLEAN 3720 "or more), " BYK-UV3500 "," BYK-UV3510 ", "BYK- (Manufactured by Algin Chemie), trade names "POLYFLOW KL-400X", "POLYFLOW KL-400HF", and "ACF FS 400" (Manufactured by Kyoeisha Kagaku K.K.), "Polyflow KL-401", "Polyflow KL-402", "Polyflow KL-403" KP-310 "," KP-323 "," KP-326 "," KP-341 "," KP- KP-355 "," KP-356 "," KP-351 "," KP- 368, KP-369, KP-359, KP-359, KP-362, KP-365, KP- 330 ", "KP-650 LP-7001 ", "LP-7002 " (trade names, manufactured by Shin-Etsu Chemical), " KP-391 "," KP- FZ-2105 "," 67 ADDITIVE "," 8618 ADDITIVE "," 3 ADDITIVE "," 56 ADDITIVE "(manufactured by Toray Dow Corning Co., Ltd.)," TEGO WET 270 "(manufactured by Evonik Degussa Japan Co., Ltd.) and" NBX-15 " Can be used.

The content of the silicon-based liquid phase compound in the temporary fixing adhesive of the present invention is preferably 0.009% by mass or more, more preferably 0.01% by mass or more, and still more preferably 0.05% by mass or more based on the total amount of the elastomers contained in the temporary fixing adhesive. More preferably 0.1% by mass or more, and still more preferably 0.2% by mass or more. The upper limit value is preferably 10 mass% or less, more preferably 5 mass% or less, more preferably less than 2.5 mass%, even more preferably 1 mass% or less, still more preferably 0.6 mass% or less .

When the content of the silicon-based liquid phase compound is within the above range, the adhesive property and the peeling property are more excellent. In particular, in the present invention, the amount of the temporary fixing adhesive is at least high in that the effect of the present invention can be achieved.

The silicon-based liquid-phase compound may be used singly or in combination of two or more. When two or more kinds are used in combination, it is preferable that the total content is in the above range.

<< Elastomers >>

The temporary fixing 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 substrate and by an appropriate anchoring effect. Further, when the support is peeled from the substrate, the support can be peeled from the substrate without giving stress to the substrate or the like, so that breakage or peeling of the device on the substrate can be prevented.

In the present specification, the elastomer refers to a polymer compound exhibiting elastic deformation. That is, when an external force is applied, the polymer is instantaneously deformed according to the external force, and when the external force is removed, it is defined as a polymer compound having a property of restoring the original shape in a short time.

The elastomer contained as an essential component in the present invention is an elastomer X containing repeating units derived from styrene in a proportion of 50% by mass or more and 95% by mass or less in the total repeating units, and the total of repeating units derived from styrene It is preferable to include the elastomer Y containing 10% by mass or more and less than 50% by mass of the repeating units.

When the elastomer X and the elastomer Y are used in combination, the flatness of the polished surface of the base material (hereinafter also referred to as flat polishability) is good and the occurrence of warpage of the base material after polishing can be effectively suppressed while having excellent releasability. The mechanism by which such an effect can be obtained is presumed to be as follows.

That is, since the elastomer X is a relatively hard material, an adhesive layer having excellent releasability can be produced by including the elastomer X. Further, since the elastomer Y is a relatively soft material, it is easy to form an adhesive layer having elasticity. Thus, when a laminate of a base material and a support is produced by using the temporary fixing adhesive of the present invention and the base material is polished to form a thin film, even if the pressure at the time of polishing is locally applied, the adhesive layer is elastically deformed, It is easy to go back. As a result, excellent flat polishing performance can be obtained. Also, even if the laminate after polishing is subjected to heat treatment and then cooled, the internal stress generated during cooling can be reduced by the adhesive layer, and the occurrence of warpage can be effectively suppressed.

Further, even when the elastomer Y is blended with the elastomer X, the region where the elastomer X is phase-separated exists, and the like, and the excellent releasability by the elastomer X is sufficiently achieved.

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

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

The weight average molecular weight of the polystyrene-based elastomer is preferably 2,000 to 200,000, more preferably 10,000 to 200,000, and still more preferably 50,000 to 100,000. Within this range, the solubility of the temporary fixing adhesive in the solvent is improved, and the coating property is improved. Also, when the substrate is peeled off from the support and the remaining adhesive layer is removed, since the solubility in a solvent is excellent, there is an advantage that no residue remains on the substrate or the support.

In the present invention, examples of the polystyrene-based elastomer include block copolymers, random copolymers and graft copolymers. Block copolymers are preferred. More preferred are block copolymers of styrene at one terminal or both terminals, It is particularly preferred that both ends are block copolymers of styrene. When the both ends of the polystyrene-based elastomer are made into a block copolymer of styrene (a repeating unit derived from styrene), the thermal stability tends to be further improved. This is because the repeating unit derived from styrene having high heat resistance is present at the terminal. Particularly, when the block portion of the repeating unit derived from styrene is a reactive polystyrene-based hard block, heat resistance and chemical resistance tends to be more excellent, which is preferable. When these are used as a block copolymer, it is considered that phase separation is performed between the hard block and the soft block at 200 캜 or higher. It is believed that the shape of the phase separation contributes to suppressing the occurrence of irregularities on the substrate surface of the device wafer. 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-based elastomer is preferably a hydrogenated product. When the polystyrene-based elastomer is a hydrogenated product, thermal stability and storage stability are improved. Further, the peelability and the removability of the adhesive layer after peeling are improved. The hydrogenated substance means a polymer having a structure in which an elastomer is hydrogenated (hydrogenated).

The polystyrenic elastomer preferably has a 5% thermal mass reduction temperature from 25 占 폚 to 20 占 폚 / min of 250 占 폚 or higher, more preferably 300 占 폚 or higher, still more preferably 350 占 폚 or higher, Is particularly preferable. The upper limit value is not particularly limited, but is preferably 1000 占 폚 or lower, more preferably 800 占 폚 or lower. According to this embodiment, it is easy to form an adhesive layer having excellent heat resistance.

When the original size is 100%, the polystyrene elastomer can be deformed to 200% at a room temperature (20 ° C) with a small external force. Further, when the external force is removed, the polystyrene elastomer returns to 130% or less in a short time .

The amount of the unsaturated double bond of the polystyrene type elastomer is preferably less than 15 mmol / g, more preferably 7 mmol / g or less, still more preferably less than 5 mmol / g, and less than 0.5 mmol / g in view of releasability after the heating step . The lower limit value is not specifically defined, but may be 0.001 mmol / g or more, for example.

The amount of the unsaturated double bond referred to herein does not include an unsaturated double bond in the benzene ring derived from styrene. The amount of unsaturated double bond can be calculated by nuclear magnetic resonance (NMR) measurement.

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

Examples of commercially available polystyrene elastomers include toughprene A, toughprene 125, toughprene 126S, solfrene T, asaprene T-411, asaprene T-432, asaprene T-437, Toughtech H1052, Tuftec H1052, Tuftec M1943, Tuftec M1911, Tuftec H1041, Tuftec MP10, Tuftec M1913, Tuftec H1051, Tuftec H1053, Tuftec H1052, Elastomer AR-815C, elastomer AR-840C, elastomer AR-830C, elastomer AR-860C, elastomer AR-875C, elastomer AR- Elastomer AR-SC-0, Elastomer AR-SC-5, Elastomer AR-710, Elastomer AR-SC-65, Elastomer AR-SC-30, Elastomer AR- 75, Elastomer AR-SC-45, Elastomer AR-720, Elastomer AR-741, Elastomer AR-731, FL-85N, elastomer AR-FL-60N, elastomer AR-1050, elastomer AR-1060, elastomer AR-760, elastomer AR-770, elastomer AR-781, elastomer AR- Elastomer AR-1040 (trade name, available from Alon Gassel), Kraton D1111, Kraton D1113, Kraton D1114, Kraton D1117, Kraton D1119, Kraton D1124, Kraton D1126, Kraton D1161, Kraton D1162, Kraton D1163, Kraton D1164, Kraton D1165, Kraton D1183, Kraton D1193, Kraton DX406, Kraton D4141, Kraton D4150, Kraton D4153, Kraton D4158, Kraton D4270, Kraton D4271, Kraton Kleiton D1170, Kreaton D1171, Kreaton D1173, Kreighton D1118, Kreiflex IR 0310, Kreiflex IR 0401, Kreighton D0242, Layton D1133, Creighton D1152,

Kraton D1153, Kraton D1155, Kraton D1184, Kraton D1186, Kraton D1189, Kraton D1191, Kraton D1192, Kraton DX405, Kraton DX408, Kraton DX410, Kraton DX414, Kraton DX415, Kraton Kleiton G1650, Craton G1651, Craton G1652, Craton G1643, Craton G1643, Craton G1645, Craton G1633, Craton G1650, Craton G1651, Craton G1652, Craton G1641, Craton G1510, Craton A1536, Craton FG1901, Craton FG1924, Kraton G1654, Kraton G1657, Kraton G1660, Kraton G1726, Kraton G1701, Kraton G1702, Kraton G1730, Kraton G1750, Kraton G1765, Kraton G4609, Kraton G4610 ), TR2000, TR2001, TR2003, TR2250, TR2500, TR2601, TR2630, TR2787, TR2827, TR1086, TR1600, SIS5002, SIS5200, SIS5250, SIS5405, SIS5505, Dynalon 6100P, Dynalon 4600P, Dynalon 6200P, Dynalon 4630P, DYNARON 8601P, DYNARON 8630P, DYNARON 8600P, (Trade names, manufactured by JSR Corporation), Denka STR Series (trade name, manufactured by Denki Kagaku Kogyo K.K.), and DENARON 9901P (trade names, manufactured by JSR Corporation), DENARON 6201B, DINARON 1321P, DINARON 1320P, DINARON 2324P, (Trade names, manufactured by Sumitomo Chemical Co., Ltd.), Lavalon series (trade name, manufactured by Sumitomo Chemical Co., Ltd.), Quintex 3520, Quintex 3433N, Quintax 3421, Quintax 3620, Quintax 3450, Quintax 3460 (Manufactured by Mitsubishi Kagaku), Septon 1001, Septon, 8004, Septon 4033, Septon 2104, Septon 8007, Septon 2007, Septon 2004, Septon 2063, Septon HG 252, Septon 8076, Septon 2002, Septon 1020, Septon 8104, (Trade names, trade names, trade names, trade names, trade names, trade names, trade names, trade names, trade names, trade names, (Trade name, manufactured by Sumitomo Bakelite Co., Ltd.), rheostomer (trade name, manufactured by Sumitomo Bakelite Co., Ltd.) Manufactured by Nihon Kohyo Co., Ltd.).

Next, a preferable range specific to "elastomer X" will be described.

The elastomer X is an elastomer containing repeating units derived from styrene in a proportion of 50% by mass or more and 95% by mass or less in the total repeating units, and the content of the repeating units derived from styrene is more than 50% by mass and 95% More preferably 50% by mass or more and 90% by mass or less, still more preferably 50% by mass or more but 80% by mass or less, still more preferably 55% by mass to 75% by mass, still more preferably 56% Do.

The hardness of the elastomer X is preferably 83 or more, more preferably 85 or more, and even more preferably 90 or more. The upper limit value is not particularly limited, but is, for example, 99 or less. The hardness is a value measured by 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.

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

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

The difference between the hardness of the elastomer X and the hardness of the elastomer Y is preferably 5 to 40, more preferably 10 to 35, even more preferably 15 to 33, even more preferably 17 to 29 . By setting this range, the effect of the present invention can be exerted more effectively.

In the present invention, elastomers other than the elastomer X and the elastomer Y may be blended. As the other elastomer, a polyester elastomer, a polyolefin elastomer, a polyurethane elastomer, a polyamide elastomer, a polyacrylic elastomer, a silicone elastomer, a polyimide elastomer, a rubber-modified epoxy resin and the like can be used.

The total amount of the elastomer X, the elastomer Y and the other elastomer in the temporary fixing adhesive of the present invention is preferably 50.00 to 99.99 mass%, more preferably 70.00 to 99.99 mass% with respect to the mass of the temporary fixing agent excluding the solvent , And particularly preferably from 88.00 to 99.99 mass%. When the content of the elastomer is within the above range, the adhesive property and the peeling property are more excellent.

The elastomer X, the elastomer Y and the other elastomer in the temporary fixing adhesive of the present invention may be combined in plural kinds.

The total amount of the elastomer X and the elastomer Y in the total amount of the elastomer contained in the temporary fixing adhesive of the present invention preferably accounts for 90 mass% or more, more preferably 95 mass% or more, and more preferably 98 mass% Is particularly preferable.

In a case where the elastomer Y is blended, the mass ratio of the elastomer X and the elastomer Y is preferably 5:95 to 95: 5, more preferably 20:80 to 90:10, To 85:15 are particularly preferred. Within the above range, warpage suppression and peelability are more effectively obtained.

<< Antioxidants >>

The temporary fixing adhesive of the present invention may contain an antioxidant from the viewpoint of preventing low molecular weight or gelation of the elastomer due to oxidation at the time of heating. As the antioxidant, phenol antioxidants, sulfur antioxidants, phosphorus antioxidants, quinone antioxidants, amine antioxidants and the like can be used.

Examples of the phenol antioxidant include para-methoxyphenol, 2,6-di-tert-butyl-4-methylphenol, Irganox1010, Irganox1330, Irganox3114, Irganox 1035 Sumilizer MDP-S "and" Sumilizer GA-80 "manufactured by Sumitomo Chemical Co., Ltd., and the like.

Examples of the sulfur-based antioxidant include 3,3'-thiodipropionate di-stearyl, Sumilizer TPM, Sumilizer TPS, Sumilizer TP-D and the like available from Sumitomo Chemical Co., .

Examples of the phosphorus antioxidant include tris (2,4-di-tert-butylphenyl) phosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, poly Dialkyldiphenylphosphite, triphenylphosphite, "Irgafos 168", "Irgafos 38" manufactured by BASF Co., Ltd., and the like.

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

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

Of the above 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.

Among the above-mentioned antioxidants, it is preferable to use a phenolic antioxidant in combination with a sulfur-based antioxidant or a phosphorus-based antioxidant, and it is particularly preferable to use a phenolic antioxidant in combination with a sulfur-based antioxidant. Particularly when a polystyrene-based elastomer is used as the elastomer, it is preferable to use a phenolic antioxidant and a sulfur-based antioxidant in combination. By using such a combination, it is expected that the deterioration of the elastomer due to the oxidation reaction can be effectively suppressed. When the phenolic antioxidant and the sulfur antioxidant are used in combination, the mass ratio of the phenol antioxidant to the sulfur antioxidant is preferably 95: 5 to 5:95, : 25 is more preferable.

As the combination of the antioxidants, Irganox 1010, Sumilizer TP-D, Irganox 1330 and Sumilizer TP-D, Sumilizer GA-80 and Sumilizer TP-D are preferable, Irganox 1010 and Sumilizer TP-D, Irganox 1330 and Sumilizer TP- Irganox 1010 and Sumilizer TP-D are particularly preferred.

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

When the temporary fixing adhesive has an antioxidant, the content of the antioxidant is preferably 0.001 to 20.0% by mass, more preferably 0.005 to 10.0% by mass, based on the total solid content of the temporary fixing adhesive.

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

<< Solvent >>

The temporary fixing adhesive of the present invention preferably contains a solvent. Particularly, in the case of forming the adhesive layer by applying the temporary fixing adhesive of the present invention, it is preferable to add a solvent. As the solvent, any known solvent can be used without limitation, and an organic solvent is preferable.

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

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

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

Butylbenzene, isobutylbenzene, tert-butylbenzene, amylbenzene, isoamylbenzene, (2,2-dimethylbenzyl) benzene, toluene, xylene, anisole, mesitylene, ethylbenzene, propylbenzene, cumene, 1-phenyloctane, 1-phenylnonane, 1-phenyldecane, cyclopropylbenzene, cyclohexylbenzene, 2-ethyltoluene, 1 , 2-diethylbenzene, o-cymene, indene, 1,2,3,4-tetrahydronaphthalene, 3-ethyltoluene, m-cymene, 1,3-diisopropylbenzene, , 1,4-diethylbenzene, p-cymene, 1,4-diisopropylbenzene, 4-tert-butyltoluene, 1,4-di-tert-butylbenzene, , 2,3-trimethylbenzene, 1,2,4-trimethylbenzene, 4-tert-butyl-ozylene, 1,2,4-triethylbenzene, 1,3,5- 1,3,5-triisopropylbenzene, 5-tert-butyl-m-xylene, 3,5-di-tert-butyltoluene, 1,2,3,5-tetramethyl Zhen, 1,2,4,5-tetramethyl benzene, be an aromatic hydrocarbon such as benzene pentamethyl soryu;

And hydrocarbons such as limonene, p-mentine, nonene, decane, dodecane and decalin, and the like.

Of these, methylethylene, tert-butylbenzene, 1,2,4-trimethylbenzene, p-menthane,? -Butyrolactone, anisole, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl But are not limited to, cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, ethylcarbitol acetate, butylcarbitol acetate, propylene glycol And propylene glycol methyl ether acetate are preferable, and mesitylene is more preferable.

These solvents are preferably mixed with two or more kinds of them from the viewpoints of improvement of coating surface properties and the like. In this case, particularly preferable examples include mesitylene, tert-butylbenzene, 1,2,4-trimethylbenzene, p-mentine, y-butyrolactone, anisole, methyl 3-ethoxypropionate, 3- Ethyl propionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, ethylcarbitol acetate, butyl carbitol Acetate, propylene glycol methyl ether, and propylene glycol methyl ether acetate.

When the temporary fixing adhesive contains a solvent, the content of the solvent in the temporary fixing adhesive is preferably such that the total solid content concentration of the temporary fixing adhesive is 5 to 80% by mass and 10 to 50% by mass , And particularly preferably from 15 to 40 mass%.

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

When the temporary fixing adhesive of the present invention is used for the adhesive layer of the adhesive film or the adhesive backing, as described later, the solvent content is preferably 1% by mass or less, more preferably 0.1% by mass or less, Is particularly preferable.

<< Radical 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 the flow deformation of the adhesive layer during heating. This makes it possible to suppress the flow deformation of the adhesive layer at the time of heating, for example, when the laminate after polishing the substrate is heated, and the occurrence of warpage can be effectively suppressed. In addition, since an adhesive layer having a hardness can be formed, even if a pressure is locally applied at the time of polishing the substrate, the adhesive layer is hardly deformed, and the 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 capable of being polymerized by a radical can be used. Such compounds are well known in the art, and they can be used without any particular limitation in the present invention. These may be, for example, monomers, prepolymers, oligomers or mixtures thereof and their chemical forms such as their multimers. As the radical polymerizing compound, reference can be made to the disclosure of Japanese Laid-Open Patent Publication No. 2015-087611, paragraphs 0099 to 080, the contents of which are incorporated herein by reference.

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

Examples of commercially available radically polymerizable compounds include urethane oligomers UAS-10, UAB-140 (manufactured by Sanyo Kogaku Pulp), NK Ester M-40G, NK Ester 4G, NK Ester A-9300, NK Ester M- NK Ester A-BPE-4, UA-7200 (manufactured by Shin Nakamura Kagaku), DPHA-40H (manufactured by Nippon Kayaku), UA-306H, UA-306T, UA- 306I, AH-600, T-600, AI-600 (manufactured by Kyoeisha Chemical Co., Ltd.) and Blemmer PME400 (manufactured by Nichiyu Corporation).

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

(2)

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

The content of the radically polymerizable compound in the temporary fixing adhesive of the present invention is preferably from 1 to 5 parts by mass with respect to the mass of the temporary fixing adhesive excluding the solvent from the viewpoints of good adhesiveness and flat abrasion resistance, To 50 mass%, more preferably from 1 to 30 mass%, and still more preferably from 5 to 30 mass%. The radical polymerizing compound may be used singly or in combination of two or more kinds.

In the temporary fixing adhesive of the present invention, the mass ratio of the elastomer to the radical polymerizable compound in the case of adding the radical polymerizable compound is preferably 98: 2 to 10:90, and more preferably 95: : 5 to 30:70, and particularly preferably 90:10 to 50:50. When the mass ratio of the elastomer to the radical polymerizable compound is within the above range, an adhesive layer excellent in adhesiveness, flat abrasion resistance, peelability and flexural restraint can be formed.

<< Polymer compound >>

The temporary fixing adhesive of the present invention may contain a polymer compound other than the silicon-based liquid phase compound and the elastomer described above as needed in order to adjust the coating property, adhesive property, releasability, heat resistance and the like. The coating property referred to herein means the uniformity of the film thickness after application and the film formability after application.

In the present invention, any of the polymer compounds may 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 even more preferably 100,000 to 300,000.

Specific examples of the polymer compound include a hydrocarbon resin, a novolac resin, a phenol resin, an epoxy resin, a melamine resin, an urea resin, an unsaturated polyester resin, an alkyd resin, a polyimide resin, a polyvinyl chloride resin, , Teflon (registered trademark), polyamide resin, polyacetal resin, polycarbonate resin, polyphenylene ether resin, polystyrene terephthalate resin, polyethylene terephthalate resin, polyphenylene sulfide resin, polysulfone resin, Polyester resins, polyester resins, polyester resins, polyamideimide resins, and the like. Among them, a hydrocarbon resin, a novolac resin, and a polyimide resin are preferable, and a hydrocarbon resin is more preferable. The polymer compound may be used in combination of two or more as necessary.

As the hydrocarbon resin, any one can be used.

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

Examples of hydrocarbon resins conforming to the above conditions include terpene resins, terpene phenol resins, modified terpene resins, hydrogenated terpene resins, hydrogenated terpenephenol resins, rosins, rosin esters, hydrogenated rosins, hydrogenated rosin esters, An alicyclic petroleum resin, an aromatic petroleum resin, a hydrogenated petroleum resin, a modified petroleum resin, an alicyclic petroleum resin, a coumarone petroleum resin, an indene petroleum resin, etc. .

The hydrocarbon resin is preferably terpene resin, rosin, petroleum resin, hydrogenated rosin, or polymerized rosin, more preferably terpene resin or rosin.

From the viewpoint of improving the coating property, releasability and heat resistance, it is preferable to contain a polymer compound having a non-three-dimensional crosslinked structure having a fluorine atom. The non-three-dimensional crosslinked structure means that the ratio of the crosslinked structure that does not contain a crosslinked structure in the compound or forms a three-dimensional crosslinked structure with respect to the total crosslinked structure in the compound is 5% or less, preferably 1% or less. As the polymer compound of a non-three-dimensional crosslinked structure having a fluorine atom, a polymer comprising one or two or more fluorine-containing monofunctional monomers can be preferably used. More specifically, there may be mentioned tetrafluoroethylene, hexafluoropropene, tetrafluoroethylene oxide, hexafluoropropene oxide, perfluoroalkyl vinyl ether, chlorotrifluoroethylene, vinylidene fluoride, purple (Meth) acrylic acid ester containing at least one fluoroalkyl group, a fluoroalkyl group-containing (meth) acrylic acid ester, and a fluoroalkyl group-containing (meth) acrylate ester, or copolymers of these monomers, , At least one fluorinated resin selected from a copolymer of one or more fluorinated monofunctional monomers and chlorotrifluoroethylene, and the like.

The polymer compound having a non-three-dimensional crosslinked structure having a fluorine atom is preferably a (meth) acrylic resin containing a perfluoroalkyl group which can be synthesized from a perfluoroalkyl group-containing (meth) acrylic acid ester.

As the (meth) acrylic acid ester containing a perfluoroalkyl group, specifically, it is preferably a compound represented by the following formula (101).

(101)

(3)

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

Examples of the alkyl group represented by R ¹⁰¹ , R ¹⁰² and R ¹⁰³ in the general formula (101) are preferably an alkyl group having 1 to 8 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, an octyl group, tert-butyl group, isopentyl group, 2-ethylhexyl group, 2-methylhexyl group, cyclopentyl group and the like. The aryl group is preferably an aryl group having 6 to 12 carbon atoms, and examples thereof include a phenyl group, a 1-naphthyl group and a 2-naphthyl group. As R ¹⁰¹ to R ¹⁰³ , a hydrogen atom or a methyl group is particularly preferable.

Y ¹⁰¹ represents a single bond or a divalent linking group selected from the group consisting of -CO-, -O-, -NH-, a divalent aliphatic group, a divalent aromatic group and a combination thereof, and the divalent aliphatic group may be a cyclic A straight chain structure is preferable to a straight chain structure having branches. The number of carbon atoms of the divalent aliphatic group is preferably from 1 to 20, more preferably from 1 to 15, still more preferably from 1 to 12, still more preferably from 1 to 10, even more preferably from 1 to 8 Still more preferably 1 to 4 carbon atoms.

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.

As Y ¹⁰¹ , it is preferable that the Y ¹⁰¹ is an aliphatic group having a bivalent straight-chain 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 particularly preferably a fluorinated alkyl group having 1 to 15 carbon atoms desirable. The fluorinated alkyl group is a straight chain {e.g. _{-CF 2 CF 3, -CH 2 (} CF 2) 4 H, -CH 2 (CF 2) 8 CF 3, -CH 2 CH 2 (CF 2) 4 H , etc. }, and even, for example, {branch structure _{-CH (CF 3) 2, -CH} 2 CF (CF 3) 2, -CH (CH 3) CF 2 CF 3, -CH (CH 3) (CF 2) 5 CF ₂ H, etc.), and may have an alicyclic structure (preferably, a 5-membered ring or a 6-membered ring such as a perfluorocyclohexyl group, a perfluorocyclopentyl group, (E.g., -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.). It may also be a perfluoroalkyl group.

Specific examples of the perfluoroalkyl group-containing (meth) acrylic resin include a repeating unit represented by the following formula (102).

Equation (102)

[Chemical Formula 4]

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

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

More specifically, acrylic acid esters such as alkyl acrylates (preferably having 1 to 20 carbon atoms in the alkyl group) (e.g., methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, amyl acrylate , Ethylhexyl acrylate, octyl acrylate, t-octyl acrylate, chloroethyl acrylate, 2,2-dimethylhydroxypropyl acrylate, 5-hydroxypentyl acrylate, trimethylolpropane monoacrylate, (For example, phenyl acrylate), alkyl (meth) acrylates such as methyl acrylate, ethyl acrylate, butyl acrylate, Methacrylic acid esters such as methacrylate (the alkyl group preferably has 1 to 20 carbon atoms) (e.g., methyl methacrylate Acrylates such as 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 (Methacrylic acid, methacrylic acid, methacrylic acid, methacrylic acid, methacrylic acid, methacrylic acid and the like), glycidyl methacrylate, furfuryl methacrylate, tetrahydrofurfuryl methacrylate and the like), aryl methacrylate Etc.), styrenes such as styrene and alkylstyrene (e.g., methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, , Diethylstyrene, isopropylstyrene, butylstyrene, hexylstyrene, cyclohexylstyrene, decylstyrene, benzylstyrene, chloromethylstyrene, trifluoromethylstyrene, ethoxymethylstyrene, Acetoxymethylstyrene, etc.), alkoxystyrene (e.g., methoxystyrene, 4-methoxy-3-methylstyrene, dimethoxystyrene, etc.), halogensilane But are not limited to, styrene, styrene, dichlorostyrene, trichlorostyrene, tetrachlorostyrene, pentachlorostyrene, bromostyrene, dibromostyrene, iodostyrene, fluorostyrene, -Bromo-4-trifluoromethylstyrene, 4-fluoro-3-trifluoromethylstyrene, etc.), acrylonitrile, methacrylonitrile acrylic acid, and carboxylic acid (Methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, para-carboxy styrene, and metal salts and ammonium salt compounds of these acid groups). In view of releasability, (Meth) acrylic acid esters having a hydrocarbon group of 1 to 24 carbon atoms are preferred, and examples thereof include methyl, butyl, 2-ethylhexyl, lauryl, stearyl and glycidyl esters of (meth) (Meth) acrylates, particularly acrylates, of higher alcohols such as ethylhexyl, lauryl and stearyl are preferred.

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), Teflon (DuPont), Fluon (Asahi Glass), Hyler (SolvaySolexis), Haier (SolvaySolexis), Lumipro Fluorine resins such as Arplose (Asahi Glass Co.), Saitot (Asahi Glass Co.), Sephrill Soft (Central Glass Co.), Sephrill Coat (Central Glass Co.) and Daionin (3M) (DuPont), Pombulin (DaiTokuTech), and DEMNUM (DaiKingo), which are trademarks, such as SILIC (DuPont), SIREL (DuPont), SIFEL Various fluorine oils including perfluoropolyether oils, and fluorine-containing mold release agents such as DieFree FB series (Daikin Kogyu Co., Ltd.) and Megapak series (DIC).

The weight average molecular weight in terms of polystyrene in the gel permeation chromatography (GPC) method of a polymer compound having a fluorine atom-containing non-three-dimensional crosslinked structure is preferably 100000 to 2000, more preferably 50000 to 2000, 2000 is most preferable.

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

<< Surfactant >>

The temporary fixing adhesive of the present invention may contain a surfactant. The surfactant referred to herein does not include a silicon-based liquid phase compound.

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

Preferable examples of the nonionic surfactant 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, reference can be made to the description in paragraphs 0173 to 0177 of Japanese Laid-Open Patent Publication No. 2015-065401, the contents of which are incorporated herein by reference.

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, more preferably 0.01 to 0.5% by mass, based on the total solid content of the temporary fixing adhesive, Particularly preferred. The surfactant may be one kind or two or more kinds. When two or more kinds of surfactants are used, the total amount is preferably in the above range.

<< Fluorine-based liquid phase compound >>

From the viewpoint of improving the coating property or releasability, the temporary fixing adhesive of the present invention preferably contains a fluorinated liquid compound.

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

The viscosity of the fluorine-based liquid phase compound at 25 占 폚 is more preferably 10 to 20,000 mPa 占 퐏, and still more preferably 100 to 15,000 mPa 占 퐏. When the viscosity of the fluorine-based liquid-phase compound is within the above range, the fluorine-based liquid compound tends to be unevenly distributed in the surface layer of the adhesive layer.

The fluorine-based liquid phase compound may be any of oligomer and polymer compounds. It may also be a mixture of an oligomer and a polymer. Such a mixture may further contain a monomer. The fluorine-based liquid-phase compound may be a monomer.

The fluorine-based liquid phase compound is preferably an oligomer, a polymer and a mixture thereof from the viewpoint of heat resistance and the like.

Examples of the oligomer and polymer include a radical polymer, a cationic polymer, and an anionic polymer, all of which can be preferably used. Vinyl polymers are particularly preferred.

The weight average molecular weight of the fluorine-based liquid phase compound is preferably from 500 to 100,000, more preferably from 1,000 to 50,000, and still more preferably from 2,000 to 20,000.

The fluorine-based liquid phase compound is preferably a compound which is not denatured during the treatment of a substrate used for adhesion. For example, a compound which can be present as a liquid phase even after heating at 250 DEG C or higher or after treating the substrate with various chemical solutions is preferable. As a specific example, the viscosity at 25 ° C after heating from 250 ° C to 25 ° C at a temperature elevation rate of 10 ° C / min from 25 ° C is preferably from 1 to 100,000 mPa · s, more preferably from 10 to 20,000 mPa · s · S is more preferable, and 100 to 15,000 mPa · s is even more preferable.

The fluorine-based liquid phase compound having such characteristics is preferably a non-thermosetting compound having no reactive group. The term reactive group as used herein refers to the whole period of the reaction in the heating at 250 ° C, and includes a polymerizable group and a hydrolyzable group. Specific examples thereof include (meth) acrylic groups, epoxy groups, and isocyanato groups.

The fluorine-based liquid-phase compound preferably has a 10% thermal mass reduction temperature at 25 ° C or higher and 20 ° C / minute at 250 ° C or higher, more preferably 280 ° C or higher. The upper limit value is not particularly limited, but is preferably 1000 占 폚 or lower, for example, and more preferably 800 占 폚 or lower. According to this embodiment, it is easy to form an adhesive layer having excellent heat resistance. The mass reduction temperature is a value measured under the temperature elevation condition under a nitrogen stream by a thermogravimetric analyzer (TGA).

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

The number of carbon atoms of the alkyl group is preferably from 2 to 30, more preferably from 4 to 30, still more preferably from 6 to 30, and particularly preferably from 12 to 20. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a dodecyl group, a tetradecyl group, , Isobutyl group, sec-butyl group, tert-butyl group, 1-ethylpentyl group and 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 carbon number of the alkoxy group is preferably from 1 to 30, more preferably from 1 to 20, and even more preferably from 1 to 10. The alkoxy group is preferably straight-chain or branched.

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

The cycloalkyl group may be monocyclic or polycyclic. The number of carbon atoms of the cycloalkyl group is preferably from 3 to 30, more preferably from 4 to 30, still more preferably from 6 to 30, and most preferably from 6 to 20. 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 an adamantyl group, a norbornyl group, a vinyl group, a camphanyl group, a decahydronaphthyl group, a tricyclodecanyl group, a tetracyclodecanyl group, a camphoryl group, a dicyclohexyl group, .

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 from 6 to 20, more preferably from 6 to 14, and most preferably from 6 to 10. It is preferable that the aromatic group does not contain a hetero atom (for example, a nitrogen atom, an oxygen atom, a sulfur atom, etc.) in the element constituting the ring. Specific examples of the aromatic group include a benzene ring, a naphthalene ring, a pentane ring, an indene ring, an azuren ring, a heptane ring, an indene ring, a perylene ring, a pentacene ring, an acenaphthalene ring, a phenanthrene ring, an anthracene ring, a naphthacene ring, A thiophene ring, a fluorene ring, a biphenyl ring, a pyrrole ring, a furan ring, a thiophen ring, an imidazole ring, an oxazole ring, a thiazole ring, a pyridine ring, a pyrazine ring, a pyrimidine ring, , Indole ring, benzofuran ring, benzothiophen ring, isobenzofuran ring, quinoline ring, quinoline ring, phthalazine ring, naphthyridine ring, quinoxaline ring, quinoxazoline ring, isoquinoline ring, carbazole ring, phenan Triazine ring, acridine ring, phenanthroline ring, thianthrene ring, cromene ring, zanthen ring, phenoxathiine ring, phenothiazine ring, and phenanthrene ring.

The aromatic group may have the substituent described above.

The fluorine-based liquid-phase compound may be a compound containing only one kind of oil-cooling group, or may contain two or more kinds. The organic group may contain a fluorine atom. That is, the fluorine-based liquid-phase compound in the present invention may be a compound in which only a hydrophilic group contains a fluorine atom. Further, in addition to a hydrophilic group, a compound having a fluorine atom-containing group (also referred to as a fluorine group) may be used. Preferably, it is a compound containing a mineral oil and a fluorine group. When the fluorine-based liquid-phase 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 preferably contains no fluorine atom.

The fluorine-based liquid-phase compound preferably 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. For example, fluorinated alkyl groups, fluorinated alkylene groups and the like. Among the fluorine groups, those functioning as a lipophilic group are assumed to be included in lipophilic groups.

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

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

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

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

As the fluorine-based liquid phase compound, a commercially available product may be used. For example, F-251, F-281, F-477, F-553, F-554, F-555, F-556, F-557, F- F-560, F-561, F-563, F-565, F-567, F-568, F-571, R-40, R-41, R- 710F, 710FM, 710FS, 730FL, and 730LM.

In the temporary fixing adhesive of the present invention, when the fluorinated liquid compound is used, the content thereof is preferably 0.01 to 10% by mass, more preferably 0.02 to 5% by mass, based on the mass of the temporary fixing adhesive excluding the solvent . The lower limit is preferably 0.03 mass% or more. The upper limit is preferably 1% by mass or less, more preferably 0.5% by mass or less. When the content of the fluorine-based liquid phase compound is within the above range, the adhesive property and the peeling property are excellent. The fluorinated liquid-phase compound may be used singly or in combination of two or more. When two or more kinds are used in combination, it is preferable that the total content is in the above range.

<< Other Ingredients >>

The temporary fixing adhesive in the present invention may contain various additives such as a plasticizer, a curing agent, a catalyst other than the above, a filler, an adhesion promoter, an ultraviolet absorber, an aggregation inhibitor , An elastomer and other polymer compounds, and the like. When these additives are compounded, the amount thereof is preferably 3% by mass or less, more preferably 1% by mass or less, based on the total solid content of the fixed adhesive. The lower limit value in the case of blending is preferably 0.0001 mass% or more. The total amount of these additives to be added is preferably 10 mass% or less, more preferably 3 mass% or less, of the total solid content of the temporary fixing adhesive. The lower limit of the total amount of the components to be blended is preferably 0.0001 mass% or more.

The temporary fixing adhesive in the present invention preferably does not contain impurities such as metals. The content of the impurities contained in the adhesive is preferably 1 ppm or less, more preferably 1 ppb or less, more preferably 100 ppt or less, even more preferably 10 ppt or less, Is particularly preferable.

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

As a method for reducing the impurities such as metals contained in the temporary fixing adhesive, a raw material having a small metal content is selected as a raw material constituting the temporary fixing adhesive, the raw material constituting the temporary fixing adhesive is subjected to filter filtration, And lining the inside with polytetrafluoroethylene or the like to perform distillation under conditions in which contemination is suppressed as much as possible. Preferable conditions for the filter filtration performed on the raw material constituting the temporary fixing adhesive are the same as the above-mentioned conditions.

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

&Lt; Preparation of temporary fixing adhesive >

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

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

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

When using a filter, other filters may be combined. At this time, the filtering using the first filter may be performed once, or may be performed two or more times. When filtering is performed two or more times in combination with other filters, it is preferable that the pore diameters of the second and subsequent pores are equal to or smaller than the pore diameters of the first filtering. The first filter having different pore diameters may be combined within the above-described range. The hole diameter here can refer to the nominal value of the filter manufacturer. As a commercially available filter, there may be selected, for example, various filters provided by Nippon Oil Corporation, Advantech Toyokawa Co., Ltd., Nippon Integrity Corporation (formerly Nihon Micro-Roller Corporation) or Kitsch Microfilter .

&Lt; Use of temporary fixing adhesive >

The temporary fixing adhesive of the present invention can form an adhesive layer having excellent adhesive property and peeling property. Thus, for example, when a mechanical or chemical treatment is applied to a device wafer, the device wafer and the support can be stably stuck to each other, and adhesion 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 semiconductor devices.

&Lt; 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 fixing adhesive of the present invention.

In the adhesive film of the present invention, the silicon-based liquid phase compound is localized on the surface layer of the adhesive layer. As a result, the peelability is excellent. Further, since the adhesive layer contains an elastomer, excellent adhesion can be obtained by following the fine irregularities of the support and the base material and by proper anchor effect. As a result, both adhesion and peelability can be achieved.

In the adhesive layer of the adhesive film of the present invention, the concentration of the silicon-based liquid phase compound ranges from 5% to 50% of the thickness in the thickness direction from the surface of the adhesive layer to 5% It is preferable that the region is different.

The concentration of the silicon-based liquid phase compound in the adhesive layer can be measured by, for example, a method of performing X-ray photoelectron spectroscopy (ESCA) measurement while performing etching or a method of performing oblique cutting and flight time type secondary ion mass spectrometry (TOF-SIMS) Can be measured by a combination method.

The adhesive film of the present invention preferably has a solvent content of 1% by mass or less, more preferably 0.1% by mass or less, and particularly preferably contains no solvent. 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 탆, more preferably 0.1 to 200 탆, more preferably 10 to 200 탆, Particularly preferred. If the average thickness of the adhesive layer is within the above range, the adhesive film is easily formed into an excellent flatness. In the present invention, the average thickness of the adhesive layer is defined as an average value of five points measured by ellipsometry.

The adhesive film of the present invention may be a single layer of an adhesive layer or may have another layer on one side or both sides of the adhesive layer. As the other layer, a release layer is exemplified.

The average thickness of the release layer is preferably 0.001 to 1 mu m, more preferably 0.01 to 0.5 mu m. Within this range, the adhesive film has an appropriate adhesive force, and the adhesive property to the substrate or the support is good, and the adhesive film can be easily peeled off from the substrate or the support. In the present invention, the average thickness of the release layer is defined as an average value of five points measured by ellipsometry. The releasing layer preferably contains a compound containing a fluorine atom. Details of the release layer can be found in paragraphs 0068 to 0145 of Japanese Laid-Open Patent Publication No. 2014-066385, the contents of which are incorporated herein by reference.

Further, the adhesive film of the present invention may be configured so as not to have a release layer. This is because the adhesive layer itself made of the temporary fixing adhesive in the present invention has peelability.

The adhesive film of the present invention may be a "release film-adhered film" by adhering a release film to one side or both sides of the adhesive layer. According to this aspect, it is possible to prevent troubles that may occur on the surface of the adhesive layer when the long adhesive film is wound in the form of a roll, or in which the adhesive film adheres during storage.

The release film can be peeled and removed in use. For example, in the case where the releasing film is adhered to both sides, the release film on one side is peeled off, the adhesive surface is laminated on the base material or the support, and the remaining release film is peeled off, One can keep.

&Lt; Method of 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 formation method, a solution film formation method, or the like.

The melt film-forming method is a method for obtaining a film (sheet) by realizing fluidity by heating and melting a raw material composition, forming the melt into a sheet form using an extrusion molding apparatus or an injection molding apparatus, and cooling the melt.

In the extrusion molding method, a roll-shaped long film can be obtained. In the injection molding method, it is difficult to obtain a long film, but a high film thickness precision is obtained. Other additives may be added by mixing, melting and stirring. A release film may be laminated on one or both sides of the film to form a "release film-adhered film ".

The solution film-forming method is a method of obtaining a film (sheet) by realizing fluidity by dissolving a raw material composition in a solvent and coating the solution on a support such as a film, a drum or a band to form a sheet and drying. For coating, there are a method of extruding the solution from the slit-shaped opening by pressure and coating the solution, a method of transferring the solution by gravure or anilox roller to coat the solution, a method of coating by spraying the solution while spraying the solution from the dispenser, A method in which a film, a drum or a band is passed through it, a method in which the film is dipped, a method in which the film is coated by scraping while a wire bar solution is pushed out, and the like. Other additives may also be added to the solution by dissolving and mixing and stirring. After the solution is coated on the support and dried to give a solidified sheet, the sheet can be mechanically peeled off from the support to obtain a single film (sheet). As the treatment for imparting releasability to the support in advance, the release layer may be applied, immersed, gas treated, electromagnetic wave irradiated, plasma irradiated, or the like so as to facilitate peeling. Alternatively, the film may be left as it is without being peeled from the support, and the adhesive film with the release film may be left while the sheet is adhered on the film support. By performing such treatment continuously, a roll-shaped long film can be obtained. Alternatively, a release film may be laminated on both sides of the adhesive film to form a "double-side release film-attached sheet ".

<Adhesive Support>

Next, the adhesive support of the present invention will be described.

The adhesive support of the present invention has a support and an adhesive layer made of the temporary fixing adhesive of the present invention. The adhesive layer preferably includes the above-described elastomer X and elastomer Y as the elastomer.

The average thickness of the adhesive layer varies depending on the application, but is preferably 0.1 to 500 mu m, for example.

The adhesive layer is formed by applying the temporary fixing adhesive of the present invention onto the surface of the support using a spin coating method, a spraying method, a roller coating method, a float coating method, a doctor coating method, a dipping method, or the like, followed by drying . The drying is carried out, 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 m, more preferably 1 to 10 m, for example.

The adhesive layer may be formed on the support by laminating the above-mentioned adhesive film of the present invention. By forming an adhesive layer using an adhesive film, an adhesive layer can be formed even by using a material such as an elastomer having poor solubility in a solvent, so that an adhesive layer having excellent heat resistance and chemical resistance can be easily formed. In addition, the thick adhesive layer of 10 탆 or more can be made flat without any variation in thickness. The average thickness of the adhesive layer in this case is not particularly limited. For example, the average thickness is preferably 0.1 to 200 占 퐉, more preferably 10 to 200 占 퐉, and particularly preferably 50 to 200 占 퐉.

In order to form an adhesive layer on a support using an adhesive film, for example, an adhesive film is set on a vacuum laminator, the adhesive film is placed on the support in this apparatus, the adhesive film and the support are brought into contact with each other under vacuum, And a method of fixing (laminating) the adhesive film to a support by pressing with a roller or the like. The adhesive film (adhesive layer) fixed to the support may be cut into a desired shape such as a circular shape.

In the adhesive support of the present invention, the adhesive layer is formed such that the concentration of the silicon-based liquid phase compound in the range of 5% from the surface on the opposite side of the support to the thickness direction of the adhesive layer is larger than the thickness of the adhesive layer Direction is higher than the range in the range of more than 5% and 50%. According to this aspect, when the adhesive support is adhered to a substrate such as a device wafer and then peeled off from the device wafer, the peelability is improved. Further, the adhesive layer can be easily removed from the surface of the substrate or the device wafer by a method such as mechanical peeling.

The concentration of the silicon-based liquid phase compound is such that the area in the range of 5% in the thickness direction of the adhesive layer from the surface on the opposite side of the support is larger than 5% and 50% in the thickness direction of the adhesive layer from the surface opposite to the support By mass or more, more preferably 30% by mass or more.

In the adhesive support of the present invention, the support (also referred to as carrier support) is not particularly limited, and examples thereof include a silicon substrate, a glass substrate, a metal substrate, and a compound semiconductor substrate. Among them, a silicon substrate is preferable in view of the fact that it is difficult to contaminate a silicon substrate which is typically used as a substrate of a semiconductor device, and an electrostatic chuck generally used in a semiconductor device manufacturing process can be used.

The thickness of the support is not particularly limited, but is preferably 300 탆 to 100 mm, more preferably 300 탆 to 10 mm, for example.

The support may have a release layer on its surface. That is, the support may be a release layer adherend having a release layer on the surface of a substrate such as a silicon substrate.

As the release layer, a low surface energy layer containing a fluorine atom and / or a silicon atom is preferable, and it is preferable to have a material containing a fluorine atom and / or a silicon atom. The fluorine content of the release layer is preferably 30 to 80 mass%, more preferably 40 to 76 mass%, and particularly preferably 60 to 75 mass%.

As the material of the release layer, the same material as the release layer which may be formed on the surface layer of the above-mentioned adhesive film can be used.

<Laminate>

Next, the laminate of the present invention will be described. The laminate of the present invention comprises a support, an adhesive layer comprising 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. 1 and 2. Fig. It goes without saying that the embodiment of the laminate of the present invention is not limited to these. 1 and 2, reference numeral 1 denotes a substrate, 2 denotes a support, and 3, 3A and 3B denote adhesive layers, respectively.

1, the adhesive layer 3 is placed on the surface of the support 2 and the substrate 1 is bonded to the surface of the adhesive layer 3 opposite to the support . In this way, 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 that the throughput of the laminate formation can be improved. That is, in the laminate, an embodiment in which only the adhesive layer is provided between the substrate and the support without including the release layer is exemplified.

In the first embodiment, the peel strength A between the support and the adhesive layer made of the temporary fixing adhesive of the present invention and the peel strength B between the adhesive layer made of the temporary fixing adhesive of the present invention and the substrate satisfy the following formulas (1) and It is preferable to satisfy the expression (2).

A <B ... (1)

B? 4 N / cm ... (2)

By satisfying the relationship of the above formula (1), the peel strength A and the peel strength B can be peeled from the interface between the support and the adhesive layer comprising the temporary fixing adhesive of the present invention when peeling off the support from the substrate.

By satisfying the relationship of the above formula (2), the peeling strength B can easily peel off the adhesive layer from the substrate surface in a film-like state. That is, the adhesive layer can be easily peeled off by mechanical peeling.

The peel strength B is preferably 3 N / cm or less, more preferably 2 N / cm or less.

The peel strength in the present invention is a value obtained by measuring the strength applied when pulled up in the 90 占 direction. The peel strength A represents the force applied when the substrate is fixed and the end portion of the support is pulled up at a rate of 50 mm / min in the 90 占 direction. The peel strength B represents the force applied when the base material is fixed and the film-like adhesive layer is pulled up at a rate of 50 mm / min in the 90 占 direction.

In the laminate of the present invention, when the support is peeled off from the substrate, the adhesive layer made of the temporary fixing adhesive of the present invention is peeled from the interface between the substrate and the adhesive layer to be in a range of 50% Based liquid phase compound is present or the adhesive layer is peeled off from the interface between the support and the adhesive layer so that the residue of the silicon-based liquid phase compound is in the range of 50% or more of the area of the release surface of the adhesive layer of the support It is preferable that it is attached. It is preferable that the residue derived from the elastomer is not adhered in a range of 50% or more of the area of the release surface, and more preferably, it is not adhered in a range of 99% or more.

The residue of the silicon-based liquid phase compound and the residue derived from the elastomer can be observed with the naked eye, optical microscope, scanning electron microscope, X-ray photoelectron spectroscopy or the like. In the present invention, however, Shall be measured.

In the present specification, the term " residue of the silicon-based liquid phase compound "is a silicon-based liquid phase compound component of the adhesive layer, and the term" residue derived from an elastomer "means an elastomer component of the adhesive layer.

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

The second embodiment of the laminate of the present invention is an embodiment shown in Fig. 2, in which the support 2, the adhesive layer 3A and the substrate 1 are laminated in this order, 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, it is preferable that the substrate 1 and the adhesive layer 3A, the adhesive layer 3A and the second adhesive layer 3B, the second adhesive layer 3B, and the support 2 are in contact with each other on the surface.

As in the case of the second embodiment, there is an advantage that two or more adhesive layers make it possible to easily bond the substrate and the substrate to each other with good filling properties (no voids). Especially, the filling property can be improved more effectively by providing the adhesive layer 3B on the side of the support 2 and providing the second adhesive layer 3A on the side of the substrate 1 and bonding them together.

The third embodiment of the laminate of the present invention is characterized in that the support 2, the adhesive layer 3A and the substrate 1 are laminated in this order and the adhesive layer between the adhesive layer 3A and the substrate And a second adhesive layer having a different composition. In the present embodiment, it is preferable that the support 2 and the adhesive layer 3A, the adhesive layer 3A, the second adhesive layer 3B, and the second adhesive layer 3B are in contact with 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 limited as long as it is an adhesive layer different in composition from the adhesive layer 3A made of the temporary fixing adhesive of the present invention. Therefore, the second adhesive layer 3B may also be an adhesive layer composed of the same constituent components as the temporary fixing adhesive of the present invention. In this case, however, the adhesive layer 3A and the adhesive layer 3B have different compositions from each other.

In the present invention, it is preferable that the second adhesive layer contains an elastomer X containing 50% by mass or more and 95% by mass or less of the repeating units derived from styrene in the total repeating units. By using such an adhesive layer, the adhesiveness can be further improved. The content of the compound containing silicon atoms in a liquid phase at 25 占 폚 in the second adhesive layer is preferably 10% by mass or less of the content of the compound containing silicon atoms in the liquid phase at 25 占 폚 desirable. By adopting such a second adhesive layer, it is easier to adjust the peeling interface.

For example, in the adhesive layer / support (carrier) composed of the base material (device wafer) / second adhesive layer / temporary fixing adhesive of the present invention, the force required for peeling between the base material and the second adhesive layer, If the force necessary to peel off the adhesive layer made of the positive adhesive and the support is larger than the force necessary to peel off the adhesive layer made of the positive adhesive and the support, peeling can be performed between the support and the adhesive layer made of the temporary fixing adhesive of the present invention. With such a constitution, the peeling becomes easier.

The second adhesive layer in the present invention preferably contains an elastomer Y containing repeating units derived from styrene in a proportion of 10% by mass or more and less than 50% by mass in the total repeating units. With such a configuration, the warpage of the wafer can be effectively suppressed.

The mixing ratio of the elastomer X and the elastomer Y in the second adhesive layer is the same as that described in the item of the temporary fixing adhesive of the present invention, and the preferable range is also the same. The second adhesive layer may also be blended with various additives described in the item of the temporary fixing adhesive of the present invention.

The fourth embodiment of the laminate of the present invention is an embodiment having another layer in the first to third embodiments. As another layer, a layer called a release layer, a release layer or a separation layer is exemplified. As the release layer, reference can be made, for example, to paragraphs 0025 to 0055 of Japanese Laid-Open Patent Publication No. 2014-212292, the contents of which are incorporated herein by reference. As the separation layer, reference can be made to the description of paragraphs 0069 to 0124 of International Publication No. WO2013 / 065417, the content of which is incorporated herein by reference.

The substrate is preferably a device wafer. The device wafer can be any known one without limitation, and examples thereof include a silicon substrate and a compound semiconductor substrate. Specific examples of the compound semiconductor substrate include SiC substrate, SiGe substrate, ZnS substrate, ZnSe substrate, GaAs substrate, InP substrate, GaN substrate and the like.

A mechanical structure or a circuit may be formed on the surface of the device wafer. As a device wafer on which a mechanical structure or a circuit is formed, a device wafer such as MEMS (Micro Electro Mechanical Systems), a power device, an image sensor, a microsensor, a light emitting diode (LED), an optical device, an interposer, a buried device, .

The device wafer preferably has a structure such as a metal bump. According to the present invention, a device wafer having such a structure on the surface can be stably bonded, and adhesion of the device wafer to the device wafer can be easily released. The height of the structure is not particularly limited, but is preferably 1 to 150 mu m, more preferably 5 to 100 mu m.

The thickness of the device wafer before mechanical or chemical treatment is preferably 500 탆 or more, more preferably 600 탆 or more, and more preferably 700 탆 or more. The upper limit is preferably, for example, 2000 占 퐉 or less, more preferably 1500 占 퐉 or less.

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

In the laminate of the present invention, the support (carrier support) is in agreement with the support described in the above-mentioned adhesive support, and the preferable range is also the same.

Alternatively, the adhesive layer 3A may be provided on the substrate and the adhesive layer 3B may be provided on the substrate and adhered. In this case, the adhesive layer 3A and the adhesive layer 3B may be the same or different. In other cases, the peeling selectivity (peeling selectivity between the substrate interface and the support interface) and the peeling selectivity can be improved by changing the kind of the compound containing the silicon atom, or by changing kinds and addition amounts of other additives such as a compound containing a hydrophilic group and a fluorine atom The peeling force can be appropriately adjusted.

Alternatively, the above-described adhesive sheet of the present invention may be disposed between the support and the substrate, followed by hot pressing.

The laminate of the present invention can be obtained by forming an adhesive layer on one side of a support and a substrate using the temporary fixing adhesive of the present invention and applying the temporary fixing adhesive of the present invention or the above- The adhesive layer may be formed using an adhesive, and the surfaces on which the adhesive layer of the substrate and the substrate are formed may be heated and pressed. According to this method, since the adhesive layers are bonded to each other, the substrate and the substrate can be bonded with good filling property.

The laminate of the present invention can be obtained by laminating an adhesive layer containing one or more adhesive layers (3A) and an adhesive layer (3B) on one side of a support and a substrate using the temporary fixing adhesive of the present invention and another temporarily fixed adhesive And the other of the substrate and the substrate is disposed on the adhesive layer, and the substrate and the substrate are heat-pressed.

<Method of Manufacturing Semiconductor Device>

&Lt; First Embodiment &gt;

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

3 (A) to 3 (E) are schematic cross-sectional views (Figs. 3A and 3B) for explaining adherence between a support and a device wafer, a state in which a device wafer adhered to a support is thin (FIG. 3 (C)), a state in which the support and the device wafer are peeled off (FIG. 3 (D)), and a state after the adhesive layer is removed from the device wafer (FIG.

In this embodiment, as shown in Fig. 3 (A), first, an adhesive supporting body 100 in which an adhesive layer 11 is provided on a supporting body 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 the surface 61a of the silicon substrate 61. [

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

In the process of forming the adhesive layer 11, a step of cleaning the back surface of the support 12 or the device wafer 60 with a solvent may be provided. Concretely, it is possible to prevent the apparatus from being contaminated by removing the residue of the adhesive layer adhered to the end faces and back faces of the support 12 and the device wafer 60 by using a solvent in which the adhesive layer is dissolved, The TTV (Total Thickness Variation) As the solvent used in the step of cleaning the back side of the support 12 or the device wafer 60 with a solvent, a solvent included in the temporary fixing adhesive described above may be used.

Subsequently, as shown in Fig. 3 (B), the adhesive support 100 and the device wafer 60 are pressed together, and the support 12 and the device wafer 60 are bonded together.

It is preferable that the adhesive layer 11 completely covers the device chip 62. When the height of the device chip is X m and the thickness of the adhesive layer is Y m, it is preferable that the adhesive layer 11 satisfies the relationship of "X + 100 & desirable.

The reason why the adhesive layer 11 completely covers the device chip 62 is that the TTV (Total Thickness Variation) of the thin device wafer is further lowered (that is, when the flatness of the thin device wafer is to be further improved ).

That is, when the device wafer is thinned, the plurality of device chips 62 are protected by the adhesive layer 11 so that the irregularities on the contact surface with the support 12 can be substantially eliminated. Therefore, even if the wafer is thinned in such a supported state, the possibility that the shape derived from the plurality of device chips 62 is transferred to the back surface 61b1 of the thin device wafer is reduced, and as a result, TTV can be lowered.

Next, as shown in Fig. 3 (C), the surface 61b of the silicon substrate 61 is subjected to mechanical or chemical treatment (though not particularly limited, for example, thinning such as grinding or chemical mechanical polishing Treatment with high temperature and vacuum such as chemical vapor deposition (CVD) or physical vapor deposition (PVD), treatment with chemicals such as organic solvents, acidic treatment solution or basic treatment solution, plating treatment, irradiation with active rays, heating The thickness of the silicon substrate 61 is reduced (for example, the average thickness is preferably less than 500 탆 and more preferably 1 to 200 탆) as shown in Fig. 3 (C) To obtain a thin device wafer 60a.

A step of cleaning the adhesive layer protruding outward beyond the area of the substrate surface of the device wafer with a solvent may be provided at a stage before the processing of the device wafer is performed at a high temperature and under vacuum. Specifically, after the device wafer is thinned, the protruding adhesive layer is removed by using a solvent dissolving the adhesive layer, so that the deformation and deterioration of the adhesive layer caused by the treatment under high temperature and vacuum applied directly to the adhesive layer can be prevented . As the solvent used in the step of cleaning the adhesive layer protruding outward beyond the area of the substrate surface of the device wafer with a solvent, a solvent included in the temporary fixing adhesive may 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, it is more preferable that (C-200)? T? D is satisfied when the diameter of the substrate surface of the support is C m, the diameter of the substrate surface of the device wafer is D m, and the diameter of the film surface of the adhesive layer is T m desirable. Further, the diameter of the film surface of the adhesive layer on the side in contact with the device wafer is represented by _C m, the diameter of the substrate surface of the device wafer is _D m, the diameter of the film surface on the side of the adhesive layer in contact with the support is T _C m, T _D? M, it is preferable that (C-200)? T _C > T _D ? _D be satisfied. By such a constitution, the deformation and deterioration of the adhesive layer can be further suppressed by the treatment directly under the high temperature and vacuum under the adhesive layer.

The area of the film surface of the adhesive layer refers to the area when viewed in a direction perpendicular to the support, and the irregularities on the film surface are not considered. The same applies to the substrate surface of the device wafer. That is, here, the substrate surface of the device wafer is, for example, a surface corresponding to the surface 61a of Fig. The same is applied to the diameter of the film surface of the adhesive layer or the like.

Further, with respect to the diameter T of the adhesive film surface, when the diameter of the diameter of the side in contact with the adhesive support film surface T _C μm, the side in contact with the device wafer of the adhesive film surface to T _D μm, T = ( T _C + T _D ) / 2. The diameter of the substrate surface of the support and the diameter of the substrate surface of the device wafer refer to the diameter of the surface on the side in contact with the adhesive layer.

Further, although the support body and the like are defined as "diameter ", it is not essential that the support body or the like has a circular shape in a mathematical sense. In the case of not a garden, the diameter when converted into a garden having the same area is defined as the above diameter.

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

The heat treatment may be performed between the support 12 and the device wafer 60 until they are peeled off. As an example of the heat treatment, a heat treatment is performed in a mechanical or chemical treatment.

The maximum attained temperature in the heat treatment is preferably 80 to 400 占 폚, more preferably 130 to 400 占 폚, and more preferably 180 to 350 占 폚. It is preferable that the maximum reaching temperature in the heat treatment is lower than the decomposition temperature of the adhesive layer. The heat treatment is preferably heating for 30 seconds to 30 minutes at the maximum attained temperature, and more preferably for 1 minute to 10 minutes at the maximum attained temperature.

Subsequently, as shown in Fig. 3 (D), the support 12 is removed from the thin device wafer 60a. The method of desorption is not particularly limited, but it is preferable to pull up the end portion of the thin device wafer 60a in the vertical direction with respect to the thin device wafer 60a and peel it off without any treatment. At this time, it is preferable that the peeling interface is peeled from the interface between the support 12 and the adhesive layer 11. [ In this case, the peel strength A of the interface between the support 12 and the adhesive layer 11 and the peel strength B of the adhesive layer 11 from the device wafer surface 61a preferably satisfy the following equations.

A <B ... (1)

After the adhesive layer 11 is brought into contact with the release liquid to be described later and then the thin device wafer 60a is slid with respect to the support 12 as required, It can be pulled up in the vertical direction to peel off.

<Release liquid>

Hereinafter, the release liquid will be described in detail.

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

As the peeling liquid, an organic solvent which dissolves the adhesive layer 11 is preferable. Examples of the organic solvent include aliphatic hydrocarbon such as aliphatic hydrocarbon such as hexane, heptane, Isopar E, H, G (manufactured by Esso Gagaku), limonene, para-menthane, nonane, decane, dodecane , Decalin, etc.), aromatic hydrocarbons (toluene, xylene, anisole, mesitylene, ethylbenzene, propylbenzene, cumene, n-butylbenzene, sec-butylbenzene, isobutylbenzene, tert- , Isoamylbenzene, (2,2-dimethylpropyl) benzene, 1-phenylhexane, 1-phenylheptane, 1-phenyloctane, 1-phenylnonane, 1-phenyldecane, cyclopropylbenzene, Cyclohexylbenzene, 2-ethyltoluene, 1,2-diethylbenzene, ortho-cymene, indine, 1,2,3,4-tetrahydronaphthalene, 3-ethyltoluene, meta- Diisopropylbenzene, 4-ethyltoluene, 1,4-diethylbenzene, para-cymene, 1,4-diisopropylbenzene, 4-tert-butyltoluene, 1,4- , 1,3-diethylbenzene, 1,2,3-tri Methylbenzene, 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- Benzene, pentamethylbenzene), halogenated hydrocarbons (methylene dichloride, ethylene dichloride, trichlorethylene, monochlorobenzene, etc.) and polar solvents. Examples of the polar solvent include alcohols (alcohols such as methanol, ethanol, propanol, isopropanol, 1-butanol, 1-pentanol, 1-hexanol, 1-butanol, 1-decanol, benzyl alcohol, ethylene glycol monomethyl ether, 2-ethoxy ethanol, diethylene glycol monoethyl ether, diethylene glycol mono Hexylene 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, Alcohol, etc.), ketones (acetone, methyl ethyl ketone, ethyl butyl ketone, cyclohexanone, etc.), esters But are not limited to, 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, N-phenyldiethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, N-phenyldiethanolamine, N-phenyldiethanolamine, N- (2-hydroxyethyl) morpholine, N, N-dimethylacetamide, N-methylpyrrolidone, etc.).

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

From the viewpoint of releasability, a mode of mixing two or more kinds of organic solvents and water, two or more kinds of alkali, acid and surfactant is also preferable.

The alkali includes, for example, sodium tertiary phosphate, potassium tertiary phosphate, ammonium tertiary phosphate, sodium secondary phosphate, potassium secondary phosphate, ammonium secondary phosphate, sodium carbonate, potassium carbonate, ammonium carbonate, sodium hydrogen carbonate, An inorganic alkali agent such as potassium hydrogen carbonate, ammonium hydrogen carbonate, sodium borate, potassium borate, ammonium borate, sodium hydroxide, ammonium hydroxide, potassium hydroxide and lithium hydroxide, and organic alkali agents such as monomethylamine, dimethylamine, trimethylamine, But are not limited to, ethylamine, triethylamine, monoisopropylamine, diisopropylamine, triisopropylamine, n-butylamine, monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, ethyleneimine , Ethylenediamine, pyridine, tetramethylammonium hydroxide and the like can be used. These alkaline agents may be used alone or in combination of two or more.

Examples of the acid include inorganic acids such as hydrogen halide, sulfuric acid, nitric acid, phosphoric acid and boric acid, and inorganic acids such as methanesulfonic acid, ethanesulfonic acid, benzenesulfonic acid, para-toluenesulfonic acid, trifluoromethanesulfonic acid, acetic acid, , Gluconic acid, lactic acid, oxalic acid, and tartaric acid.

As the surfactant, anionic, cationic, nonionic or amphoteric surfactants can be used. In this case, the content of the surfactant is preferably 1 to 20% by mass, more preferably 1 to 10% by mass with respect to the total amount of the alkali aqueous solution.

By setting the content of the surfactant within the above range, the peeling property of the adhesive layer 11 and the thin device wafer 60a can 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, straight chain alkylbenzene sulfonic acid salts, Benzene sulfonic acid salts, alkyl naphthalene sulfonic acid salts, alkyl diphenyl ether (di) sulfonic acid salts, alkylphenoxy polyoxyethylene alkyl sulfonic acid salts, polyoxyethylene alkyl sulfophenyl ether salts, N-alkyl- Sodium oleyl taurate, disodium salt of N-alkylsulfosuccinic acid monoamide, petroleum sulfonic acid salts, sulfated castor oil, sulfuric acid waxy oil, sulfuric acid ester salts of fatty acid alkyl ester, alkyl sulfate ester salts, polyoxyethylene alkyl Ether sulfuric acid ester salts, fatty acid monoglyceride sulfuric acid ester salts, polyoxyethylene alkylphenyl ether sulfuric acid ester salts, polyoxyethylene styrylphenyl ether sulfuric acid ester salts, Polyoxyethylene alkyl ether phosphate ester salts, polyoxyethylene alkyl phenyl ether phosphate ester salts, partially saponified products of styrene-maleic anhydride copolymer, partially saponified products of olefin-maleic anhydride copolymer, naphthalene Sulfonate phomalin condensates, and the like. Among them, alkylbenzenesulfonic acid salts, alkylnaphthalenesulfonic acid salts and alkyldiphenylether (di) sulfonic acid salts are particularly preferably used.

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

Examples of the nonionic surfactant include, but are not particularly limited to, polyethylene glycol type higher alcohol ethylene oxide adduct, alkylphenol ethylene oxide adduct, alkylnaphthol ethylene oxide adduct, phenol ethylene oxide adduct, naphthol ethylene oxide adduct, fatty acid Ethylene oxide adducts, polyhydric alcohol fatty acid ester ethylene oxide adducts, higher alkylamine ethylene oxide adducts, fatty acid amide ethylene oxide adducts, ethylene oxide adducts of fats, polypropylene glycol ethylene oxide adducts, 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 sorbitol, fatty acids of sucrose Esther, da Alkyl ethers of alcohols, fatty acid amides of alkanolamines, and the like. Of these, those having an aromatic ring and an ethylene oxide chain are preferable, and alkyl-substituted or unsubstituted phenol ethylene oxide adducts or alkyl-substituted or unsubstituted naphthol ethylene oxide adducts are more preferable.

Examples of the amphoteric surfactant include, but are not limited to, amine oxides such as alkyl dimethyl amine oxide, betaine based ones such as alkyl betaine, and amino acid based ones such as alkylamino fatty acid sodium. 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 Japanese Laid-Open Patent Publication No. 2008-203359, the compound represented by the formula (I), the formula (II) Compounds represented by the formula (VI) and compounds represented by the paragraphs [0022] to [0029] of JP-A No. 2009-47927 can be used.

If necessary, the release liquid may contain an additive such as a defoaming agent and a water softening agent.

Then, as shown in Fig. 3 (E), by removing the adhesive layer 11 from the thin device wafer 60a, a thin device wafer can be obtained.

The method of removing the adhesive layer 11 may be, for example, a method in which the adhesive layer is peeled off (film peeling off) in the form of a film, a method in which the adhesive layer is peeled off after swelling the peeling liquid, A method of dissolving and removing the adhesive layer in the exfoliating liquid, a method of decomposing and vaporizing the adhesive layer by irradiation or irradiation with actinic rays or radiation, and the like. A method of peeling off the adhesive layer in a film form, and a method of dissolving and removing the adhesive layer in an aqueous solution or an organic solvent can be preferably used. As the organic solvent, the organic solvent described in the above-mentioned removing solution can be used. From the viewpoint of reducing the use amount of the solvent, it is preferable to remove the film in a film-like state. From the viewpoint of damage reduction on the surface of the device wafer, dissolution and removal are preferable.

It is preferable that the peeling strength B of the device wafer surface 61a and the adhesive layer 11 satisfy the following formula (2).

B? 4 N / cm ... (2)

When the peel strength of the interface between the support 12 and the adhesive layer 11 is A and the peel strength between the device wafer surface 61a and the adhesive layer 11 is B, by satisfying the above equations (1) and (2) The thin film device wafer 60a can be peeled off from the end of the thin device wafer 60a in the vertical direction with respect to the device wafer and peeled from the device wafer surface 60a without peeling off the thin film device wafer 60a, 61a can be removed in the form of a film.

After removing the support member 12 from the thin device wafer 60a, various known processes are performed on the thin device wafer 60a, if necessary, to manufacture a semiconductor device having the thin device wafer 60a .

When the adhesive layer is attached to the support, the support can be regenerated by removing the adhesive layer. Examples of the method for removing the adhesive layer include a method of physically removing the adhesive layer by peeling in the form of a film, a brush, an ultrasonic wave, an ice particle or an aerosol, a method of dissolving and removing in an aqueous solution or an organic solvent, And a method of chemical decomposition such as decomposition and vaporization by irradiation of heat. However, depending on the support, conventionally known cleaning methods can be used.

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

From the viewpoint of adhesiveness in the case of using a regenerated support, it is preferable to use a supporter 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 an inorganic acid such as hydrogen iodide, perchloric acid, hydrogen bromide, hydrogen chloride, nitric acid, sulfuric acid, or an organic acid such as alkylsulfonic acid or arylsulfonic acid. From the viewpoint of the cleaning property of the adhesive layer on the support, it is preferably an inorganic acid, and sulfuric acid is particularly preferable.

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

&Lt; Embodiment 2 &gt;

A second embodiment of a method of manufacturing a semiconductor through a process of manufacturing a laminate will be described with reference to FIG. The same portions as those of the first embodiment described above are denoted by the same reference numerals, and a description thereof will be omitted.

Figs. 4A to 4E are schematic cross-sectional views (Figs. 4A and 4B) for explaining adherence between a support and a device wafer, a state in which a device wafer adhered to a support is thin (Fig. 4 (C)), a state in which the support and the device wafer are peeled off (Fig. 4 (D)), and a state after the adhesive layer is removed from the device wafer (Fig.

This embodiment differs from the first embodiment in that an adhesive layer is formed on the surface 61a of the device wafer as shown in Fig. 4 (A).

When the adhesive layer 11a is provided on the surface 61a of the device wafer 60, a temporary adhesive is applied (preferably applied) to the surface of the surface 61a of the device wafer 60, , And dried (baked). The drying can be performed at, for example, 60 to 150 ° C for 10 seconds to 2 minutes.

Subsequently, as shown in Fig. 4 (B), the support 12 and the device wafer 60 are pressed together, and the support 12 and the device wafer 60 are bonded together. 4 (C), the back surface 61b of the silicon substrate 61 is mechanically or chemically treated to thin the silicon substrate 61 to form the thin device wafer 60a, . Subsequently, as shown in Fig. 4 (D), the support 12 is removed from the thin device wafer 60a. Then, as shown in Fig. 4 (E), the adhesive layer 11 is removed from the thin device wafer 60a.

&Lt; Third Embodiment &gt;

A third embodiment of a method of manufacturing a semiconductor through a process of manufacturing a laminate will be described with reference to FIG. The same portions as those of the first embodiment described above are denoted by the same reference numerals, and a description thereof will be omitted.

5A to 5E are schematic cross-sectional views (Figs. 5A and 5B) for explaining adhesion between a support and a device wafer, a state in which a device wafer adhered to a support is thin (FIG. 5C), a state in which the support and the device wafer are peeled off (FIG. 5D), and a state after the adhesive layer is removed from the device wafer (FIG.

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 support 12 and the device wafer 60 are adhered to each other) by press-bonding the surfaces of the side on which the adhesive layer is formed, to form a laminate.

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 may be formed using the temporary fixing adhesive of the present invention or the temporary fixing adhesive of the present invention may be used for only one of the adhesive layers, Or may be formed using a temporary fixing adhesive B. It is preferable that the adhesive layer 11b is formed by using the temporary fixing adhesive B described above and the adhesive layer 11c is formed by using the temporary fixing adhesive of the present invention.

Each of the adhesive layers 11b and 11c may be composed of only one layer, or may be a laminate composed of two or more adhesive layers laminated. That is, each of the adhesive layers may be formed by overlaying two or more temporary fixing adhesives.

The back surface 61b of the silicon substrate 61 is subjected to a mechanical or chemical treatment to bond the support 12 and the device wafer 60 to the silicon substrate 61 as shown in Fig. The thickness of the substrate 61 is reduced to obtain a thin device wafer 60a. Subsequently, as shown in Fig. 5 (D), the support 12 is removed from the thin device wafer 60a. Then, as shown in Fig. 5 (E), the adhesive layer 11d is removed from the thin device wafer 60a.

<< Conventional Embodiment >>

Next, a conventional embodiment will be described.

6 is a schematic cross-sectional view illustrating the release of the adhesion state between the conventional adhesive support and the device wafer.

6, an adhesive supporting body 100a having an adhesive layer 11a formed by a conventional temporary fixing adhesive is used as the adhesive supporting body, 3, the adhesive supporting body 100a and the device wafer are adhered to each other, and the thinning treatment of the silicon substrate on the device wafer is performed. Subsequently, in the same manner as described above, The thin device wafer 60a is peeled from the adhesive support 100a.

However, according to the conventional temporary fixing adhesive, it is difficult to easily hold the device wafer without damaging the device wafer by having the device wafer with high adhesive force. For example, in order to sufficiently bond the device wafer and the support to each other, if a high affinity adhesive is used among the conventional temporary fixing adhesives, adhesion between the device wafer and the support tends to be too strong. 6, a tape (for example, a dicing tape) 70 is attached to the back surface of the thin device wafer 60a so as to release the adhesion (adhesion) In the case of delaminating the thin device wafer 60a from the support 100a, there is a problem that the device chip 62 is broken by detaching the structure 63 from the device chip 62 provided with the structure 63 .

On the other hand, among the conventional temporary fixing adhesives, if a low adhesive property is employed, it is possible to easily release the device wafer, but the adhesive between the original device wafer and the support is so weak that the device wafer can be reliably supported There is a problem that there is no problem.

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

The manufacturing method of the semiconductor device of the present invention is not limited to the above-described embodiment, but can be appropriately modified and improved.

In the above-described embodiment, the adhesive layer has a single-layer structure, but the adhesive layer may have a multi-layer structure.

In the above-described embodiment, a silicon wafer is used as the device wafer. However, the present invention is not limited to this, and in the manufacturing method of the semiconductor device, any material to be processed that can be used for mechanical or chemical treatment may be used. For example, a compound semiconductor substrate may be used. Specific examples of the compound semiconductor substrate include SiC substrate, SiGe substrate, ZnS substrate, ZnSe substrate, GaAs substrate, InP substrate, GaN substrate and the like.

In the above-described embodiment, the thinning process of the device wafer and the process of forming the silicon through electrode are described as the mechanical or chemical process for the device wafer (silicon substrate). However, the present invention is not limited to this, And any process necessary for the production method.

In addition, the shape, size, number, location, etc. of the device chip in the device wafer exemplified in the above-described embodiments are arbitrary and not limited.

<Kit>

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

The kit of the present invention comprises the above-mentioned first temporary fixing adhesive of the present invention and the elastomer X containing 50% by mass or more and 95% by mass or less of styrene-derived repeating units in the total repeating units, And a second adhesive different in composition from the first temporary fixing adhesive. The second adhesive preferably includes an elastomer X containing 50% by mass or more and 95% by mass or less of the repeating units derived from styrene in the total repeating units. In the second adhesive, the content of the compound containing a silicon atom in a liquid phase at 25 占 폚 is preferably in a liquid phase at 25 占 폚, contained in the first temporary fixing adhesive, of 10 mass% of the content of the compound containing silicon atoms % Or less. The second adhesive in the present invention preferably comprises an elastomer Y containing repeating units derived from styrene in a proportion of 10% by mass or more and less than 50% by mass in the total repeating units. With such a configuration, warpage of the wafer can be more effectively suppressed.

The blend ratio of the elastomer X and the elastomer Y in the second adhesive is the same as that described in the item of the temporary fixing adhesive of the present invention, and the preferable range is also the same. The second adhesive may also be blended with various additives described in the items of the temporary fixing adhesive of the present invention. The blending amount and the like are also preferably within the ranges described in the item of the temporary fixing adhesive of the present invention.

The kit of the present invention preferably further comprises a substrate and a support. As the substrate and the support, there can be mentioned the substrate and the support described in the above-mentioned laminate, and these can be used.

By further having the substrate and the 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 can be manufactured between the substrate and the support.

Example

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

In addition, propylene glycol-1-methyl ether acetate is referred to as "PGMEA ".

In the present embodiment, 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 (manufactured by Big Chemie)

(a-10) Polyfluor KL-700 (manufactured by Kyoeisha Chemical Co., Ltd.)

(a-11) TEGO WET 270 (manufactured by Ebonic Degussa Japan K.K.)

(a-12) SH28PA (manufactured by Toray Dow Corning Co., Ltd.)

(a-13) NBX-15 (manufactured by Neos Co., Ltd.)

(Ra-1) KR220L (silicone resin solid, manufactured by Shin-Etsu Chemical Co., Ltd.)

(Ra-2) 1-dodecene (hydrogenated hydrocarbon oil, manufactured by Tokyo Kasei Kogyo Co., Ltd.)

(a-1) to (a-13) at 25 ° C was within the range of 10 to 20,000 mPa · s.

[Component B]

(B-1): Septon 2104 (hydrogenated polystyrene elastomer having a styrene content of 65% by weight, an unsaturated double bond content of less than 0.5 mmol / g, a thermal mass reduction temperature of not less than 400 ° C and less than 450 ° C, Less than 50,000 and less than 100,000, hardness (type A durometer) = 98, manufactured by Kuraray Co., Ltd.)

(b-2): Tuftec P2000 (hydrogenated polystyrene elastomer, styrene content = 67 mass%, unsaturated double bond amount = 0.5 mmol / g or more and less than 5 mmol / g, ° C, Mw = 50,000 or more and less than 100,000, hardness (type A durometer) = 90 or more, manufactured by Asahi Kasei Corporation)

(b-3): Sephton 8104 (hydrogenated polystyrene elastomer, styrene content = 60% by mass, unsaturated double bond content = less than 0.5 mmol / g, Type A durometer) = 98, manufactured by Kuraray Co., Ltd.)

(b-4): Kraton A1535 (hydrogenated polystyrene elastomer, styrene content = 58 mass%, unsaturated double bond amount = less than 0.5 mmol / g, (Type A durometer) = 83, manufactured by Kraton)

(b-5): Septon 2002 (hydrogenated polystyrene elastomer, styrene content = 30 mass%, unsaturated double bond amount = less than 0.5 mmol / g, Less than 50,000 and less than 100,000, hardness (type A durometer) = 80, manufactured by Kuraray Co., Ltd.)

(b-6): Septon 4033 (hydrogenated polystyrene elastomer having a styrene content of 30 mass%, an unsaturated double bond content of less than 0.5 mmol / g, a thermal mass reduction temperature of not less than 400 ° C and less than 400 ° C, Type A durometer) = 76, manufactured by Kuraray Co., Ltd.)

(b-7): Kraton G1650 (hydrogenated polystyrene elastomer, content of styrene = 30 mass%, amount of unsaturated double bonds = less than 0.5 mmol / g, (Type A durometer) = 70, manufactured by Kraton)

(b-8): Septon 8004 (hydrogenated polystyrene elastomer, styrene content = 31 mass%, unsaturated double bond amount = less than 0.5 mmol / g, Less than 50,000 and 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 amount = less than 0.5 mmol / g, Less than 50,000 and less than 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 amount = 5 mmol / g or more and less than 15 mmol / g, , Mw = 100,000 or more and less than 200,000, manufactured by JSR Corporation)

(Rb-1): RB810 (polybutadiene-based elastomer, unsaturated double bond amount of 15 mmol / g or more, 5% thermal mass reduction temperature = 100 ° C or more and less than 250 ° C, Mw = )My)

(Rb-2): ZEONEX 480R (cycloolefin-based polymer manufactured by Nippon Zeon)

(Rb-3): Durimide (registered trademark) 284 (polyimide manufactured by Fuji Film)

(Rb-4): PCZ300 (polycarbonate manufactured by Mitsubishi Gas Chemical)

(Rb-5): Hytrel 7247 (polyester elastomer, 5% thermal mass reduction temperature = 383 DEG C, hardness (type A durometer) = 90 or more, manufactured by Toray DuPont)

(Rb-6): Primaloy CP300 (polyester elastomer, 5% thermal mass reduction temperature = 399 DEG C, hardness (type A durometer) = 90 or more, manufactured by Mitsubishi Kagaku)

The amount of unsaturated double bond is a value calculated by NMR measurement.

The 5% thermal mass reduction temperature is a temperature at which 5% of the mass at the start of measurement is decreased by a thermogravimetric analyzer (TGA) under the condition that the temperature is raised from 25 占 폚 to 20 占 폚 / Measured value.

[Test Example 1]

&Lt; Formation of Adhesive Support 1 >

The application liquid 1 for forming an adhesive layer was spin-coated on a Si wafer (support wafer) having a diameter of 100 mm and a thickness of 525 m, baked at 110 DEG C for 1 minute and further baked at 190 DEG C for 4 minutes to obtain an adhesive support 1.

&Lt; Composition of Coating Liquid 1 for Adhesive Layer Formation &

Component A: The component A shown in Table 1 was added to the mass parts shown in Table 1

Component B: The component B shown in Table 1 was added to the mass parts shown in Table 1

Irganox 1010 (manufactured by BASF): 0.9 parts by mass

Sumilizer TP-D (manufactured by Sumitomo Chemical Co., Ltd.): 0.9 parts by mass

Solvent: The solvent shown in Table 1 was added to the mass part

&Lt; Preparation of test piece &

The device side of the Si wafer (device wafer) equipped with the Cu bump with a diameter of 100 mm, a thickness of 525 mu m and a height of 10 mu m on the side where the adhesive layer of the adhesive supporting member 1 was formed was cleaned at 190 DEG C under a pressure of 0.11 MPa And pressed for 3 minutes to prepare a test piece.

<Adhesiveness>

The shear adhesive strength of the test piece was measured by tensile test in the direction along the surface of the adhesive layer at a rate of 250 mm / min using a tensile tester (digital force gauge manufactured by Imada Corporation, model: ZP-50N) did.

A: Adhesion of 50 N or more

B: Adhesion of 10N or more and less than 50N

C: Adhesion less than 10N

<Peelability>

The test piece was set in the center of the dicing tape mounter together with the dicing frame, and the dicing tape was placed from above. The test piece and the dicing tape were fixed with a roller under vacuum, the dicing tape was cut on the dicing frame, and the test piece was mounted on the dicing tape.

Under the conditions of 25 占 폚, the test piece was stretched in the direction (90 占 direction) perpendicular to the surface of the adhesive layer at a rate of 50 mm / min, and the peelability was evaluated according to the following criteria. The prepared test piece was heated at 250 占 폚 for 30 minutes and then stretched in the vertical direction of the adhesive layer at 25 占 폚 under the condition of 50 mm / min to confirm the peelability after the heat treatment. I appreciated. The presence or absence of breakage of the Si wafer was visually confirmed.

A: The maximum peel force was less than 12N and peeling was possible.

B: The maximum peeling force was 12N or more and less than 16N, and peeling was possible.

C: The maximum peeling force was 16N or more and less than 20N, and peeling was possible.

D: The maximum peeling force was 20N or more and less than 25N, and peeling was possible.

E: The maximum peel force was 25 N / cm or more, or the Si wafer was broken.

&Lt; Removability (dissolution removal) >

An Si wafer (device wafer) having an adhesive layer after completion of the peelability test was set on a spin coater with the adhesive layer facing up. Using the same solvent as the solvent for the adhesive layer forming coating solution described in Table 1 below as a cleaning solvent, I sprayed. In Comparative Examples 5, 6 and 7 in which mesitylene was not used for spraying for 5 minutes, isopropyl alcohol (IPA) was sprayed while rotating the Si wafer to rinse. Further, spin drying was performed. Thereafter, the appearance was observed, and the presence or absence of the remaining adhesive layer was checked with the naked eye and the amount of carbon atoms on the surface of the Si wafer by X-ray photoelectron spectroscopy, and the evaluation was made according to the following criteria.

<< Measurement method of X-ray photoelectron spectroscopy >>

Using a PHI Quantera SXM (manufactured by ULVAC, Pa.), A monochromatic AlK alpha ray was irradiated at 25W in an analysis area range of 1400 mu m x 700 mu m on the base surface of the wafer and detected at an extraction angle of 45 DEG, (Atm%) was measured. The measurement temperature was 25 占 폚, and the measurement pressure was 10 ^-8 Pa or less.

The area of the substrate surface of the wafer means the area of the surface of the substrate when it is assumed that there is no irregularity even when the surface of the substrate surface has irregularities.

Evaluation was made according to the following evaluation categories.

A: As a result of ESCA measurement, the presence ratio of carbon atoms was less than 1%.

B: As a result of ESCA measurement, the presence ratio of carbon atoms was 1% or more and less than 3%.

C: As a result of ESCA measurement, the presence ratio of carbon atoms was 3% or more.

<Removability (film removal)>

The Si wafer (device wafer) having the adhesive layer after completion of the peelability test was immovably fixed at 25 캜, and a peeling tape (manufactured by LINTEC CORPORATION) was affixed to the adhesive layer on the Si wafer having the adhesive layer, The tape was pulled in the direction perpendicular to the adhesive layer, and the adhesive layer was pulled up at a rate of 50 mm / min in the 90 占 direction to peel the adhesive layer from the device surface of the Si wafer (device wafer) in a film form. Thereafter, the appearance was observed, and the presence or absence of the peeling residue of the adhesive layer remaining on the Si wafer was visually checked and evaluated according to the following criteria.

A: With the peeling strength of 4 N / cm or less, the adhesive layer can be removed in a film form without breaking, and the peeling residue of the adhesive layer can not be confirmed.

B: With the peel strength exceeding 4 N / cm, the adhesive layer can be removed in a film form without breaking, and the peeling residue of the adhesive layer can not be confirmed.

C: Not applicable to either A or B above (broken during peeling)

&Lt; Wafer bending >

The surface of the device wafer of the produced test piece which did not contact the adhesive layer was polished until the thickness of the device wafer became 35 탆 and then the temperature and rate of cooling were measured using FLX-2320 manufactured by KLA-Tencor Was set at 10 占 폚 / min, and then heated from room temperature to 200 占 폚, and then cooled to 25 占 폚 to measure a Bow value (flexural strength).

A: Bow value is 40μm or less

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

C: Bow value is more than 80μm and less than 200μm

D: Bow value of 200μm or more

[Table 1]

As is apparent from the above results, when the temporary fixing adhesive of the present invention was used, the adhesive property and the room temperature peeling property were good. Further, the peelability after heating and the removability of the adhesive layer were satisfactory, and warpage of the wafer was suppressed.

In addition, in the example in which the above-mentioned elastomer X and the elastomer Y were used together as the elastomer, warpage of the wafer was more effectively suppressed.

[Test Example 2]

&Lt; Formation of Adhesive Support 2 >

The application liquid 2 for forming an adhesive layer was spin-coated on a Si wafer (support wafer) having a diameter of 100 mm and a thickness of 525 占 and baked at 110 占 폚 for 1 minute and further baked at 190 占 폚 for 4 minutes to obtain an adhesive support 2.

The application liquid 3 for forming an adhesive layer was spin-coated on a Si wafer (device wafer) having a diameter of 100 mm, a thickness of 525 mu m and a height of 10 mu and equipped with Cu bumps, baked at 110 DEG C for 1 minute, For 4 minutes to prepare an adhesive base material having an adhesive layer.

<Composition of Adhesive Layer Forming Coating Liquid 2, 3>

Component A: The component A shown in Table 2 was added to the mass portion

Component B: The component B shown in Table 2 was added to the mass component

Irganox 1010 (manufactured by BASF): 0.9 parts by mass

Sumilizer TP-D (manufactured by Sumitomo Chemical Co., Ltd.): 0.9 parts by mass

Mesitylene: 30 parts by mass

&Lt; Preparation of test piece &

The surface of the adhesive support 2 on which the adhesive layer was formed and the surface of the adhesive base material on which the adhesive layer was formed were pressed under vacuum at 190 DEG C and 0.11 MPa for 3 minutes to prepare a test piece.

<Adhesiveness>

The adhesiveness was evaluated by the same method and standard as the evaluation of the adhesion in Test Example 1.

<Fillability>

The presence or absence of voids in the adhesive layer after the bonding (including the interface between the adhesive layers, the bonding surface between the adhesive layer and the substrate, and the bonding surface between the adhesive layer and the support) was confirmed using a C-SAM (ultrasonic microscope).

A: No voids.

B: Small voids less than 10μm in diameter can be identified from 1 to 5 but no substantial damage.

C: No less than 5 but less than 10 small voids less than 10μm in diameter, but no substantial damage.

D: More than 10 voids exceeding 10μm in diameter, resulting in substantial damage.

<Peelability>

The peelability was evaluated by the same method and criterion as the peelability evaluation in Test Example 1.

&Lt; Removability (dissolution removal) >

The removability (dissolution removal) was evaluated by the same method and criterion as the removability (dissolution removal) in Test Example 1.

<Removability (film removal)>

(Film removal) was evaluated by the same method and criterion as the removability (film removal) in Test Example 1.

&Lt; Wafer bending >

Wafer bending was evaluated by the same method and criterion as wafer bending in Test Example 1.

[Table 2]

As apparent from the above results, when the temporary fixing adhesive of the present invention was used, the adhesive property and the room temperature peeling property were good. Further, the peelability after the heating and the removability of the adhesive layer were good.

In addition, in the example in which the above-mentioned elastomer X and the elastomer Y were used together as the elastomer, 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 filling property was good.

[Test Example 3]

&Lt; Method for producing adhesive film &

The composition for forming an adhesive film of Examples 42 to 50 and Comparative Examples 12 to 15 and 18 to 21 was applied on a 75 占 퐉 -thick polyethylene terephthalate (PET) film with a wire bar at a speed of 1 m / min, And dried at 140 DEG C for 10 minutes to produce an adhesive film having a film thickness of 100 mu m.

The composition for forming an adhesive film of Comparative Examples 16 and 17 was melt-stirred at 300 DEG C for 5 minutes and extruded from a slit having a width of 100 mu m to produce an adhesive film (extrusion-molded sheet).

(Composition of composition for forming an adhesive film)

Component A: Component A shown in Table 3 was added to the mass parts shown in Table 3

Component B: The component B shown in Table 3 was added to the component

Solvent: The solvent shown in Table 3 was added to the mass parts shown in Table 3

&Lt; Preparation of test piece &

A Si wafer having a diameter of 100 mm and a side of the adhesive support 2 on which the adhesive layer was formed was pressed under vacuum at 190 DEG C and 0.11 MPa for 3 minutes to prepare a test piece.

<Adhesiveness>

The adhesiveness was evaluated by the same method and standard as the evaluation of the adhesion in Test Example 1.

<Peelability>

The peelability was evaluated by the same method and criterion as the peelability evaluation in Test Example 1.

&Lt; Removability (dissolution removal) >

The Si wafer having the adhesive layer after the peelability test was set on the spin coater with the adhesive layer facing up and sprayed on the wafer for 5 minutes using the solvent shown in Table 3 as a cleaning solvent. Further, spin drying was performed. Thereafter, the appearance was observed, and the presence or absence of the remaining adhesive layer was visually checked and evaluated according to the following criteria.

A: Remaining adhesive layer is not confirmed

B: Remaining adhesive layer is confirmed

<Removability (film removal)>

(Film removal) was evaluated by the same method and criterion as the removability (film removal) in Test Example 1.

&Lt; Wafer bending >

Wafer bending was evaluated by the same method and criterion as wafer bending in Test Example 1.

[Table 3]

As is apparent from the above results, when the temporary fixing adhesive of the present invention was used, the adhesive property and the room temperature peeling property were good. Further, the peelability after heating and the removability of the adhesive layer were satisfactory, and warpage of the wafer was suppressed.

In addition, in the example in which the above-mentioned elastomer X and the elastomer Y were used together as the elastomer, warpage of the wafer was more effectively suppressed.

1: substrate
2: Support
3, 3A, 3B, 11, 11a to 11d:
12: Support
60: device wafer
60a: thin device wafer
61: silicon substrate
61a: Surface
61b, 61b1:
62: Device chip
63: structure
100, 100a: Adhesive support

Claims (25)

A compound which is liquid at 25 占 폚 and contains silicon atoms,
And an elastomer X containing repeating units derived from styrene in a proportion of not less than 50% by mass and not more than 95% by mass in the total repeating units. The method according to claim 1,
Wherein the 10% thermal mass reduction temperature of the compound containing silicon atoms is raised from 25 占 폚 to 20 占 폚 / min at 250 占 폚 or higher. The method according to claim 1 or 2,
Wherein the hardness of the elastomer X measured by a Type A durometer according to the method of JIS K6253 is 83 or more. The method 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 the total repeating units. The method of claim 4,
Wherein the mass ratio of the elastomer X and the elastomer Y is 5: 95 to 95: 5. The method according to any one of claims 1 to 5,
Wherein the 5% thermal mass reduction temperature of at least one of the elastomers contained in the temporary fixing adhesive is increased from 25 占 폚 to 20 占 폚 / min at 250 占 폚 or higher. The method according to any one of claims 1 to 6,
Wherein the amount of the unsaturated double bond of at least one of the elastomers contained in the temporary fixing adhesive is 7 mmol / g or less. The method 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 method 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 method 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 thereof. The method according to any one of claims 1 to 10,
Wherein the content of the compound containing a silicon atom relative to the total amount of the elastomers in the temporary fixing adhesive is 0.01% by mass or more and less than 2.5% by mass. The method according to any one of claims 1 to 11,
Wherein the silicon atom-containing compound is selected from dimethyl polysiloxane, methylphenyl polysiloxane, diphenyl polysiloxane and polyether modified polysiloxane. The method according to any one of claims 1 to 12,
An antioxidant, and at least one of a solvent and a solvent. The method according to any one of claims 1 to 13,
Wherein the temporary fixing adhesive is a temporary fixing 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 backing having an adhesive layer comprising the temporary fixing adhesive according to any one of claims 1 to 14 and a support. A laminate having a support and an adhesive layer comprising the temporary fixing adhesive according to any one of claims 1 to 14 and a substrate. 18. The method of claim 17,
Wherein the adhesive layer is located on the surface of the support and the substrate is located on a surface of the adhesive layer opposite to the support. 18. The method of claim 17,
Wherein the support, the adhesive layer, and the substrate are laminated in this order, and a second adhesive layer having a composition different from that of the adhesive layer is provided between the support and the adhesive layer. 18. The method of claim 17,
Wherein the support, the adhesive layer, and the substrate are stacked in this order, and a second adhesive layer is formed between the adhesive layer and the substrate, the second adhesive layer being different in composition from the adhesive layer. The method according to claim 19 or 20,
And the second adhesive layer comprises an elastomer X containing repeating units derived from styrene in a proportion of 50% by mass or more and 95% by mass or less in the total repeating units. The method according to any one of claims 19 to 21,
Wherein the second adhesive layer comprises an elastomer Y containing repeating units derived from styrene in a proportion of 10% by mass or more and less than 50% by mass in the total repeating units. The method as claimed in any one of claims 19 to 22,
Wherein the content of the silicon atom-containing compound contained in the adhesive layer in the liquid phase at 25 占 폚 in the second adhesive layer is 10% by mass or less of the content of the silicon- Laminates. The method of any one of claims 17 to 23,
Wherein the substrate is a device wafer. An adhesive composition comprising the temporary fixing agent according to any one of claims 1 to 14 and an elastomer X containing 50% by mass or more and 95% by mass or less of styrene-derived repeating units in the total repeating units, And a second adhesive different in composition from the positive adhesive.

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