TW201617423A - Method for manufacturing temporary adhesive film, temporary adhesive film, layered body, layered body provided with device wafer, and temporary adhesive composition - Google Patents

Abstract

Provided are a method for manufacturing a temporary adhesive film having excellent release properties and whereby a release interface can be controlled, a temporary adhesive film, a layered body, a layered body provided with a device wafer, and a temporary adhesive composition. A method for manufacturing a temporary adhesive film, the method including a step for applying a temporary adhesive composition in layered fashion to a support and drying the temporary adhesive composition, the method for manufacturing a temporary adhesive film wherein the temporary adhesive composition includes a compound having a fluorine atom, and the temporary adhesive film 11 being configured so that the abundance ratio A of fluorine atoms on the surface a of the temporary adhesive film on the reverse side thereof from the support and the abundance ratio B of fluorine atoms on the support-side surface of the temporary adhesive film satisfy the relationship of equation (1) and the abundance ratio A of fluorine atoms is 5-40% in the abundance ratios of fluorine atoms on the surfaces of the temporary adhesive film measured using X-ray photoelectron spectroscopy. Equation (1): A/B ≥ 1.3.

Description

Method for manufacturing a film, a dummy film, a laminate, a laminate with a device wafer, and a dummy composition

The present invention relates to a method for producing a pseudo-adhesive film, a pseudo-adhesion film, a laminate, a laminate with a device wafer, and a composition for false bonding. More specifically, the present invention relates to a method for producing a dummy film which can be preferably used for the production of a semiconductor device or the like, a laminated film, a laminate, a laminate with a device wafer, and a composition for false bonding.

In a manufacturing process of a semiconductor device such as an integrated circuit (IC) or a large scale integrated circuit (LSI), a plurality of IC wafers are formed on a device wafer and diced by dicing And singular. With the demand for further miniaturization and high performance of electronic devices, the IC chips mounted on electronic devices are required to be further miniaturized and integrated, but the integrated circuits in the surface direction of the device wafers are high. The integration is close to the limit.

As a method of electrically connecting an integrated circuit in an IC chip to an external terminal of an IC chip, a wire bonding method has been widely known from the past, but in order to realize miniaturization of an IC chip, it has been known in recent years. The element wafer is provided with a through hole, and a metal plug as an external terminal is connected to the integrated circuit so as to penetrate the through hole (a method of forming a through-silicon via (TSV)). However, the demand for further high integration of the IC wafer in recent years cannot be sufficiently coped with only the method of forming the tantalum through electrode.

In view of the above, there has been known a technique for improving the total body area per unit area of an element wafer by multilayering an integrated circuit in an IC wafer. However, the multilayering of the integrated circuit increases the thickness of the IC wafer, and therefore it is necessary to make the members constituting the IC wafer thin. In order to reduce the thickness of the device, for example, it is possible to reduce the size of the IC wafer, and it is possible to reduce the size of the IC wafer and to save the through-hole manufacturing process of the device wafer in the manufacture of the through-electrode. Considered to have a future. Further, in a semiconductor element such as a power element or an image sensor, in order to improve the degree of integration or to improve the degree of freedom of the element structure, thinning has also been attempted.

As the element wafer, a thickness of about 700 μm to 900 μm is widely known. However, in recent years, attempts have been made to reduce the thickness of the element wafer to 200 μm or less for the purpose of miniaturization of the IC wafer. However, since the element wafer having a thickness of 200 μm or less is very thin, and the member for manufacturing a semiconductor element using the substrate as a base material is also very thin, it is difficult to perform further processing on such a member or to move only such a member. The member is supported stably and without damage.

In order to solve the above-mentioned problems, it is known that the element wafer before thinning and the carrier substrate are temporarily fixed by a dummy adhesive (falsely), and the back surface of the element wafer is ground and thinned, and then A technique in which a carrier substrate is detached from a component wafer.

Patent Document 1 discloses an underlying sheet for semiconductor device manufacturing including a substrate and a resin-containing adhesive layer provided on one surface of the substrate, and is detachably attached to a lead frame of a semiconductor device (lead frame) In the adhesive sheet for manufacturing a semiconductor device of the wiring board, a fluorine-containing additive which is liquid at 25 ° C is prepared in the adhesive layer.

Further, Patent Document 2 discloses that a support and a substrate are pseudo-fixed via a pseudo-fixing material containing a cycloolefin polymer and a compound containing an anthrone structure, a fluorinated alkyl structure, or a fluorinated alkenyl group. At least one structure of a structure and an alkyl structure having a carbon number of 8 or more, and at least one structure of a polyoxyalkylene structure, a structure having a phosphate group, and a structure having a sulfo group.

Further, Patent Document 3 discloses that an element wafer and a support are attached by using an adhesive composition containing an elastomer and an wax containing a structural unit having a styrene unit as a main chain. [Prior Art Document] [Patent Literature]

[Patent Document 1] Japanese Laid-Open Patent Publication No. 2013-346568 (Patent Document 3)

[Problems to be solved by the invention]

In the case where the element wafer and the carrier substrate are falsely connected, it is required to easily cancel the characteristics of the dummy wafer state of the element wafer and the carrier substrate. Further, when the dummy wafer state of the element wafer and the carrier substrate is released, the film is peeled off at the interface between the device wafer and the dummy film or is peeled off at the interface between the carrier substrate and the dummy film, but is not fixed each time. At the time of peeling, if the interface between the element wafer and the dummy film is peeled off or the interface between the carrier substrate and the dummy film is peeled off, it is necessary to change the process of removing the dummy film from the element wafer or the carrier substrate every time, and the production is caused. The reduction in sexuality. Further, if the peeling interface between the element wafer and the carrier substrate and the dummy film can be controlled, for example, the dummy film can be left on the side where the dummy film can be easily removed, and the dummy wafer state of the element wafer and the carrier substrate can be released. Therefore, the dummy film can be removed from the component wafer or the carrier substrate after the dummy is removed efficiently.

In order to improve the peeling property with the element wafer or the carrier substrate, the release film is also coated with a release agent to form a release layer on the surface of the dummy film. However, in the case of the method, the film is increased. Since the step of forming the release layer is performed, the number of processes is increased, and the throughput is improved.

In addition, as described in Patent Document 1 and Patent Document 2, studies have been conducted to prepare a compound having a fluorine atom in a composition for pseudo-adhesion. However, in Patent Document 1 and Patent Document 2, there is no description or suggestion that the peeling interface between the element wafer and the carrier substrate and the dummy film when the element wafer and the carrier substrate are in a false state is released. control.

Further, in the invention disclosed in Patent Document 3, the peeling property is insufficient. In Patent Document 3, for the purpose of easily separating the element wafer from the carrier substrate, a carrier substrate provided with a plurality of holes penetrating in the thickness direction or a carrier substrate and a component wafer is used. There is a layer (reaction layer) having a property of being deteriorated by absorbing light, but a special carrier substrate is required in the method.

The present invention has been made in view of the above-described background, and provides a method for producing a pseudo-adhesive film which is excellent in releasability and which can control a peeling interface, a pseudo-adhesive film, a laminate, a laminate with a device wafer, and a composition for false bonding. [Means for solving the problem]

The inventors of the present invention have diligently studied to solve the above problems, and as a result, have found that the object can be attained by adjusting the ratio of the presence of fluorine atoms on the surface of the pseudo-adhesive film, and completed the present invention. The present invention provides the following. <1> A method for producing a pseudo-adhesive film, comprising the steps of applying a composition to a layer and drying it on a support, and then using a composition containing a compound having a fluorine atom, X-ray photoelectron spectroscopy was used to illuminate the surface of the pseudo-adhesive film by measuring 25 W of monochromated AlKα rays on the surface of the 1400 μm ́700 μm surface of the pseudo-adhesive film and detecting it at an exit angle of 45°. The ratio of the existence of the obtained fluorine atom to the ratio A of the fluorine atom in the surface on the opposite side of the support from the support, and the ratio B of the fluorine atom in the surface on the support side of the pseudo-adhesive film satisfy the following The relationship of the formula (1), and the existence ratio A of the fluorine atom is 5% to 40%, and A/B ≧ 1.3 (1) A is a fluorine atom in the surface of the pseudo-adhesive film opposite to the support. The existence ratio A, B is the existence ratio B of the fluorine atoms in the surface of the support side of the film. <2> The method for producing a pseudo-adhesive film according to the above aspect, wherein the ratio B of the existence ratio of the fluorine atom of the film to the fluorine atom of the pseudo-attachment film satisfies the relationship of the following formula (2), and the fluorine atom The existence ratio A is 10% to 30%, A/B≧1.5 (2) A is the existence ratio A of the fluorine atoms in the surface of the pseudo-adhesive film opposite to the support, and B is the support of the pseudo-adhesion film The ratio B of the fluorine atoms in the surface of the body side. <3> The method for producing a pseudo-adhesion film according to <1>, wherein the compound having a fluorine atom contains an oleophilic group. The method for producing a pseudo-adhesive film according to any one of the aspects of the present invention, wherein the composition is contained in at least one selected from the group consisting of a binder and a radical polymerizable compound. <5> The method for producing a pseudo-adhesive film according to <4>, wherein the binder is a block copolymer. <6> The method for producing a pseudo-adhesive film according to <4>, wherein the binder is a styrene block copolymer having a single terminal or a styrene block at both ends. The method for producing a pseudo-adhesive film according to any one of the aspects of the present invention, wherein the binder is a hydrogenated product of a block copolymer. <8> The method for producing a pseudo-adhesive film according to <4>, wherein the binder is an elastomer. <9> The method for producing a pseudo-adhesive film according to <8>, wherein the elastomer contains a repeating unit derived from styrene. <10> The method for producing a pseudo-adhesive film according to <8>, wherein the elastomer is a hydride. The method for producing a pseudo-adhesive film according to any one of the above aspects, wherein the elastomer is a styrene block copolymer having a single terminal or a styrene block at both ends. The method for producing a pseudo-adhesive film according to any one of <8>, wherein the elastomer contains the elastomer A and the elastomer B, and the elastomer A is 10 in all the repeating units. The proportion of the mass% or more and 50% by mass or less contains a repeating unit derived from styrene, and the elastomer B contains a repeating unit derived from styrene in a ratio of more than 50% by mass and 95% by mass or less in all the repeating units. <13> The method for producing a pseudo-adhesive film according to <12>, wherein the mass ratio of the elastomer A to the elastomer B is 5:95 to 95:5. <14> The method for producing a pseudo-adhesive film according to the above aspect, wherein the radically polymerizable compound is a compound having two or more radical polymerizable groups. <15> The method for producing a pseudo-adhesive film according to the above aspect, wherein the radically polymerizable compound has at least one of partial structures represented by the following (P-1) to (P-4) Where * is the link key, [Chemical 1] . The method for producing a pseudo-adhesive film according to any one of <4>, wherein the radically polymerizable compound is selected from trimethylolpropane tri(meth)acrylic acid. Ester, isocyanuric acid ethylene oxide modified di(meth)acrylate, isocyanuric acid ethylene oxide modified tri(meth)acrylate, triallyl isocyanurate, pentaerythritol three ( Methyl) acrylate, pentaerythritol tetra(meth) acrylate, dimethylolpropane tetra(meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and tetrahydroxyl At least one of methyl methane tetra(meth)acrylate. The method for producing a pseudo-adhesive film according to any one of the aspects of the present invention, wherein the composition is used in the total solid content of the composition for false squeezing, 0.03 mass% or more and less than The proportion of 0.5% by mass contains a compound having a fluorine atom. The method for producing a pseudo-adhesion film according to any one of the above aspects, wherein the film has an average film thickness of from 0.1 μm to 500 μm. <19> A pseudo-attachment film containing a compound having a fluorine atom, the pseudo-attachment film being a single-layer film, and irradiating 25 W of monochromatic AlKα rays on an analysis area of 1400 μm ́ 700 μm on the surface of the pseudo-adhesion film And the ratio of the presence of fluorine atoms in the surface of the pseudo-adhesive film measured by the X-ray photoelectron spectroscopy measured at an emission angle of 45°, and the ratio A1 of the fluorine atoms in one surface a of the film The existence ratio B1 of the fluorine atoms in the surface b of the film located on the opposite side to the surface a satisfies the relationship of the following formula (11), and the existence ratio A1 of the fluorine atoms is 5% to 40%, A1/B1≧ 1.3 (11) A1 is a ratio A1 in which the fluorine atoms in the surface a of the film are abbreviated, and B1 is a ratio B1 of the fluorine atoms in the surface b of the pseudo-attachment film. <20> The pseudo-adhesion film according to <19>, wherein the ratio B1 of the existence ratio of the fluorine atom of the pseudo-adhesion film to the fluorine atom B1 satisfies the relationship of the following formula (12), and the existence ratio of the fluorine atom A1 10% to 30%, A1/B1≧1.5 (12) A1 is a ratio of the presence of fluorine atoms in the surface a of the pseudo-attachment film A1, and B1 is the existence ratio of the fluorine atoms in the surface b of the pseudo-film. . <21> The pseudo-attachment film according to <19>, wherein the compound having a fluorine atom contains a lipophilic group. The pseudo-adhesive film according to any one of the above aspects, wherein the pseudo-adhesion film contains at least one selected from the group consisting of a binder and a radical polymerizable compound. The pseudo-adhesive film according to any one of the above aspects, wherein the pseudo-adhesive film contains 0.03 mass% or more and less than 0.5 mass% of the total solid content of the pseudo-adhesive film. A compound of a fluorine atom. <24> A laminated body obtained by the production method according to any one of <1> to <18>, or a false one according to any one of <19> to <23> Next, the film and the substrate provided on one or both sides of the dummy film. <25> A laminated body with a component wafer, which has a dummy film obtained by the manufacturing method according to any one of <1> to <18>, or The pseudo-adhesive film according to any one of <19>, wherein one side of the film is in contact with the element surface of the element wafer, and the other side is in contact with the surface of the carrier substrate. <26> The laminated body with a component wafer according to <25>, wherein the area of the film surface of the dummy film is smaller than the area of the substrate surface of the carrier substrate. <27> The laminated body with a component wafer according to <25>, wherein the diameter of the substrate surface of the carrier substrate is set to C μm, and the diameter of the substrate surface of the component wafer is set to D μm. When the diameter of the film surface of the dummy film is set to T μm, (C-200) ≧T≧D is satisfied. <28> The laminated body with a component wafer according to <25>, wherein the diameter of the substrate surface of the carrier substrate is set to C μm, and the diameter of the substrate surface of the component wafer is set to D μm. The diameter of the film surface on the side in contact with the carrier substrate of the dummy film is T _C μm, and when the diameter of the film surface on the side of the contact film on the surface of the dummy film is T _D μm, it satisfies (C- 200) ≧T _C >T _D ≧D. <29> A composition for a compound containing a fluorine atom, and a compound having a fluorine atom in a proportion of 0.03 mass% or more and less than 0.5 mass% in the total solid content of the composition. <30> The composition according to <29>, wherein the compound having a fluorine atom contains a lipophilic group. <31> The composition according to <29> or <30>, which further comprises at least one selected from the group consisting of a binder and a radical polymerizable compound. <32> The composition according to <31>, wherein the binder is an elastomer.

According to the present invention, it is possible to provide a method for producing a pseudo-adhesive film which is excellent in releasability and which can control a peeling interface, a pseudo-adhesive film, a laminate, a laminate with a device wafer, and a composition for a dummy.

Hereinafter, embodiments of the present invention will be described in detail. In the expression of the group (atomic group) in the present specification, the substituted and unsubstituted expressions are not described as including a group having no substituent (atomic group), and also a group having a substituent (atomic group). For example, the "alkyl group" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group). The "actinic ray" or "radiation" in the present specification means, for example, visible light, ultraviolet light, far ultraviolet light, electron beam, X-ray, or the like. In the present specification, "light" means actinic rays or radiation. In the present specification, the term "exposure" is used not only by mercury lamps, ultraviolet rays, far ultraviolet rays typified by excimer lasers, X-rays, extreme ultraviolet (EUV) light, etc., unless otherwise specified. Exposure also refers to the use of particle beams such as electron beams and ion beams. In the present specification, the total solid content refers to the total mass of the components obtained by removing the solvent from all the compositions of the composition. In the present specification, "(meth)acrylate" means acrylate and methacrylate, "(meth)acrylic" means acrylic acid and methacrylic acid, and "(meth)acryloyl group" means "acryloyl fluorenyl group". And "methacryl oxime". In the present specification, the weight average molecular weight and the number average molecular weight are defined as polystyrene-converted values measured by gel permeation chromatography (GPC). In the present specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) can be, for example, by using HLC-8220 (manufactured by Tosoh), using TSK gel Super AWM-H (Tosoh) (manufactured by Ltd.), 6.0 mm (inner diameter) × 15.0 cm) as a column, and using N-methyl pyrrolidinone (NMP) solution of 10 mmol/L lithium bromide as a washing liquid . In the present specification, the term "lipophilic group" means a functional group which does not contain a hydrophilic group. In addition, the "hydrophilic group" means a functional group which exhibits affinity with water. In the embodiments described below, the description of the components and the like which are already described in the drawings will be simplified or omitted by the same reference numerals or the corresponding reference numerals. In the present specification, the viscosity can be measured using a B-type viscometer, and the method for measuring the viscosity is performed using a B-type viscometer (in consideration of viscorido advance, manufactured by Fungilab). The value obtained by measuring the viscosity.

<Manufacturing Method of Membrane Substrate> The manufacturing method of the pseudo-adhesive film of the present invention includes a step of coating a dummy composition with a layer on a support and drying it, and the composition for the film is contained with a fluorine atom. Compound, regarding the pseudo-adhesive film, used as a pseudo-adhesive film surface as a result of irradiating 25 W of monochromated AlKα rays on an analysis area of 1400 μm ́700 μm on the surface of the pseudo-adhesive film and detecting at an exit angle of 45°. The ratio of the presence of fluorine atoms obtained by X-ray photoelectron spectroscopy, the ratio A of the fluorine atoms in the surface of the film opposite to the support, and the fluorine atom in the surface of the support side of the pseudo-attachment film The existence ratio B satisfies the relationship of the following formula (1), and the existence ratio A of the fluorine atoms is 5% to 40%. A/B≧1.3 (1) A is the existence ratio A of the fluorine atoms in the surface of the film opposite to the support on the side of the film, and B is the existence of fluorine atoms in the surface of the support side of the dummy film. Ratio B. In the present invention, the measurement conditions in the X-ray photoelectron spectroscopy method are a temperature of 20 ° C to 25 ° C and a pressure of 10 ^-8 Pa or less. As a device of the X-ray photoelectron spectroscopy, PHI Quantera SXM (manufactured by ULVAC PHI) can be used.

In the present invention, a pseudo-attachment film is produced by using a compound containing a fluorine atom as a pseudo-construction composition. A compound having a fluorine atom generally has a property of being hard to be present inside a film such as a pseudo-adhesion film and tending to be biased toward both surfaces of the film. Furthermore, the inventors of the present invention conducted research and found that a compound having a fluorine atom particularly has a property of being easily biased toward a surface having a high hydrophobicity, and if a compound having a fluorine atom is contained on a support, When the composition is applied in a layered form, the compound having a fluorine atom is further biased to a surface having a high hydrophobicity, that is, a surface of the pseudo-adhesive film opposite to the support (hereinafter also referred to as an air side interface). Therefore, according to the present invention, the ratio of the existence ratio of the fluorine atom to the fluorine atom B can be produced only by coating the pseudo-constituent composition containing the compound having a fluorine atom on the support as a layer and drying it. A pseudo-attachment film satisfying the relationship of the formula (1) and having a fluorine atom presence ratio A of 10% to 40%. Moreover, the ratio B of the existence ratio of the fluorine atom of the pseudo-attachment film obtained by the present invention to the fluorine atom satisfies the relationship of the formula (1), so that the carrier substrate and the element can be bonded to the air side interface of the dummy film. Wafer stripping. Further, since the ratio A of the fluorine atoms in the air side interface of the film is 10% to 40%, the carrier substrate and the element wafer can be peeled off with a small peeling force.

Further, as described above, the compound having a fluorine atom has a property of being easily present in the inside of the film and tends to be biased toward both surfaces of the film, and particularly has a property of being easily biased to the surface existing on the side having high hydrophobicity. Therefore, when a composition is applied to the support and the composition is abrupt, a large amount of a compound having a fluorine atom tends to be present on the air side interface which is a surface having high hydrophobicity. On the other hand, it is found that if the proportion of the compound having a fluorine atom in the air-side interface is increased, the hydrophobicity at the air-side interface is lowered, and it is also likely to be biased toward the surface existing on the support side, and it is found that the fluorine atom is adjusted by adjustment. The content of the compound can easily bias more of the compound having a fluorine atom to the air side interface existing in the pseudo-attachment film. For example, a compound having a fluorine atom can be more easily obtained by using a pseudo-construction composition containing a compound having a fluorine atom in a ratio of 0.03 mass% or more and less than 0.5 mass% in the total solid content of the composition. The bias exists in the air side interface of the dummy film. Hereinafter, the present invention will be described.

<<Fake Next Composition>> <<<Compound having fluorine atom (fluorine-containing compound)>>> The composition for pseudo-conversion of the present invention contains a compound having a fluorine atom (also referred to as a fluorine-containing compound). It is preferable to contain a fluorine-containing compound in a ratio of 0.03 mass% or more and less than 0.5 mass% in the total solid content of the composition. The lower limit is more preferably 0.03% by mass or more, still more preferably 0.04% by mass or more, and still more preferably 0.05% by mass or more. The upper limit is more preferably less than 0.5% by mass, still more preferably 0.4% by mass or less, and particularly preferably 0.2% by mass or less. The fluorine-containing compound may contain a plurality of kinds, and in this case, it is preferred that the total amount satisfies the above range. As described above, when the content of the fluorine-containing compound is in the above range, more fluorine-containing compounds can be easily biased toward the air interface side of the pseudo-adhesion film, and the existence ratio of fluorine atoms and the presence of fluorine atoms can be easily produced. The pseudo-adhesion film in which the ratio B satisfies the relationship of the formula (1) and the fluorine atom is present in a ratio A of 10% to 40%.

The fluorine-containing compound is preferably a liquid compound. In the present invention, the liquid is a compound having fluidity at 25 ° C, and is, for example, a compound having a viscosity at 25 ° C of 1 mPa·s to 100,000 mPa·s. The viscosity at 25 ° C of the fluorine-containing compound is, for example, more preferably from 10 mPa·s to 20,000 mPa·s, particularly preferably from 100 mPa·s to 15,000 mPa·s. When the viscosity of the fluorine-containing compound is in the above range, the fluorine-containing compound tends to be biased toward the surface of the pseudo-attachment film.

In the present invention, as the fluorine-containing compound, a compound of any form of an oligomer or a polymer can be preferably used. Alternatively, it may be a mixture of an oligomer and a polymer. The mixture may further contain a monomer. Further, the fluorine-containing compound may be a monomer. From the viewpoint of heat resistance and the like, the fluorine-containing compound is preferably an oligomer, a polymer, and a mixture thereof. Examples of the oligomer and the polymer include a radical polymer, a cationic polymer, an anionic polymer, and the like, and any of them can be preferably used. Particularly preferred is a vinyl polymer. The weight average molecular weight of the fluorine-containing compound is preferably from 500 to 100,000, more preferably from 1,000 to 50,000, still more preferably from 2,000 to 20,000.

In the present invention, the fluorine-containing compound is preferably a compound which does not undergo modification when the substrate for the false substrate is treated. For example, a compound which can be present in a liquid form even after heating at 250 ° C or higher or treating the substrate with various chemical solutions is preferred. As a specific example, it is preferable to heat to 250 ° C under the temperature rising condition of 10 ° C / minute from the state of 25 ° C, and the viscosity at 25 ° C after cooling to 25 ° C is 1 mPa·s to 100,000 mPa·s. More preferably, it is 10 mPa·s to 20,000 mPa·s, and particularly preferably 100 mPa·s to 15,000 mPa·s. As the fluorine-containing compound having such characteristics, a non-thermosetting compound having no reactive group is preferred. The reactive group as used herein refers to the entire group of the reaction which is reacted by heating at 250 ° C, and examples thereof include a polymerizable group and a hydrolyzable group. Specific examples thereof include a methyl (acrylic acid) group, an epoxy group, and an isocyanate group. The non-thermosetting compound is preferably a non-polymerizable polymer compound having a fluorine atom. As the non-polymerizable polymer compound having a fluorine atom, a polymer containing one or two or more kinds of fluorine-containing monofunctional monomers can be preferably used. More specifically, a fluorine-containing resin or the like selected from at least one of the following polymers selected from the group consisting of tetrafluoroethylene, hexafluoropropylene, tetrafluoroethylene oxide, hexafluoropropylene oxide, and perfluoroalkylethylene may be mentioned. Homopolymer of one or two or more fluorine-containing monofunctional monomers of a vinyl ether, chlorotrifluoroethylene, vinylidene fluoride, a perfluoroalkyl group-containing (meth) acrylate or copolymerization of the monomers A copolymer of one or two or more copolymers of fluorine, a fluorine-containing monofunctional monomer and ethylene, or one or more of fluorine-containing monofunctional monomers and chlorotrifluoroethylene.

The non-polymerizable polymer compound having a fluorine atom is preferably a perfluoroalkyl group-containing (meth)acrylic resin synthesized from a (meth) acrylate containing a perfluoroalkyl group.

From the viewpoint of the releasability, in addition to the (meth) acrylate containing a perfluoroalkyl group, the (meth)acrylic resin containing a perfluoroalkyl group can be arbitrarily selected as a copolymerization component. Examples of the radically polymerizable compound capable of forming a copolymerization component include acrylates, methacrylates, N,N-2 substituted acrylamides, and N,N-2 substituted methacrylamides. A radically polymerizable compound in styrene, acrylonitrile, methacrylonitrile or the like.

More specifically, for example, an acrylate such as an alkyl acrylate (preferably having an alkyl group having 1 to 20 carbon atoms) (for example, methyl acrylate, ethyl acrylate, propyl acrylate or butyl acrylate) , amyl acrylate, ethylhexyl acrylate, octyl acrylate, trioctyl acrylate, chloroethyl acrylate, 2,2-dimethylhydroxypropyl acrylate, 5-hydroxypentyl acrylate, trishydroxyl Propane monoacrylate, pentaerythritol monoacrylate, glycidyl acrylate, benzyl acrylate, methoxybenzyl acrylate, decyl acrylate, tetrahydrofurfuryl acrylate, etc.; aryl acrylate (eg acrylic acid) a methacrylate such as a phenyl ester or the like; an alkyl methacrylate (preferably having an alkyl group having 1 to 20 carbon atoms) (for example, methyl methacrylate, ethyl methacrylate, methyl group) Propyl acrylate, isopropyl methacrylate, amyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, chlorobenzyl methacrylate, octyl methacrylate Methacrylic acid-4 -hydroxybutyl ester, 5-hydroxypentyl methacrylate, 2,2-dimethyl-3-hydroxypropyl methacrylate, trimethylolpropane monomethacrylate, pentaerythritol monomethacrylate , glycidyl methacrylate, decyl methacrylate, tetrahydrofurfuryl methacrylate, etc.; aryl methacrylate (eg phenyl methacrylate, cresyl methacrylate, A) Nylyl acrylate, etc.; styrene, alkylstyrene, etc. (such as methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, diethyl styrene, isopropyl Styrene, butyl styrene, hexyl styrene, cyclohexyl styrene, mercaptophenethyl, benzyl styrene, chloromethyl styrene, trifluoromethyl styrene, ethoxymethyl styrene, Ethyloxymethylstyrene, etc., alkoxystyrene (such as methoxystyrene, 4-methoxy-3-methylstyrene, dimethoxystyrene, etc.), halogen styrene ( For example, chlorostyrene, dichlorostyrene, trichlorostyrene, tetrachlorostyrene, pentachlorostyrene, bromophenyl , dibromostyrene, iodine styrene, fluorostyrene, trifluorostyrene, 2-bromo-4-trifluoromethylstyrene, 4-fluoro-3-trifluoromethylstyrene, etc.; acrylonitrile; Methacrylonitrile; a radically polymerizable compound containing acrylic acid or a carboxylic acid (acrylic acid, methacrylic acid, itaconic acid, crotonic acid, methacrylic acid, maleic acid, p-carboxystyrene, and acid groups thereof) Metal salt, ammonium salt compound, etc.). From the viewpoint of the releasability, a (meth) acrylate having a hydrocarbon group having 1 to 24 carbon atoms is particularly preferable, and examples thereof include methyl ester, butyl ester, 2-ethylhexyl ester of (meth)acrylic acid, and laurel. The base ester, stearyl ester, glycidyl ester or the like is preferably a (meth) acrylate of a higher alcohol such as 2-ethylhexyl, lauryl or stearyl, and particularly preferably an acrylate.

In the present invention, the 10% thermal mass reduction temperature at which the fluorine-containing compound is heated at 25 ° C / min from 25 ° C is preferably 250 ° C or higher, more preferably 280 ° C or higher. Further, the upper limit is not particularly limited, and is, for example, preferably 1000 ° C or lower, more preferably 800 ° C or lower. According to this aspect, it is easy to form a pseudo-adhesion film excellent in heat resistance. In addition, the 10% thermal mass reduction temperature is a temperature which is measured by the thermogravimetric measuring apparatus under the nitrogen gas flow rate, and it is confirmed that the weight before measurement is reduced by 10%.

In the present invention, the fluorine-containing compound is preferably a compound containing a lipophilic group and a fluorine atom. Examples of the lipophilic group include an alkyl group and an aromatic group.

The alkyl group may, for example, be a linear alkyl group, a branched alkyl group or a cyclic alkyl group. The carbon number of the linear alkyl group is preferably from 2 to 30, more preferably from 4 to 30, still more preferably from 6 to 30, particularly preferably from 12 to 20. The number of carbon atoms of the branched alkyl group is preferably from 3 to 30, more preferably from 4 to 30, still more preferably from 6 to 30, particularly preferably from 12 to 20. The cyclic alkyl group may be a single ring or a polycyclic ring. The number of carbon atoms of the cyclic alkyl group is preferably from 3 to 30, more preferably from 4 to 30, still more preferably from 6 to 30, most preferably from 12 to 20. Specific examples of the linear alkyl group or the branched 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 decyl group, a decyl group, and a dodecyl group. , tetradecyl, octadecyl, isopropyl, isobutyl, t-butyl, tert-butyl, 1-ethylpentyl, 2-ethylhexyl. Specific examples of the cyclic alkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, an adamantyl group, a norbornyl group, a borneyl group, and a nonenyl group. , decahydronaphthyl, tricyclodecyl, tetracyclodecyl, camphoroyl, dicyclohexyl, nonenyl. The alkyl group may have a substituent. Examples of the substituent include a halogen atom, an alkoxy group, and an aromatic group. The halogen atom may, for example, be a chlorine atom, a fluorine atom, a bromine atom or an iodine atom, and is preferably a fluorine atom. The alkoxy group preferably has 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, still more preferably 1 to 10 carbon atoms. The alkoxy group is preferably a linear alkoxy group or a branched alkoxy group. The aromatic group may be a single ring or a polycyclic ring. The carbon number of the aromatic group is preferably from 6 to 20, more preferably from 6 to 14, most preferably from 6 to 10.

The aromatic group may be a single ring or a polycyclic ring. The carbon number of the aromatic group is preferably from 6 to 20, more preferably from 6 to 14, most preferably from 6 to 10. The aromatic group preferably has no hetero atom (for example, a nitrogen atom, an oxygen atom, a sulfur atom or the like) in the element constituting the ring. Specific examples of the aromatic group include a benzene ring, a naphthalene ring, a pentalene ring, an indene ring, an anthracene ring, a heptalene ring, and an indecene ring. , anthracene ring, pentacene ring, anthracene ring, phenanthrene ring, anthracene ring, fused tetraphenyl ring, 1,2-benzophene ring, triphenylene ring, anthracene ring, Benzene ring, pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, pyridazine ring, anthracene ring, benzofuran ring, Benzothiophene ring, isobenzofuran ring, quinolizine ring, quinoline ring, pyridazine ring, naphthyridine ring, quinoxaline ring, quinazoline ring, isoquinoline ring, indazole ring, phenanthridine a ring, an acridine ring, a phenanthroline ring, a thianthrene ring, a chromene ring, a xanthene ring, a phenoxathiin ring, a phenothiazine ring And the phenazine ring. The aromatic group may have the substituent.

The fluorine-containing compound may be a compound containing only one lipophilic group, or may contain two or more kinds. Further, the lipophilic group may also contain a fluorine atom. That is, the fluorine-containing compound may be a compound containing only a fluorine atom in the lipophilic group. Further, it may be a compound containing a group having a fluorine element (also referred to as a fluorine group) in addition to the lipophilic group. A compound containing a lipophilic group and a fluorine group is preferred. In the case where the fluorine-containing compound is a compound containing a lipophilic group and a fluorine group, the lipophilic group may contain a fluorine atom or may not contain a fluorine atom, and preferably the lipophilic group does not contain a fluorine atom. The fluorine-containing compound has one or more lipophilic groups in one molecule, preferably from 2 to 100, particularly preferably from 6 to 80.

As the fluorine group, a known fluorine group can be used. For example, a fluorine-containing alkyl group, a fluorine-containing alkylene group, etc. are mentioned. Further, those having a function as a lipophilic group in the fluorine group are contained in the lipophilic group. The fluorine-containing alkyl group preferably has 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, still more preferably 1 to 15 carbon atoms. The fluorine-containing alkyl group may be any of a straight chain, a branched group, and a cyclic group. In addition, it may have an ether bond. Further, the fluorine-containing alkyl group may be a perfluoroalkyl group in which all of the hydrogen atoms are substituted with a fluorine atom. The fluorine-containing alkylene group preferably has 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, still more preferably 2 to 15 carbon atoms. The fluorine-containing alkyl group may be any of a straight chain, a branched chain, and a cyclic group. In addition, it may have an ether bond. Further, the fluorine-containing alkylene group may be a perfluoroalkylene group in which all of the hydrogen atoms are substituted with a fluorine atom.

The content of the fluorine atom in the fluorine-containing compound is preferably from 1% by mass to 90% by mass, more preferably from 2% by mass to 80% by mass, even more preferably from 5% by mass to 70% by mass. When the fluorine content is in the above range, the peeling property is excellent. The content of the fluorine atom is defined by "{(the mass of the fluorine atom in one molecule, the mass of the fluorine atom) / the mass of all the atoms in one molecule} ́100".

A commercially available product can also be used for the fluorine-containing compound. As a non-thermosetting compound, commercially available ones include Teflon (registered trademark) (DuPont), Tefzel (DuPont), and Fluon. (Asahi Glass Co., Ltd.), Heira (SolvaySolexis), Hailer (SolvaySolexis), Lumiflon (Asahi Glass) Company), Aflas (Asahi Glass), Cefralsoft (Central Glass), Cefralcoat (Central Glass), etc. Resin; fluoroelastomers such as Viton (DuPont), Kalrez (DuPont), SIFEL (Shin-Etsu Chemical Industries); Krytox (DuPont), Fomblin (Daitoku Tech), Demnum (Daikin Industries), Surflon (Surflon) (For example, Surflon S243, etc., AGC Seimi Chemical Co., Ltd.), etc., various fluoro oils represented by perfluoropolyether oil; or Dairy FB962, etc. Daihexine (Daifree) ) Fluoride-containing release agent such as FB series (Daikin Industrial Co., Ltd.) and Megafac series (Di-Aisheng (DIC) Co., Ltd.). In addition, as a fluorine-containing compound containing an oleophilic group, for example, F-251, F-281, F-477, and F-553 of the Megafac series manufactured by DiCai (DIC) Co., Ltd. may be mentioned. , F-554, F-555, F-556, F-557, F-558, F-559, F-560, F-561, F-563, F-565, F-567, F-568, F -571, R-40, R-41, R-43, R-94; or 710F, 710FM, 710FS, 710FL, 730FL, 730LM of the Ftergent series manufactured by NEOS.

In the present invention, a fluorine-containing decane coupling agent may be used as the fluorine-containing compound. The fluorine-containing decane coupling agent is preferably a non-halogen decane coupling agent, particularly preferably a fluorine-containing alkoxy decane. As a commercial item, Optool DAC-HP and Optool DSX by Daikin Industrial Co., Ltd. are mentioned.

<<Binder>> The composition for pseudo-adhesive of the present invention preferably contains at least one selected from the group consisting of a binder and a radical polymerizable compound. The binder and the radically polymerizable compound may be used in combination or may be used alone. First, the adhesive will be described.

In the present invention, any of the binders may be used. The binder may, for example, be a block copolymer, a random copolymer or a graft copolymer, and is preferably a block copolymer. In the case of the block copolymer, the flow of the pseudo-adhesive composition during the heating process can be suppressed. Therefore, even if it is heated during the heating process, it is expected that the peeling property does not change after the heating process. The type of the binder is not particularly limited, and a polystyrene copolymer, a polyester copolymer, a polyolefin copolymer, a polyurethane copolymer, a polyamine copolymer, or a polyacrylic acid can be used. A copolymer, an anthrone-based copolymer, a polyimide-based copolymer, or the like. In particular, a polystyrene copolymer, a polyester copolymer, and a polyamine copolymer are preferable, and a polystyrene copolymer is more preferable from the viewpoint of heat resistance and peelability. Among them, the binder is preferably a block copolymer of styrene and other monomers, particularly preferably a styrene block copolymer having a single terminal or a styrene block at both ends. Further, the binder is preferably a hydride of a block copolymer. If the binder is a hydride, thermal stability or storage stability is improved. Further, the peeling property and the cleaning removal property of the pseudo-adhesive film after peeling are improved. Further, the hydride refers to a polymer having a structure in which a block copolymer is hydrogenated.

In the present description, the binder is preferably an elastomer. By using an elastomer as a binder, it is possible to follow the fine concavities and convexities of the carrier substrate or the element wafer, and to form a pseudo-adhesion film excellent in adhesion by an appropriate anchor effect. The elastomer may be used alone or in combination of two or more. In the present specification, the elastomer is a polymer compound which exhibits elastic deformation. That is, it is defined as a polymer compound having a property that when an external force is applied, deformation occurs instantaneously in response to the external force, and when the external force is removed, the original shape is restored in a short time.

<<<Elastomer>>> In the present invention, the weight average molecular weight of the elastomer is preferably from 2,000 to 200,000, more preferably from 10,000 to 200,000, still more preferably from 50,000 to 100,000. By being in this range, there is an advantage in that, when the support substrate is peeled off from the element wafer, when the residue derived from the elastomer remaining on the element wafer and/or the support substrate is removed, the solubility in the solvent is also Excellent, so the residue does not remain on the component wafer or carrier substrate.

In the present invention, the elastomer is not particularly limited, and an elastomer (polystyrene elastomer) containing a repeating unit derived from styrene, a polyester elastomer, a polyolefin elastomer, or a polyamine group can be used. An acid ester-based elastomer, a polyamine-based elastomer, a polyacryl-based elastomer, an anthrone-based elastomer, a polyimide-based elastomer, or the like. In particular, a polystyrene-based elastomer, a polyester-based elastomer, and a polyamide-based elastomer are preferable, and from the viewpoint of heat resistance and peelability, a polystyrene-based elastomer is preferable.

In the present invention, the elastomer is preferably a hydride. Particularly preferred is a hydride of a polystyrene elastomer. If the elastomer is a hydride, thermal stability or storage stability is improved. Further, the peeling property and the cleaning removal property of the pseudo-adhesive film after peeling are improved. The effect is remarkable when a hydride of a polystyrene elastomer is used. Further, the hydride refers to a polymer having a structure in which an elastomer is hydrogenated.

In the present invention, the 5% thermal mass reduction temperature of the elastomer from 25 ° C at 20 ° C / min is preferably 250 ° C or higher, more preferably 300 ° C or higher, further preferably 350 ° C or higher, and most preferably 400 ° C. the above. Further, the upper limit is not particularly limited, and is, for example, preferably 1000 ° C or lower, more preferably 800 ° C or lower. According to this aspect, it is easy to form a pseudo-adhesion film excellent in heat resistance. The elastomer of the present invention preferably has such a property that when the original size is set to 100%, it can be deformed to 200% at a small external force at room temperature (20 ° C), and is short when the external force is removed. Recover to below 130% within the time.

<<<<Polystyrene Elastomer>>>> The polystyrene 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 embedded Segment copolymer (SEBS), styrene-butadiene-butene-styrene block copolymer (SBBS) and these hydrides, styrene-ethylene-butylene styrene block copolymer (SEBS), Styrene-ethylene-propylene-styrene block copolymer (SEPS), styrene-ethylene-ethylene-propylene-styrene block copolymer, and the like.

The content of the styrene-derived repeating unit in the polystyrene-based elastomer is preferably 10% by mass to 90% by mass. From the viewpoint of the peelability, the lower limit is preferably 25% by mass or more, and more preferably 51% by mass or more.

In the present invention, it is preferable that the polystyrene elastomer is used in combination with the elastomer A and the elastomer B, and the elastomer A is contained in a ratio of 10% by mass or more and 50% by mass or less in all the repeating units. A repeating unit of styrene containing a repeating unit derived from styrene in a ratio of more than 50% by mass and 95% by mass or less in all the repeating units. By using the elastomer A and the elastomer B in combination, the flatness of the polished surface of the substrate (hereinafter also referred to as flat polishing property) is excellent, and the warpage of the substrate after polishing can be effectively suppressed. produce. The mechanism for obtaining such an effect can be presumed to be the following. That is, since the elastomer A is a relatively soft material, it is easy to form a pseudo-adhesive film having elasticity. Therefore, when the laminate of the substrate and the support is produced by using the composition of the present invention and the substrate is subjected to polishing and thinning, even if the pressure at the time of polishing is locally applied, the film can be elastically deformed. And it is easy to return to the original shape. As a result, excellent flatness is obtained. Further, even if the laminated body after polishing is subjected to heat treatment and then cooled, the internal stress generated during cooling can be relieved by the dummy film, whereby the occurrence of warpage can be effectively suppressed. Further, since the elastic body B is a relatively hard material, a pseudo-adhesion film excellent in peelability can be produced by containing the elastic body B.

The elastomer A preferably contains 13% by mass to 45% by mass of repeating units derived from styrene in all repeating units, more preferably 15% by mass to 40% by mass. In this case, more excellent flatness can be obtained. Further, it is possible to effectively suppress the occurrence of warpage of the substrate after polishing. The hardness of the elastomer A is preferably from 20 to 82, more preferably from 60 to 79. Further, the hardness is a value measured by a method of Japanese Industrial Standards (JIS) K6253 and measured by a Type A durometer.

The elastomer B preferably contains 55 to 90% by mass of repeating units derived from styrene in all repeating units, more preferably 60% by mass to 80% by mass. According to this aspect, the peeling property can be more effectively improved. The hardness of the elastomer B is preferably from 83 to 100, more preferably from 90 to 99.

The quality of the elastomer A and the elastomer B is preferably elastomer A: elastomer B = 5: 95 to 95: 5, more preferably 10: 90 to 80: 20, and even more preferably 15: 85 ~60:40, the best is 25~75:60~40. If it is the range, the effect can be obtained more effectively.

The polystyrene elastomer is preferably a block copolymer of styrene and other monomers, more preferably a block copolymer having a single terminal or a styrene block at both ends, and particularly preferably a styrene block at both ends. . When both ends of the polystyrene elastomer are styrene blocks (repeating units derived from styrene), heat resistance tends to be further improved. The reason for this is that a repeating unit derived from styrene having high heat resistance exists at the terminal. In particular, the block portion derived from the repeating unit derived from styrene is preferably a reactive polystyrene-based hard block, and is preferably more excellent in heat resistance and chemical resistance. Further, it is considered that when these are block copolymers, phase separation is performed between the hard block and the soft block at 200 ° C or higher. It is considered that the shape of the phase separation contributes to suppression of generation of irregularities on the surface of the element wafer. Further, such an elastomer is more preferable from the viewpoint of solubility in a solvent and resistance in a resist solvent. Further, when the polystyrene elastomer is a hydride, the stability to heat is improved and it is less likely to cause deterioration such as decomposition or polymerization. Further, it is also more preferable from the viewpoint of solubility in a solvent and resistance in a resist solvent. The amount of the unsaturated double bond as the polystyrene-based elastomer is preferably less than 15 mmol, more preferably less than 5 mmol, per 100 g of the polystyrene-based elastomer, from the viewpoint of the releasability. Less than 0.5 mmol. Furthermore, the amount of unsaturated double bonds described herein does not comprise unsaturated double bonds in the benzene ring derived from styrene. The amount of unsaturated double bonds can be calculated by nuclear magnetic resonance (NMR) measurement.

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

As a commercial item of a polystyrene type elastomer, for example, Tufprene A, Tufprene 125, Tufprene 126S, Solprene are mentioned. T, Asaprene T-411, Asaprene T-432, Asaprene T-437, Asaprene T-438, Asapron (Asaprene) T-439, Tuftec H1272, Tuftec P1500, Tuftec H1052, Tuftec H1062, Tuftec M1943, Tuftec M1911, Tuftec H1041, Tuftec MP10, Tuftec M1913, Tuftec H1051, Taft Tuftec H1053, Tuftec P2000, Tuftec H1043 (made by Asahi Kasei Co., Ltd.); Elastomer AR-850C, Elastomer AR-815C, Elastomer AR-840C, Elastomer AR-830C, Elastomer AR-860C, Elastomer AR-875C, Elastomer AR-885C, Elastomer AR-SC-15, Elastomer AR-SC-0, Elastomer AR-SC-5, Elastomer ( Elastomer) AR-710, Elastomer AR-SC-65, Elastomer AR-SC-30, Elastomer AR-SC-75, Elastomer AR-SC-45, Elastomer AR-720, Elastomer AR-741, Elastomer AR-731, Elastomer AR-750, Elastomer AR-760, Elastomer AR-770, Elastomer AR-781, Elastomer AR-791, Elastomer AR-FL-75N, Elastomer AR-FL-85N, Elastomer AR -FL-60N, Elastomer AR-1050, Elastomer AR-1060, Elastomer AR-1040 (manufactured by Aronkasei); Kraton D1111, Kraton (Kraton) D1113, Kraton D1114, Kraton D1117, Kraton D1119, Kraton D1124, Kraton Kraton) D1126, Kraton D1161, Kraton D1162, Kraton D1163, Kraton D1164, Kraton D1165, Kraton D1183, Kraton ) D1193, Kraton DX406, Kraton D4141, Kraton D4150, Kraton D4153, Kraton D4158, Kraton D4270, Kraton D4271, Kraton D4433, Kraton D1170, Kraton D1171, Kraton D1173, Cariflex IR0307, Cariflex IR0310, Cali Cariflex IR0401, Kraton D0242, Kraton D1101, Kraton D1102, Kraton D1116, Kraton D1118, Kraton D1133, Section Kraton D1152, Kraton D1153, Kraton D1155, Kraton D1184, Kraton D1186, Kraton D1189, Kraton D1191, Kraton (Kraton) D1192, Kraton DX405, Kraton D X408, Kraton DX410, Kraton DX414, Kraton DX415, Kraton A1535, Kraton A1536, Kraton FG1901, Kraton FG1924 Kraton G1640, Kraton G1641, Kraton G1642, Kraton G1643, Kraton G1645, Kraton G1633, Kraton G1650, Kraton G1651, Kraton G1652, Kraton G1654, Kraton G1657, Kraton G1660, Kraton G1726, Kraton G1701 Kraton G1702, Kraton G1730, Kraton G1750, Kraton G1765, Kraton G4609, Kraton G4610 (made by Kraton); TR2000 , TR2001, TR2003, TR2250, TR2500, TR2601, TR2630, TR2787, TR2827, TR1086, TR1600, SIS5002, SIS5200, SIS5250, SIS5405, SIS5505, Dynaron 6100P, Dynaron 4600P, Dynalong (Dynaron) 6200P, Dyaron (Dynaron) 4630P, Dynaron 8601P, Dynaron 8630P, Dynaron 8600P, Dynaron 8903P, Dynaron 6201B, Dynaron 1321P, Dynaron 1320P, Dynaron 2324P, Dynaron 9901P (manufactured by JSR); Denka STR series (manufactured by Electrochemical Industry); Quinta Quintac 3520, Quintac 3433N, Quintac 3421, Quintac 3620, Quintac 3450, Quintac 3460 (Japanese Ryeon (Japanese) ZEON) Manufactured; TPE-SB series (manufactured by Sumitomo Chemical Co., Ltd.); Rabalon series (manufactured by Mitsubishi Chemical Co., Ltd.); Septon 1001, Septon 8004, competition Septon 4033, Septon 2104, Septon 8007, Septon 2007, Septon 2004, Septon 2063, Saipton (Septon) HG252, Septon (8074), Septon (2002), Septon 1020, Septon 8104, Septon 2005, Septon 2006, Septon 4055, Septon 4044, Saipton (Septon) 4077, Septon 4099, Septon 8006, Septon V9461, Septon V9475, Septon V9827, Hybrar ) 7311, Hybrar 7125, Hybrar 5127, Hybrar 5125 (made by Kuraray); Sumiflex (Sumitomo Bakelite) ) (manufacturing); Leostomer, Actymer (manufactured by Riken Ethylene Industries), etc.

<<<<Polyester Elastomer>>>> The polyester elastomer is not particularly limited and may be appropriately selected depending on the purpose. For example, a dicarboxylic acid or a derivative thereof, and a diol compound or a derivative thereof may be polycondensed. Examples of the dicarboxylic acid include an aromatic dicarboxylic acid such as terephthalic acid, isophthalic acid or naphthalene dicarboxylic acid, and a hydrogen atom of the aromatic nucleus substituted with a methyl group, an ethyl group, a phenyl group or the like. An aromatic dicarboxylic acid; an aliphatic dicarboxylic acid having 2 to 20 carbon atoms such as adipic acid, sebacic acid or dodecane dicarboxylic acid; and an alicyclic dicarboxylic acid such as cyclohexanedicarboxylic acid. These may be used alone or in combination of two or more. Examples of the diol compound include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,10-nonanediol, and 1,4-cyclohexanediol. An aliphatic diol; an alicyclic diol; a divalent phenol represented by the following structural formula.

[Chemical 2]

In the formula, Y ^DO represents any of an alkylene group having 1 to 10 carbon atoms, a cycloalkyl group having 4 to 8 carbon atoms, -O-, -S- and -SO ₂ -, or benzene. Rings each other's direct keys (single key). R ^DO1 and R ^DO2 each independently represent a halogen atom or an alkyl group having 1 to 12 carbon atoms. p ^do1 and p ^do2 each independently represent an integer of 0 to 4, and n ^do1 represents 0 or 1.

Specific examples of the polyester elastomer include bisphenol A, bis-(4-hydroxyphenyl)methane, bis-(4-hydroxy-3-methylphenyl)propane, resorcin, and the like. These may be used alone or in combination of two or more. Further, as the polyester elastomer, an aromatic polyester (for example, polybutylene terephthalate) portion may be used as a hard segment component and an aliphatic polyester (for example, polytetramethylene glycol) may be used. A multi-block copolymer obtained by partially setting a soft segment component. The multi-block copolymer may be classified into various grades by the difference in the kind, ratio, and molecular weight of the hard segment and the soft segment. Specific examples include: Hytrel (manufactured by DuPont-Toray); Pelprene (made by Toyobo Co., Ltd.); Primalloy (Mitsubishi Chemical); Nouvelan (manufactured by Teijin Chemical Co., Ltd.); Espel 1612, 1620 (manufactured by Hitachi Chemical Co., Ltd.).

<<<<Polyolefin-based elastomer>>>> The polyolefin-based elastomer is not particularly limited and may be appropriately selected depending on the purpose. For example, a copolymer of an alkylene group having 2 to 20 carbon atoms such as ethylene, propylene, 1-butene, 1-hexene or 4-methyl-pentene can be mentioned. For example, an ethylene-propylene copolymer (EPR), an ethylene-propylene-diene copolymer (EPDM), etc. are mentioned. Further, examples thereof include carbon number 2 such as dicyclopentadiene, 1,4-hexadiene, cyclooctadiene, methylene norbornene, ethylidene norbornene, butadiene, and isoprene. 20 non-conjugated diene and α-olefin copolymer and the like. Further, a carboxyl-modified nitrile rubber obtained by copolymerizing methacrylic acid and a butadiene-acrylonitrile copolymer can be mentioned. Specific examples thereof include ethylene·α-olefin copolymer rubber, ethylene·α-olefin·non-conjugated diene copolymer rubber, propylene·α-olefin copolymer rubber, and butene·α-olefin copolymer rubber. As a commercial item, Milastomer (manufactured by Mitsui Chemicals Co., Ltd.); Thermoron (manufactured by Mitsubishi Chemical Corporation); EXACT (manufactured by Exon Chemical); EAGNGE (manufactured by Dow Chemical); Espolex (manufactured by Sumitomo Chemical); Sarlink (manufactured by Toyobo); Newcon (made by Japan Polypropylene) ); Exxlin (EXCELINK) (made by JSR).

<<<<Polyurethane-Based Elastomer>>>> The polyurethane-based elastomer is not particularly limited and may be appropriately selected depending on the purpose. For example, an elastomer including a hard segment including a low molecular weight diol and a diisocyanate, and a structural unit containing a soft segment of a polymer (long-chain) diol and a diisocyanate may be mentioned. Examples of the polymer (long-chain) diol include polypropylene glycol, polytetramethylene oxide, poly(1,4-butene adipate), and poly(ethylene·1,4-butene hexane). Acid ester), polycaprolactone, poly(1,6-hexene carbonate), poly(1,6-hexene·nepentene adipate), and the like. The number average molecular weight of the polymer (long-chain) diol is preferably from 500 to 10,000. As the low molecular weight diol, a short chain diol such as ethylene glycol, propylene glycol, 1,4-butanediol or bisphenol A can be used. The number average molecular weight of the short-chain diol is preferably from 48 to 500. As a commercial item of a polyurethane elastomer, PANDEX T-2185, T-2983N (made by DIC), Miractran is mentioned. (Miraract, Japan); Elastollan (made by BASF); Resamin (made by Daiichi Seiki Co., Ltd.); Pellethane (Tao) (made by Dow Chemical); Ironrubber (manufactured by NOK); Mobilon (manufactured by Nisshinbo Chemical Co., Ltd.).

<<<<Polyurethane-based elastomer>>>> The polyamine-based elastomer is not particularly limited and may be appropriately selected depending on the purpose. For example, polyamines such as polyamines-6, 11, and 12 may be used in the hard segment, and polyethers and/or polyesters such as polyoxyethylene, polyoxypropylene, and polybutylene glycol may be used in the soft segment. The resulting elastomer and so on. The elastomer can be roughly classified into two types: a polyether block guanamine type and a polyether ester block guanamine type. As a commercial item, UBE polyamide elastomer, UBESTA XPA (made by Ube Industries Co., Ltd.); Daiamid (made by Daicel-Evonik Co., Ltd.); PEBAX (manufactured by ARKEMA); Grilon ELX (manufactured by EMS Chemie-Japan); Novamid (manufactured by Mitsubishi Chemical Corporation); Grilux (made by Toyobo); polyether ester decylamine PA-200, PA-201, TPAE-12, TPAE-32, polyester decyl TPAE-617, TPAE-617C (manufactured by T&K TOKA) )Wait.

<<<<Polyacrylic Elastomer>>>> The polyacrylic elastomer is not particularly limited and may be appropriately selected depending on the purpose. Examples thereof include ethyl acrylate, butyl acrylate, methoxyethyl acrylate, and ethoxyethyl acrylate, which are mainly composed of acrylate, or acrylate, glycidyl methacrylate, and allyl shrinkage. Glycerol ether, etc. Further, a copolymerization of a crosslinking point monomer such as acrylonitrile or ethylene may be mentioned. Specific examples thereof include an acrylonitrile-butyl acrylate copolymer, an acrylonitrile-butyl acrylate-ethyl acrylate copolymer, an acrylonitrile-butyl acrylate-glycidyl methacrylate copolymer, and the like.

<<<<矽 ketone-based elastomer>>>> The ketone-based elastomer is not particularly limited and may be appropriately selected depending on the purpose. For example, a polydimethyl siloxane having a polyorganosiloxane as a main component, a polymethylphenyl siloxane, a polydiphenyl sulfoxide, or the like can be given. Specific examples of the commercially available product include: KE series (manufactured by Shin-Etsu Chemical Co., Ltd.); SE series, CY series, SH series (above manufactured by Toray Dow Corning Silicone) .

<<<<Other Elastomers>>>> In the present invention, a rubber-modified epoxy resin (epoxy elastomer) can be used as the elastomer. The epoxy-based elastomer can be, for example, a bisphenol F-type epoxy resin or a bisphenol A-type epoxy resin by using a two-terminal carboxylic acid-modified butadiene-acrylonitrile rubber or a terminal amine-based modified fluorenone rubber. A part or all of the epoxy groups of the salicylaldehyde type epoxy resin, the phenol novolak type epoxy resin, or the cresol novolak type epoxy resin are modified.

<<<Other polymer compound>>> In the present invention, a polymer compound (also referred to as another polymer compound) other than the above elastomer may be used as the binder. Other polymer compounds may be used alone or in combination of two or more. Specific examples of the other polymer compound include a hydrocarbon resin, a novolak resin, a phenol resin, an epoxy resin, a melamine resin, a urea resin, an unsaturated polyester resin, an alkyd resin, a polyamide resin, and a polyfluorene. Imine resin, polyamidoximine resin, polybenzimidazole resin, polybenzoxazole resin, polyvinyl chloride resin, polyvinyl acetate resin, polyacetal resin, polycarbonate resin, polyphenylene ether resin Polybutylene terephthalate resin, polyethylene terephthalate resin, polyphenylene sulfide resin, polyfluorene resin, polyether oxime resin, polyacrylate resin, polyether ether ketone resin, and the like. Among them, a hydrocarbon resin, a polyamide resin, a polycarbonate resin is preferred, and a hydrocarbon resin is more preferred. Further, in the present invention, a fluorine atom-containing binder may be used as the binder, but it is preferred that the binder containing fluorine atoms (hereinafter also referred to as a fluorine-based binder) is not substantially contained. The content of the fluorine-based binder in the total amount of the binder is, for example, preferably 0.1% by mass or less, more preferably 0.05% by mass or less, and particularly preferably not contained.

<<<<Hydrocarbon Resin>>>> In the present invention, any of them may be used as the hydrocarbon resin. The hydrocarbon resin means a resin containing substantially only carbon atoms and hydrogen atoms, and if the basic skeleton is a hydrocarbon resin, other atoms may be contained as a side chain. That is, in a hydrocarbon resin containing only carbon atoms and hydrogen atoms, such as an acrylic resin, a polyvinyl alcohol resin, a polyvinyl acetal resin, or a polyvinylpyrrolidone resin, a functional group other than a hydrocarbon group is directly bonded to The case of the main chain is also included in the hydrocarbon resin of the present invention. In this case, the content of the repeating unit in which the hydrocarbon group is directly bonded to the main chain is preferably 30 mol% or more based on all the repeating units of the resin. . Examples of the hydrocarbon resin satisfying the above conditions include a terpene resin, a terpene phenol resin, a modified terpene resin, a hydrogenated terpene resin, a hydrogenated terpene phenol resin, rosin, rosin ester, and hydrogenated rosin. Hydrogenated rosin ester, polymerized rosin, polymerized rosin ester, modified rosin, rosin modified phenol resin, alkyl phenol resin, aliphatic petroleum resin, aromatic petroleum resin, hydrogenated petroleum resin, modified petroleum resin, alicyclic petroleum resin , coumarone petroleum resin, hydrazine petroleum resin, polystyrene-polyolefin copolymer, olefin polymer (such as methyl pentene copolymer) and cyclic olefin polymer (such as norbornene copolymer, dicyclopentadiene) Copolymer, tetracyclododecene copolymer) and the like. Wherein, the hydrocarbon resin is preferably a terpene resin, a rosin, a petroleum resin, a hydrogenated rosin, a polymerized rosin, an olefin polymer or a cycloolefin polymer, more preferably a terpene resin, a rosin, an olefin polymer or a cycloolefin polymer. More preferably, it is a terpene resin, a rosin, an olefin polymer or a cycloolefin polymer, and particularly preferably a terpene resin, a rosin, a cycloolefin polymer or an olefin polymer, particularly preferably a cycloolefin polymer.

Examples of the cycloolefin polymer include a norbornene-based polymer, a monocyclic cyclic olefin polymer, a cyclic conjugated diene polymer, a vinyl alicyclic hydrocarbon polymer, and the like. Hydride, etc. Preferable examples of the cycloolefin polymer include an addition (co)polymer containing at least one repeating unit represented by the following formula (II), and further comprising a repeat represented by the formula (I) An addition (co)polymer of at least one of the units. Further, as another preferred example of the cycloolefin polymer, a ring-opening (co)polymer containing at least one cyclic repeating unit represented by the formula (III) can be mentioned.

[Chemical 3]

In the formula, m represents an integer of 0-4. R ¹ to R ⁶ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and X ¹ to X ³ and Y ¹ to Y ³ each independently represent a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, a halogen atom, and a halogen atom. a hydrocarbon group having 1 to 10 carbon atoms, -(CH ₂ )nCOOR ¹¹ , -(CH ₂ )nOCOR ¹² , -(CH ₂ )nNCO, -(CH ₂ )nNO ₂ , -(CH ₂ )nCN, -(CH ₂ nCONR ¹³ R ¹⁴ , -(CH ₂ )nNR ¹⁵ R ¹⁶ , -(CH ₂ )nOZ, -(CH ₂ )nW, or consist of X ¹ and Y ¹ , X ² and Y ² or X ³ and Y ³ (-CO) ₂ O, (-CO) ₂ NR ¹⁷ . R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ and R ¹⁷ each represent a hydrogen atom or a hydrocarbon group (preferably a hydrocarbon group having 1 to 20 carbon atoms), and Z represents a hydrocarbon group or a halogen-substituted hydrocarbon group, SiR ¹⁸ _p D _3-p (R ¹⁸ represents a hydrocarbon group having 1 to 10 carbon atoms, D represents a halogen atom and represents -OCOR ¹⁸ or -OR ¹⁸ , and p represents an integer of 0 to 3). n represents an integer of 0 to 10.

The norbornene-based polymer is disclosed in Japanese Patent Laid-Open No. Hei 10-7732, Japanese Patent Publication No. 2002-504184, No. 2004/229157 A1, and WO2004/070463A1. The norbornene-based polymer can be obtained by subjecting a norbornene-based polycyclic unsaturated compound to addition polymerization with each other. Further, if desired, the norbornene-based polycyclic unsaturated compound may be similar to ethylene, propylene, butylene, a conjugated diene such as butadiene or isoprene, such as ethylidene norbornene. The non-conjugated diene is subjected to addition polymerization. The norbornene-based polymer is sold by Mitsui Chemicals Co., Ltd. under the trade name of Apel, and has a glass transition temperature (Tg) such as APL8008T (Tg70 °C), APL6013T (Tg125 °C) or APL6015T ( Tg145 ° C) and other grades. POPs (TOP) 8007, TOPAS 5013, TOPAS 6013, TOPAS 6015 and other pellets are sold by Poly plastic. Further, Appear 3000 is sold by Ferrania.

The hydride of the norbornene-based polymer can be as disclosed in Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. As disclosed in Japanese Laid-Open Patent Publication No. 2003-1159767 or Japanese Patent Application Publication No. 2004-309979, the hydrogenation is carried out by addition polymerization or ring-opening shift polymerization of a polycyclic unsaturated compound. Manufacturing. In the formula (III), R ⁵ and R ^{6 are} preferably a hydrogen atom or a methyl group, and X ³ and Y ^{3 are} preferably a hydrogen atom, and other groups can be appropriately selected. The norbornene-based polymer is sold by JSR (share) under the trade name of Arton G or Arton F, and by Zeonor ZF14, ZF16, by ZEON, Japan. The trade names of Zeonex 250, Zeonex 280, and Zeonex 480R are commercially available and can be used.

<<<<Polyimide Resin Resin>>>> The polyimine resin can be obtained by a condensation reaction between a tetracarboxylic dianhydride and a diamine by a known method. As a known method, for example, a method in which an almost equal molar amount of tetracarboxylic dianhydride and a diamine are mixed in an organic solvent and reacted at a reaction temperature of 80 ° C to dehydrate the obtained polylysine is exemplified. closed loop. Here, the term "approximately" means that the molar amount of the tetracarboxylic dianhydride and the diamine is close to 1:1. Further, if necessary, the composition ratio of the tetracarboxylic dianhydride to the diamine may be adjusted so that the total of the tetracarboxylic dianhydride is 1.0 mol and the total of the diamine is 0.5 mol to 2.0 mol. The weight average molecular weight of the polyimine resin can be adjusted by adjusting the composition ratio of the tetracarboxylic dianhydride to the diamine within the above range.

The tetracarboxylic dianhydride is not particularly limited, and examples thereof include pyromellitic dianhydride, 3,3', 4,4'-biphenyltetracarboxylic dianhydride, and 2,2',3,3'-linked. Phenyltetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, 1,1- Bis(2,3-dicarboxyphenyl)ethane dianhydride, 1,1-bis(3,4-dicarboxyphenyl)ethane dianhydride, bis(2,3-dicarboxyphenyl)methane dianhydride , bis(3,4-dicarboxyphenyl)methane dianhydride, bis(3,4-dicarboxyphenyl)ruthenic anhydride, 3,4,9,10-decanetetracarboxylic dianhydride, double (3, 4-Dicarboxyphenyl)ether dianhydride, benzene-1,2,3,4-tetracarboxylic dianhydride, 3,4,3',4'-benzophenone tetracarboxylic dianhydride, 2,3 , 2',3'-benzophenone tetracarboxylic dianhydride, 2,3,3',4'-benzophenonetetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic acid Anhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,2,4,5-naphthalenetetracarboxylic dianhydride, 2,6 -dichloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 2,7-dichloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 2,3,6,7-tetra Chloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, phenanthrene-1,8,9,10-tetracarboxylic dianhydride, pyrazine-2,3,5,6-tetracarboxylic dianhydride, Thiophene-2,3,5,6-tetracarboxylic dianhydride, 2,3,3',4'- Phenyltetracarboxylic dianhydride, 3,4,3',4'-biphenyltetracarboxylic dianhydride, 2,3,2',3'-biphenyltetracarboxylic dianhydride, double (3, 4-Dicarboxyphenyl)dimethyl phthalane dianhydride, bis(3,4-dicarboxyphenyl)methylphenyl decane dianhydride, bis(3,4-dicarboxyphenyl)diphenyl phthalane dianhydride , 1,4-bis(3,4-dicarboxyphenyldimethyl decyl) phthalic anhydride, 1,3-bis(3,4-dicarboxyphenyl)-1,1,3,3-tetra Methyl dicyclohexane dianhydride, p-benzene bis(trimellitic anhydride), ethyltetracarboxylic dianhydride, 1,2,3,4-butane tetracarboxylic dianhydride, decalin-1, 4,5,8-tetracarboxylic dianhydride, 4,8-dimethyl-1,2,3,5,6,7-hexahydronaphthalene-1,2,5,6-tetracarboxylic dianhydride, Cyclopentane-1,2,3,4-tetracarboxylic dianhydride, pyrrolidine-2,3,4,5-tetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic acid Anhydride, double-exo (exo)-bicyclo[2,2,1]heptane-2,3-dicarboxylic anhydride, bicyclo-[2,2,2]-oct-7-ene-2,3,5, 6-tetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis[4-(3,4-dicarboxyphenyl)phenyl]propane II Anhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, 2,2-bis[4-(3,4-dicarboxyphenyl)phenyl]hexafluoropropane dianhydride, 4,4'-bis(3,4-dicarboxybenzene Diphenyl sulfide dianhydride, 1,4-bis(2-hydroxyhexafluoroisopropyl)benzene bis(trimellitic anhydride), 1,3-bis(2-hydroxyhexafluoroisopropyl)benzene Bis(trimellitic anhydride), 5-(2,5-dioxotetrahydrofuranyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic dianhydride, tetrahydrofuran-2,3,4 , 5-tetracarboxylic dianhydride, 4,4'-oxydiphthalic anhydride, 1,2-(extended ethyl) bis(trimellitic anhydride), 1,3-(trimethylene) double (p-trimellitic anhydride), 1,4-(tetramethylene) bis(trimellitic anhydride), 1,5-(pentamethylene) bis(trimellitic anhydride), 1,6-(hexa Methyl)bis(trimellitic anhydride), 1,7-(heptylene)bis(trimellitic anhydride), 1,8-(octamethylene)bis(trimellitic anhydride), 1,9 -(9-methylene)bis(trimellitic anhydride), 1,10-(decamethylene)bis(trimellitic anhydride), 1,12-(dodecyl)bis(trimellitic anhydride) , 1,16-(hexamethylene)bis(trimellitic anhydride), 1,18-(octamethylidene)bis(trimellitic anhydride), etc., which may be used alone or in combination Two or more. Preferred among these are 3,4,3',4'-benzophenonetetracarboxylic dianhydride, 2,3,2',3'-benzophenonetetracarboxylic dianhydride, 2,3, 3',4'-benzophenonetetracarboxylic dianhydride, more preferably 3,4,3',4'-benzophenonetetracarboxylic dianhydride.

The diamine is not particularly limited, and examples thereof include o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 3,3'-diaminodiphenyl ether, and 3,4'-diamino group II. Phenyl ether, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, bis(4-amino- 3,5-Dimethylphenyl)methane, bis(4-amino-3,5-diisopropylphenyl)methane, 3,3'-diaminodiphenyldifluoromethane, 3,4 '-Diaminodiphenyldifluoromethane, 4,4'-diaminodiphenyldifluoromethane, 3,3'-diaminodiphenylanthracene, 3,4'-diaminodiphenyl Base, 4,4'-diaminodiphenylanthracene, 3,3'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 4,4'-di Aminodiphenyl sulfide, 3,3'-diaminodiphenyl ketone, 3,4'-diaminodiphenyl ketone, 4,4'-diaminodiphenyl ketone, 3-( 4-aminophenyl)-1,1,3-trimethyl-5-aminoindan, 2,2-bis(3-aminophenyl)propane, 2,2'-(3,4' -diaminodiphenyl)propane, 2,2-bis(4-aminophenyl)propane, 2,2-bis(3-aminophenyl)hexafluoropropane, 2,2-(3,4 '-Diaminodiphenyl)hexafluoropropane, 2,2-bis(4-aminophenyl)hexafluoropropane, 1,3- Bis(3-aminophenoxy)benzene, 1,4-bis(3-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 3,3'-( 1,4-phenylphenylbis(1-methylethylidene))diphenylamine, 3,4'-(1,4-phenylphenylbis(1-methylethylidene))diphenylamine, 4, 4'-(1,4-phenylphenylbis(1-methylethylidene))diphenylamine, 2,2-bis(4-(3-aminophenoxy)phenyl)propane, 2,2 - bis(4-(3-aminophenoxy)phenyl)hexafluoropropane, 2,2-bis(4-(4-aminophenoxy)phenyl)hexafluoropropane, bis(4-( 3-aminophenoxy)phenyl) sulfide, bis(4-(4-aminophenoxy)phenyl) sulfide, bis(4-(3-aminophenoxy)phenyl)anthracene , bis(4-(4-aminophenoxy)phenyl)fluorene, 3,3'-dihydroxy-4,4'-diaminobiphenyl, 3,5-diaminobenzoic acid, etc. Group diamine, 1,3-bis(aminomethyl)cyclohexane, 2,2-bis(4-aminophenoxyphenyl)propane, polyoxypropylene diamine, 4,9-dioxa Decane-1,12-diamine, 4,9,14-trioxaheptadecane-1,17-diamine, 1,2-diaminoethane, 1,3-diaminopropane, 1 , 4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1 , 9-diaminodecane, 1,10-diamine Decane, 1,11-diaminoundecane, 1,12-diaminododecane, 1,2-diaminocyclohexane, 1,3-bis(3-aminopropyl)tetra Methyl dioxane and the like. Preferably, the diamines are selected from 3-(4-aminophenyl)-1,1,3-trimethyl-5-amine indane, 1,3-bis(3-aminopropyl) Tetramethyldioxane, polyoxypropylenediamine, 2,2-bis(4-aminophenoxyphenyl)propane, 4,9-dioxan-1,12-diamine, One or more of the group consisting of 1,6-diaminohexane and 4,9,14-trioxaheptadecane-1,17-diamine, more preferably 3-(4-aminobenzene) Base)-1,1,3-trimethyl-5-aminoindan.

Examples of the solvent used in the reaction of the tetracarboxylic dianhydride and the diamine include N,N-dimethylacetamide, N-methyl-2-pyrrolidone, and N,N-di. Methylformamide. In order to adjust the solubility of raw materials and the like, a nonpolar solvent (for example, toluene or xylene) may be used in combination. The reaction temperature of the tetracarboxylic dianhydride and the diamine is preferably less than 100 ° C, and more preferably less than 90 ° C. In addition, the ruthenium imidization of polylysine is carried out by heat treatment in a representative inert environment (typically a vacuum or nitrogen atmosphere). The heat treatment temperature is preferably 150 ° C or higher, and more preferably 180 ° C to 450 ° C.

The weight average molecular weight (Mw) of the polyimide resin is preferably from 10,000 to 1,000,000, more preferably from 20,000 to 100,000.

In the present invention, the polyimine resin is preferably selected from the group consisting of γ-butyrolactone, cyclopentanone, N-methylpyrrolidone, cyclohexanone, glycol ether, dimethyl hydrazine, and tetra The solubility of at least one of the methyl ureas at 25 ° C is 10 g / 100 g of the polyimine resin above Solvent. Examples of the polyamine resin having such solubility include 3,4,3',4'-benzophenonetetracarboxylic dianhydride and 3-(4-aminophenyl)-1,1,3- A polymethylenimine resin obtained by incompletely reacting a trimethyl-5-amine group. The polyimine resin is particularly excellent in heat resistance.

A commercially available product can be used as the polyimide resin. For example, Durimide (registered trademark) 200, 208A, 284 (manufactured by Fujifilm Co., Ltd.); GPT-LT (manufactured by QunRong Chemical Co., Ltd.); SOXR-S, SOXR-M, SOXR -U, SOXR-C (all manufactured by Nippon Kodoshi Industries Co., Ltd.) and the like.

<<<Polycarbonate Resin> In the present invention, the polycarbonate resin preferably has a repeating unit represented by the following formula (1).

[Chemical 4] In the formula (1), Ar ¹ and Ar ² each independently represent an aromatic group, and L represents a single bond or a divalent linking group.

Ar1 and Ar2 in the formula (1) each independently represent an aromatic group. Examples of the aromatic group include a benzene ring, a naphthalene ring, a pentylene ring, an anthracene ring, an anthracene ring, a heptene ring, a benzodioxan ring, an anthracene ring, a fused pentabenzene ring, an anthracene ring, and a phenanthrene ring. Anthracene ring, fused tetraphenyl ring, 1,2-benzophenanthrene ring, extended triphenyl ring, anthracene ring, biphenyl ring, pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyridine ring , pyrazine ring, pyrimidine ring, pyridazine ring, pyridazine ring, anthracene ring, benzofuran ring, benzothiophene ring, isobenzofuran ring, quinolizine ring, quinoline ring, pyridazine ring, naphthalene Acridine ring, quinoxaline ring, quinazoline ring, isoquinoline ring, carbazole ring, phenazin ring, acridine ring, phenanthroline ring, thioindole ring, benzopyran ring, xanthene ring, brown Oxythiophene, phenothiazine ring and phenazine ring. Among them, a benzene ring is preferred. These aromatic groups may have a substituent, and preferably have no substituent. Examples of the substituent which the aromatic group may have include a halogen atom, an alkyl group, an alkoxy group, and an aryl group. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. The alkyl group may, for example, be an alkyl group having 1 to 30 carbon atoms. The alkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms. The alkyl group may be any of a straight chain or a branched group. Further, part or all of the hydrogen atom of the alkyl group may be substituted with a halogen atom. The halogen atom may, for example, be a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, and is preferably a fluorine atom. The alkoxy group is preferably an alkoxy group having 1 to 30 carbon atoms. The alkoxy group has more preferably 1 to 20 carbon atoms, still more preferably 1 to 10 carbon atoms. The alkoxy group may be any of a straight chain, a branched chain, and a cyclic group. The aryl group is preferably an aryl group having 6 to 30 carbon atoms, more preferably an aryl group having 6 to 20 carbon atoms.

The weight average molecular weight (Mw) of the polycarbonate resin is preferably from 1,000 to 1,000,000, more preferably from 10,000 to 80,000. When it is the said range, solubility in a solvent, and heat resistance are favorable.

Examples of commercially available polycarbonate resins include PCZ-200, PCZ-300, PCZ-500, and PCZ-800 (manufactured by Mitsubishi Gas Chemical Co., Ltd.); APEC 9379 (manufactured by Bayer); Panlite) L-1225LM (made by Teijin).

The composition for false stimulator of the present invention preferably contains a binder in a proportion of from 50.00% by mass to 99.99% by mass, more preferably from 70.00% by mass to 99.99% by mass, based on the total solid content of the composition of the pseudo-substituting composition, more preferably from 70.00% by mass to 99.99% by mass. 88.00% by mass to 99.99% by mass. When the content of the binder is in the above range, the adhesion and the releasability are excellent. When an elastomer is used as the binder, it is preferred to contain the elastomer in a ratio of from 50.00% by mass to 99.99% by mass, more preferably from 70.00% by mass to 99.99% by mass, based on the total solid content of the composition. It is particularly preferably from 88.00% by mass to 99.99% by mass. When the content of the elastomer is in the above range, the adhesion and the releasability are excellent. When two or more types of elastomers are used, it is preferable to add up to the said range. Further, in the case where an elastomer is used as the binder, the content of the elastomer in the total mass of the binder is preferably 50% by mass to 100% by mass, more preferably 70% by mass to 100% by mass, and still more preferably 80% by mass. The mass % to 100% by mass, particularly preferably 90% by mass to 100% by mass. In addition, the binder may also be substantially only an elastomer. In addition, the binder is substantially only an elastomer, and it is preferable that the content of the elastomer in the total mass of the binder is 99% by mass or more, more preferably 99.9% by mass or more, and particularly preferably only an elastomer. Further, in the pseudo-composition composition of the present invention, the quality of the fluorine-containing compound and the binder is preferably fluorine-containing compound: binder = 0.001:99.999 to 10:90.00, more preferably 0.001:99.999 to 5:95.00, and further More preferably, it is 0.010:99.99 to 5:95.00. By setting the mass ratio of the fluorine-containing compound to the binder to the above range, more fluorine-containing compounds can be easily biased toward the air interface side of the pseudo-adhesion film.

<<Radical Polymerizable Compound>> The pseudo-adhesive composition of the present invention of the present invention preferably contains a radically polymerizable compound. By using a pseudo-conducting composition containing a radical polymerizable compound, it is easy to suppress flow deformation of the pseudo-adhesion film during heating. Therefore, for example, when the laminate after polishing the substrate is subjected to heat treatment or the like, flow deformation of the dummy film at the time of heating can be suppressed, and generation of warpage can be effectively suppressed. Further, since the pseudo-adhesion film having hardness can be formed, even if a pressure is locally applied when the substrate is polished, the film is less likely to be deformed, and the flatness is excellent.

In the present invention, the radically polymerizable compound is a compound having a radical polymerizable group, and a known radically polymerizable compound which can be polymerized by a radical can be used. Such a compound is widely known in the industrial field, and it can be used without particular limitation in the present invention. These may be, for example, any of a chemical form such as a monomer, a prepolymer, an oligomer or a mixture thereof and a plurality of such polymers.

In the present invention, the monomeric radical polymerizable compound (hereinafter also referred to as a polymerizable monomer) is a compound different from the polymer compound. The polymerizable monomer is typically a low molecular compound, preferably a low molecular weight compound having a molecular weight of 2,000 or less, more preferably a low molecular weight compound having a molecular weight of 1,500 or less, and still more preferably a low molecular weight compound having a molecular weight of 900 or less. Further, the molecular weight of the polymerizable monomer is usually 100 or more. Further, the oligomer-type radically polymerizable compound (hereinafter also referred to as a polymerizable oligomer) is typically a polymer having a relatively low molecular weight, preferably 10 to 100 polymerizable monomers. polymer. The molecular weight is preferably a polystyrene-equivalent weight average molecular weight obtained by a gel permeation chromatography (GPC) method of from 2,000 to 20,000, more preferably from 2,000 to 15,000, most preferably from 2,000 to 10,000.

The number of functional groups of the radically polymerizable compound in the present invention means the number of radical polymerizable groups in one molecule. The radical polymerizable group means a group which can be polymerized by the action of actinic rays, radioactivity or radicals. Examples of the radical polymerizable group include a group having an ethylenically unsaturated bond. The group having an ethylenically unsaturated bond is preferably a styryl group, a (meth)acryl fluorenyl group or a (meth)allyl group, and still more preferably a (meth) acrylonitrile group. That is, the radically polymerizable compound used in the present invention is preferably a (meth) acrylate compound, and more preferably an acrylate compound.

From the viewpoint of suppressing warpage, the radically polymerizable compound preferably contains at least one of a difunctional or higher radical polymerizable compound containing two or more radical polymerizable groups, and more preferably contains at least one trifunctional or higher functional group. A radically polymerizable compound. The upper limit of the radical polymerizable group which the radically polymerizable compound has is not particularly limited, and may be, for example, 15 or less, or may be 6 or less. In addition, the radically polymerizable compound in the present invention preferably contains at least one trifunctional or higher radical polymerizable compound in terms of a three-dimensional crosslinked structure and a heat resistance. Further, it may be a mixture of a difunctional or less radical polymerizable compound and a trifunctional or higher radical polymerizable compound.

Specific examples of the radically polymerizable compound include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, methacrylic acid, maleic acid, etc.) or esters thereof and guanamines. And such a polymer, preferably an ester of an unsaturated carboxylic acid and a polyol compound, and an amide of an unsaturated carboxylic acid and a polyamine compound, and a polymer of these. Further, an unsaturated carboxylic acid ester or a guanamine having a nucleophilic substituent such as a hydroxyl group, an amine group or a fluorenyl group, or an addition reaction product with a monofunctional or polyfunctional isocyanate or epoxy group, Or a dehydration condensation reaction with a monofunctional or polyfunctional carboxylic acid or the like. Further, an addition reaction of an unsaturated carboxylic acid ester or a guanamine having an electrophilic substituent such as an isocyanate group or an epoxy group with a monofunctional or polyfunctional alcohol, an amine or a thiol is also preferred. And a substituted carboxylic acid ester or guanamine of a destructive substituent such as a halogen group or a tosylhydrazine group, and a substituted reactant of a monofunctional or polyfunctional alcohol, an amine or a thiol. Further, as another example, a compound group in which the unsaturated carboxylic acid is substituted with a vinylbenzene derivative such as an unsaturated phosphonic acid or styrene, a vinyl ether or an allyl ether may be used.

As the specific compound, the compound described in Paragraph No. 0029 to Paragraph No. 0037 of JP-A-2014-189696 may be preferably used in the present invention.

In addition, a urethane-based addition polymerizable monomer produced by an addition reaction of an isocyanate and a hydroxyl group is also preferable, and as a specific example, for example, Japanese Patent Publication No. Sho 48-41708 The polyisocyanate compound having two or more isocyanate groups in one molecule, which is obtained by adding a hydroxyl group-containing vinyl monomer represented by the following formula (A), contains two or more in one molecule. A polymerizable vinyl vinyl urethane compound or the like. CH ₂ =C(R ⁴ )COOCH ₂ CH(R ⁵ )OH ((), wherein R ⁴ and R ⁵ represent H or CH ₃ ) Further, it is also preferably as disclosed in Japanese Patent Laid-Open No. 51-37193 Japanese Patent Publication No. 2-32293, Japanese Patent Publication No. Hei 2-16765, or Japanese Patent Publication No. Sho 58-49860, Japanese Patent Publication No. SHO-58-49860 A urethane compound having an ethylene oxide-based skeleton described in Japanese Patent Publication No. Sho 62-39417, and Japanese Patent Publication No. Sho 62-39417.

Further, as the radically polymerizable compound, the compound described in Paragraph No. 0095 to Paragraph No. 0108 of JP-A-2009-288705 can also be preferably used in the present invention.

Further, as the radical polymerizable compound, a compound having at least one addition-polymerizable ethylenically unsaturated group having a boiling point of 100 ° C or higher at normal pressure is also preferable. As an example of the compound, the compound described in Paragraph No. 0040 of JP-A-2014-189696 may be preferably used in the present invention.

Further, as a compound having a boiling point of 100 ° C or higher and having at least one addition-polymerizable ethylenically unsaturated group under normal pressure, paragraph number 0254 to paragraph number of JP-A-2008-292970 is also preferable. The compound described in 0257.

In addition to the above, a radical polymerizable compound represented by the following formula (MO-1) to formula (MO-5) can be preferably used. Further, in the formula, in the case where T is an oxygen-extended alkyl group, the terminal on the carbon atom side is bonded to R.

[Chemical 5]

[Chemical 6]

In the formula, n is an integer of 0 to 14, and m is an integer of 1 to 8. R and T, which are present in a single molecule, may be the same or different. In each of the radical polymerizable compounds represented by the above formula (MO-1) to formula (MO-5), at least one of the plurality of R represents -OC(=O)CH=CH ₂ or -OC (=O) C(CH ₃ )=the group represented by CH ₂ . Specific examples of the radically polymerizable compound represented by the above formula (MO-1) to (MO-5) are also preferably used in the present invention, which is also disclosed in JP-A-2007-269779. The compound described in Paragraph No. 0248 to Paragraph No. 0251.

In the Japanese Patent Publication No. Hei 10-62986, the following compounds described in the general formula (1) and the general formula (2) and the specific examples thereof can also be used as a radical polymerizable compound, and the compound is The addition of ethylene oxide or propylene oxide to a polyfunctional alcohol is carried out by (meth)acrylation.

As the radically polymerizable compound, dipentaerythritol triacrylate (available as KAYARAD D-330, manufactured by Nippon Kayaku Co., Ltd.) and dipentaerythritol tetraacrylate (commercially available) are preferred. KAYARAD D-320; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol penta (meth) acrylate (KAYARAD D-310 as a commercial product; Nippon Kasei Pharmaceutical Co., Ltd.), dipentaerythritol hexa(meth) acrylate (KAYARAD DPHA as a commercial product; manufactured by Nippon Kayaku Co., Ltd.) and the (meth) acrylonitrile group A structure between ethylene glycol and propylene glycol residues. These oligomer types can also be used.

The radically polymerizable compound may be a polyfunctional monomer having an acid group such as a carboxyl group, a sulfonic acid group or a phosphoric acid group. Examples of the polyfunctional monomer having an acid group include an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and it is preferred to react an unreacted hydroxyl group of the aliphatic polyhydroxy compound with a non-aromatic carboxylic anhydride to have an acid. The polyfunctional monomer is particularly preferred in the ester, and the aliphatic polyhydroxy compound is pentaerythritol and/or dipentaerythritol. As a commercial item, M-510, M-520, etc. which are polyacid-acid-modified acrylic oligomer manufactured by the East Asia Synthetic Co., Ltd. are mentioned, for example.

The polyfunctional monomer having an acid group may be used singly or in combination of two or more. The preferred acid value of the polyfunctional monomer having an acid group is from 0.1 mgKOH/g to 40 mgKOH/g, particularly preferably from 5 mgKOH/g to 30 mgKOH/g. When the acid value of the polyfunctional monomer is in the above range, the production and handling properties are excellent.

Further, a polyfunctional monomer having a caprolactone structure can also be used as the radical polymerizable compound. The polyfunctional monomer having a caprolactone structure is not particularly limited as long as it has a caprolactone structure in its molecule, and examples thereof include trimethylolethane and di-trimethylolethane. Polyols such as trimethylolpropane, di-trimethylolpropane, pentaerythritol, dipentaerythritol, tripentaerythritol, glycerin, diglycerol, trimethylol melamine and (meth)acrylic acid and ε The ε-caprolactone modified by caprolactone is modified with a polyfunctional (meth) acrylate. Among them, a polyfunctional monomer having a caprolactone structure represented by the following formula (B) is preferred.

General formula (B) [Chemical 7]

(In the formula, all of the six R groups are represented by the following formula (C), or one to five of the six R groups are groups represented by the following formula (C), and the remainder are lower The base represented by the general formula (D)

General formula (C) [Chemical 8]

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

General formula (D) [Chemical 9]

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

Such a polyfunctional monomer having a caprolactone structure is commercially available, for example, as a KAYARAD DPCA series from Nippon Kayaku Co., Ltd., and may be exemplified by DPCA-20 (in the above formula (B) - In the formula (D), m = 1, the number of groups represented by the formula (C) = 2, a compound in which R ¹ is a hydrogen atom), DPCA-30 (in the formula (B) to the formula In (D), m = 1, a compound represented by the formula (C) = 3, a compound in which R ¹ is a hydrogen atom), and DPCA-60 (in the formula (B) to the formula (D) In the formula (B) to the formula (D), m = 1, a compound represented by the formula (C) = 6 and a compound in which R ¹ is a hydrogen atom), DPCA-120 (in the formula (B) to (D) , m = 2, the number of groups of formula (C) represented by = 6, R ¹ compound are hydrogen atoms) and the like. In the present invention, the polyfunctional monomer having a caprolactone structure may be used singly or in combination of two or more.

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

[化10]

In the general formula (i) and the general formula (ii), E independently represents -((CH ₂ ) _y CH ₂ O)- or -((CH ₂ ) _y CH(CH ₃ )O)-, y are each independently The ground represents an integer of 0 to 10, and X each independently represents a (meth)acrylylene group, a hydrogen atom or a carboxyl group. In the general formula (i), the total of (meth)acrylonyl groups is three or four, and m is independently an integer of from 0 to 10, and the total of each m is an integer of from 0 to 40. In the general formula (ii), the total of (meth)acrylonyl groups is 5 or 6, and n is independently an integer of 0 to 10, and the total of n is an integer of 0 to 60.

In the formula (i), m is preferably an integer of 0 to 6, more preferably an integer of 0 to 4. Further, the total of each m is preferably an integer of 2 to 40, more preferably an integer of 2 to 16, and particularly preferably an integer of 4 to 8. In the formula (ii), n is preferably an integer of 0 to 6, more preferably an integer of 0 to 4. Further, the total of each n is preferably an integer of from 3 to 60, more preferably an integer of from 3 to 24, and particularly preferably an integer of from 6 to 12.

Further, -((CH ₂ ) _y CH ₂ O)- or -((CH ₂ ) _y CH(CH ₃ )O)- in the formula (i) or the formula (ii) is preferably on the oxygen atom side The end is bonded to the form of X.

Particularly preferred is a form in which all six of X in the formula (ii) are an acrylonitrile group.

The compound represented by the formula (i) or the formula (ii) can be synthesized by the following steps as a previously known step by subjecting pentaerythritol or dipentaerythritol to ring-opening addition reaction with ethylene oxide or propylene oxide. The step of bonding the ring-opening skeleton and the step of introducing a (meth)acryl fluorenyl group by reacting a terminal hydroxyl group of the ring-opening skeleton with, for example, (meth)acryloyl chloride. Each step is a well-known step, and a person represented by the formula (i) or the formula (ii) can be easily synthesized by a person skilled in the art.

Among the compounds represented by the formula (i) and the formula (ii), a pentaerythritol derivative and/or a dipentaerythritol derivative are more preferable. Specifically, the compounds represented by the following formulas (a) to (f) (hereinafter also referred to as "exemplary compounds (a) to exemplified compounds (f)")) are preferred, and among them, preferred compounds (a) ), exemplified compound (b), exemplified compound (e), and exemplified compound (f).

[11]

[化12]

The commercially available product of the radical polymerizable compound represented by the formula (i) or the formula (ii) is, for example, a tetrafunctional compound having four ethylene ethoxylate chains manufactured by Sartomer Co., Ltd. Acrylate SR-494, DPCA-60 manufactured by Nippon Kayaku Co., Ltd. as a hexafunctional acrylate having 6 pentyloxy chains, as a trifunctional acrylate having 3 isomerized butoxy chains TPA-330 and so on.

In addition, as a radically polymerizable compound, it is also preferable to use Japanese Patent Publication No. Sho 48-41708, Japanese Patent Laid-Open No. Sho 51-37193, Japanese Patent Laid-Open No. 2-32293, and Japanese Patent Special Fair 2 Japanese Patent Publication No. Sho-58-49860, Japanese Patent Publication No. SHO-58-17654, Japanese Patent Publication No. Sho 62-39417, and Japanese Patent Publication No. Sho 62-62 A urethane compound having an ethylene oxide skeleton as described in JP-A-39418. Further, an amino group structure or a thioether structure in the molecule described in Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. The addition polymerizable monomer is a radical polymerizable compound. The commercially available product of the radically polymerizable compound may, for example, be a urethane oligomer UAS-10 or UAB-140 (manufactured by Sanyo Kokusaku Pulp Co., Ltd.); NK ester M-40G, NK ester. M-4G, NK ester A-9300, NK ester M-9300, NK ester A-TMMT, NK ester A-DPH, NK ester A-BPE-4, UA-7200 (manufactured by Shin-Nakamura Chemical Co., Ltd.); DPHA-40H (Manufactured by Nippon Kayaku Co., Ltd.); UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoeisha); Blemmer PME400 (Japan Oil Co., Ltd.) )))).

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

[Chemistry 13]

Specific examples of the radically polymerizable compound having the partial structure include trimethylolpropane tri(meth)acrylate and isocyanuric acid ethylene oxide modified di(meth)acrylate. Isocyanuric acid ethylene oxide modified tris(meth)acrylate, triallyl isocyanurate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dimethylolpropane Tetrakis (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tetramethylol methane tetra (meth) acrylate, etc., in the present invention, particularly excellent These radically polymerizable compounds are used.

In the composition for a false singular composition of the present invention, when a radical polymerizable compound is added to the total solid content of the composition for the subsequent use, from the viewpoint of good adhesion, flatness, peelability, and warpage The content is preferably from 1% by mass to 50% by mass, more preferably from 1% by mass to 30% by mass, even more preferably from 5% by mass to 30% by mass. The radically polymerizable compound may be used alone or in combination of two or more. Further, in the case of a binder and a radical polymerizable compound, the mass ratio of the two is preferably a binder: a radical polymerizable compound = 99.5: 0.5 to 90: 10, more preferably 99: 1 to 90. :10, the best is 98:2 ~ 92:8. When the mass ratio of the binder and the radically polymerizable compound is in the above range, a pseudo-adhesion film excellent in adhesion, flatness, peeling property, and warpage suppression can be formed.

<<<Antioxidant>>> The composition for pseudo-adhesive of the present invention may contain an antioxidant. As the antioxidant, a phenol-based antioxidant, a sulfur-based antioxidant, a phosphorus-based antioxidant, a lanthanoid antioxidant, an amine-based antioxidant, or the like can be used. Examples of the phenolic antioxidant include "p-methoxyphenol", 2,6-di-tert-butyl-4-methylphenol, and "BARN" (Irganox). "1010", "Irganox 1330", "Irganox 3114", "Irganox 1035", Sumitomo Chemical (Sumilizer) ) MDP-S", "Sumilizer GA-80", etc. Examples of the sulfur-based antioxidant include 3,3'-dithiolactyl thiodipropionate, "Sumilizer TPM" manufactured by Sumitomo Chemical Co., Ltd., and "Sumi Laize ( Sumilizer) TPS", "Sumilizer TP-D", etc. Examples of the phosphorus-based antioxidant include tris(2,4-di-t-butylphenyl)phosphite, bis(2,4-di-t-butylphenyl)pentaerythritol diphosphite, Poly(dipropylene glycol) phenyl phosphite, diphenyl isodecyl phosphite, 2-ethylhexyl diphenyl phosphite, triphenyl phosphite, BASF (BASF) Irgafos 168, Irgafos 38, etc. Examples of the lanthanoid antioxidant include p-benzoquinone and 2-tert-butyl-1,4-benzoquinone. Examples of the amine-based antioxidant include dimethylaniline or phenothiazine. The antioxidant is preferably Irganox 1010, Irganox 1330, 3,3'-dithiolactyl thiodipropionate, Sumilizer TP-D, More preferably, it is Irganox 1010, Irganox 1330, and especially Irganox 1010. Further, among the antioxidants, a phenolic antioxidant, a sulfur-based antioxidant or a phosphorus-based antioxidant is preferred, and a phenolic antioxidant and a sulfur-based antioxidant are preferred. In particular, when a polystyrene elastomer is used as the elastomer, a phenolic antioxidant and a sulfur-based antioxidant are preferably used. By such a combination, it is expected that the deterioration of the binder due to the oxidation reaction can be efficiently suppressed. In the case of phenolic antioxidants and sulfur-based antioxidants, the quality of phenolic antioxidants and sulfur-based antioxidants is preferably phenolic antioxidants: sulfur-based antioxidants = 95:5 to 5:95, more preferably It is 25:75 to 75:25. As a combination of antioxidants, Irganox 1010 and Sumilizer TP-D, Irganox 1330 and Sumilizer TP-D and Sue are preferred. Sumilizer GA-80 and Sumilizer TP-D, more preferably Irganox 1010 and Sumilizer TP-D, Irganox 1330 and Sumilizer TP-D, especially good for Irganox 1010 and Sumilizer TP-D.

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

In the case where the composition has an antioxidant, the content of the antioxidant is preferably 0.001% by mass to 20.0% by mass, and more preferably 0.005% by mass to 10.0% by mass based on the total solid content of the composition. . The antioxidant may be used alone or in combination of two or more. When the amount of the antioxidant is two or more, it is preferred that the total is in the above range.

<<Solvent>> The composition for pseudo-adhesive of the present invention preferably contains a solvent. The solvent can be used without any limitation, and is preferably an organic solvent. The organic solvent may preferably be exemplified by ethyl acetate, n-butyl acetate, isobutyl acetate, amyl acetate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, Ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, alkyl oxyacetate (eg methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate (eg methoxyacetic acid) Methyl ester, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.), alkyl 3-oxopropionate (for example: 3-oxygen) Methyl propyl propionate, ethyl 3-oxypropionate, etc. (eg methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-B Ethyl oxypropionate, etc.), alkyl 2-oxopropionate (for example: methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, etc.) (eg methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, 2-ethyl 2-ethoxypropionate Ester)), methyl 2-oxy-2-methylpropanoate and ethyl 2-oxy-2-methylpropionate (eg 2- Methyl oxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetate, Ethyl acetate, 2-oxobutyric acid methyl ester, 2-oxobutyric acid ethyl ester, 1-methoxy-2-propyl acetate, etc.; diethylene glycol dimethyl ether, tetrahydrofuran , ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene Ethers such as alcohol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate; methyl ethyl ketone, cyclohexanone, 2-heptanone , 3-heptanone, N-methyl-2-pyrrolidone, γ-butyrolactone and other ketones; toluene, xylene, anisole, mesitylene, ethylbenzene, propylbenzene, cumene, N-butylbenzene, t-butylbenzene, isobutylbenzene, tert-butylbenzene, pentylbenzene, isopentylbenzene, (2,2-dimethylpropyl)benzene, 1-phenylhexane , 1-phenylheptane, 1-phenyloctane, 1-phenyldecane, 1-phenyldecane, cyclopropylbenzene, cyclohexyl , 2-ethyltoluene, 1,2-diethylbenzene, o-isopropyltoluene, indane, 1,2,3,4-tetrahydronaphthalene, 3-ethyltoluene, m-isopropyltoluene , 1,3-diisopropylbenzene, 4-ethyltoluene, 1,4-diethylbenzene, p-isopropyltoluene, 1,4-diisopropylbenzene, 4-tert-butyltoluene , 1,4-di-t-butylbenzene, 1,3-diethylbenzene, 1,2,3-trimethylbenzene, 1,2,4-trimethylbenzene, 4-tert-butyl - o-xylene, 1,2,4-triethylbenzene, 1,3,5-triethylbenzene, 1,3,5-triisopropylbenzene, 5-tert-butyl-m-xylene, Aromatic hydrocarbons such as 3,5-di-t-butyltoluene, 1,2,3,5-tetramethylbenzene, 1,2,4,5-tetramethylbenzene, pentamethylbenzene; Hydrocarbons such as menthane, decane, decane, dodecane, and decahydronaphthalene.

From the viewpoint of improving the coating surface, etc., it is preferable that these solvents are mixed in two or more forms. In this case, a mixed solution selected from the group consisting of mesitylene, tert-butylbenzene, 1,2,4-trimethylbenzene, p-menthane, γ-butyrolactone, and benzoic acid is particularly preferred. Ether, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, 3-methyl Two or more kinds of methyl oxypropionate, 2-heptanone, cyclohexanone, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether, and propylene glycol methyl ether acetate.

In the case where the composition has a solvent, the content of the solvent of the composition is preferably false, and the total solid content of the composition is 5% by mass to 80%. The amount of % is more preferably 5% by mass to 70% by mass, particularly preferably 10% by mass to 60% by mass. The solvent may be used alone or in combination of two or more. When the solvent is two or more, it is preferred that the total is in the above range.

<<Interfacial Active Agent>> The pseudo-adhesive composition used in the present invention preferably contains a surfactant. As the surfactant, any of anionic, cationic, nonionic or amphoteric may be used, and a preferred surfactant is a nonionic surfactant. Preferable examples of the nonionic surfactant include polyoxyethylene higher alkyl ethers, polyoxyethylene higher alkylphenyl ethers, higher fatty acid diesters of polyoxyethylene glycol, and anthrones. Surfactant.

From the viewpoint of coatability, it is preferred that the composition contains an anthrone-based surfactant as a surfactant. In general, when a composition having a high viscosity is used, it is difficult to apply it to a uniform thickness. However, since it is easily coated to a uniform thickness by containing an anthrone-based surfactant, it can be more preferably used. Examples of the anthrone-based surfactants include, for example, JP-A-62-36663, JP-A-61-226746, JP-A-61-226745, and JP-A-62-170950. Japanese Patent Laid-Open No. Sho 63-34540, Japanese Patent Laid-Open No. Hei 7-230165, Japanese Patent Laid-Open No. Hei 8-62834, Japanese Patent Laid-Open No. Hei 9-54432, Japanese Patent Laid-Open No. Hei 9-5988, Japanese Patent A commercially available surfactant can also be used as the surfactant described in each of the publications of JP-A-2001-330953. As a commercially available anthrone-based surfactant, for example, KP-301, KP-306, KP-109, KP-310, KP-310B, KP-323, KP-326, KP-341, KP-104, KP-110, KP-112, KP-360A, KP-361, KP-354, KP-355, KP-356, KP-357, KP-358, KP-359, KP-362, KP-365, KP- 366, KP-368, KP-369, KP-330, KP-650, KP-651, KP-390, KP-391, KP-392 (manufactured by Shin-Etsu Chemical Co., Ltd.).

In the case where the composition contains a surfactant, the content of the surfactant in the composition of the composition is preferably 0.001 with respect to the total solid content of the composition. The mass% to 5% by mass, more preferably 0.005% by mass to 1% by mass, particularly preferably 0.01% by mass to 0.5% by mass. The surfactant may be used alone or in combination of two or more. When the amount of the surfactant is two or more, it is preferable that the total amount is in the above range.

<<Other Additives>> In the range which does not impair the effect of the present invention, the composition of the pseudo-adhesive composition of the present invention may be optionally formulated with various additives such as a hardener, a hardening catalyst, a decane coupling agent, a filler, and an adhesive. Promoter, ultraviolet absorber, anti-agglomerating agent, and the like. In the case of disposing these additives, it is preferred that the total amount of the additives is 3% by mass or less based on the total solid content of the composition.

The composition for sham of the present invention preferably contains no impurities such as a metal. The content of the impurities contained in the materials is preferably 1 ppm or less, more preferably 100 ppt or less, still more preferably 10 ppt or less, and particularly preferably substantially no (below the detection limit of the measuring device). As a method of removing impurities such as metal from the dummy and then removing the composition, for example, filtration using a filter is mentioned. The filter pore diameter is preferably a pore diameter of 10 nm or less, more preferably 5 nm or less, and still more preferably 3 nm or less. The material of the filter is preferably a filter made of polytetrafluoroethylene, polyethylene or nylon. The filter can be cleaned beforehand using an organic solvent. In the filter filtration step, a plurality of filters can be used in series or in parallel. In the case of using a variety of filters, filters with different apertures and/or materials can be used in combination. In addition, various materials may be filtered multiple times, and the step of multiple filtration may also be a cyclic filtration step. In addition, as a method of reducing impurities such as a metal contained in the composition, the raw material having a small metal content is selected as a raw material constituting the composition for pseudo-adhesion, and the raw material constituting the pseudo-construction composition is used. Filter filtration is carried out; distillation is carried out under conditions in which polytetrafluoroethylene is equal to the inner liner formed in the apparatus to inhibit contamination as much as possible. The preferred conditions for filter filtration of the raw materials constituting the pseudo-constituent composition are the same as those described above. In addition to filter filtration, the adsorbent material may be used for impurity removal, and a filter may be used in combination to filter and adsorb the material. As the adsorbent, a known adsorbent can be used. For example, an inorganic adsorbent such as tannin or zeolite, or an organic adsorbent such as activated carbon can be used.

<Preparation of Substituted Composition> The pseudo-construction composition of the present invention can be prepared by mixing the above components. The mixing of the components is usually carried out in the range of 0 °C to 100 °C. Moreover, after mixing each component, it is preferable to filter by a filter, for example. Filtration can be carried out in multiple stages, or it can be repeated multiple times. Alternatively, the filtered liquid can be refiltered. The filter is not particularly limited as long as it is a filter used for filtration applications or the like. For example, a fluororesin such as polytetrafluoroethylene (PTFE), a polyamide resin such as nylon-6 or nylon-6, 6 or a polyolefin resin such as polyethylene or polypropylene (polypropylene) may be used. Filters such as density, ultra high molecular weight). Among these raw materials, polypropylene (containing high density polypropylene) and nylon are preferred. The pore diameter of the filter is, for example, suitably from about 0.003 μm to about 5.0 μm. By setting it as this range, it is possible to suppress the clogging of the filter, and it is possible to surely remove fine foreign matter such as impurities or aggregates contained in the composition. When using a filter, different filters can be combined. At this time, the filtration by the first filter may be performed only once, or may be performed twice or more. In the case where two or more filtrations are performed by combining different filters, it is preferred that the pore diameter after the second time is the same as the pore diameter of the first filtration or smaller than the pore diameter of the first filtration. Further, the first filter of different pore diameters may be combined within the above range. The aperture here can be referred to the nominal value of the filter manufacturer. As a commercially available filter, for example, from PALL Co., Ltd., Advantec Toyo Co., Ltd., and Japan's Entegris Co., Ltd. (formerly Japan's Miikeri ( Choose from various filters offered by Mykrolis) or Kitz Microfilter Co., Ltd.

<Method for Producing False Adhesive Film> Next, a method for producing the pseudo-adhesive film of the present invention will be described. In the method for producing a pseudo-adhesive film of the present invention, the pseudo-adhesive composition is applied in a layer form on a support and dried to produce the following pseudo-adhesive film of <1>. Preferably, the following <2> pseudo-adhesive film is produced. <1> A pseudo-attachment film in which the ratio of the existence of fluorine atoms obtained by X-ray photoelectron spectroscopy on the surface of the film, that is, the ratio of the fluorine atoms in the surface of the pseudo-adhesive film opposite to the support, is present A. The ratio B of the fluorine atoms in the surface on the support side of the dummy film satisfies the relationship of the following formula (1), and the existence ratio A of the fluorine atoms is 10% to 40%. A/B≧1.3 (1) A is the existence ratio A of the fluorine atoms in the surface of the film opposite to the support on the side of the film, and B is the existence of fluorine atoms in the surface of the support side of the dummy film. Ratio B. <2> A pseudo-attachment film in which the ratio B of the existence ratio of the fluorine atom to the fluorine atom satisfies the relationship of the following formula (2), and the existence ratio A of the fluorine atom is 18% to 40%. A/B≧1.5 (Formula (2) A is the ratio A of the fluorine atoms in the surface of the pseudo-adhesive film opposite to the support, and B is the existence of fluorine atoms in the surface of the support side of the pseudo-attachment film. Ratio B.

Examples of the coating method for the pseudo-concomitant composition include a spin coating method, a spray method, a roll coating method, a flow coating method, a knife coating method, a screen printing method, and a dip coating method. Further, a method in which a composition is applied from a slit-like opening by a pressure and a composition is applied to a support by a dummy may be used.

The coating amount of the composition is different depending on the application. For example, it is preferred that the average thickness of the pseudo-adhesive film after drying is 0.1 μm to 500 μm. The lower limit is preferably 1 μm or more. The upper limit is preferably 200 μm or less, more preferably 100 μm or less. Furthermore, in the present invention, the average film thickness of the film is defined as an average value of a value which is measured by a thickness gauge in a section along the direction of the dummy film, from one end thereof to the other The film thickness in five points at equal intervals on one end surface was measured. Further, in the present invention, the "cross section of the pseudo-adhesive film in one direction" means a cross section orthogonal to the longitudinal direction when the dummy film is polygonal. Further, in the case where the dummy film has a square shape, it means a cross section orthogonal to the side of either one. Further, in the case where the film is circular or elliptical, it means a cross section passing through the center of gravity.

Examples of the support include a drum, a belt, and the like. Further, a substrate such as a release film, a component wafer, or a carrier substrate may be used as the support.

The carrier substrate is not particularly limited, and examples thereof include a ruthenium substrate, a glass substrate, a metal substrate, and a compound semiconductor substrate. In particular, the ruthenium substrate is preferably used in view of the fact that the ruthenium substrate which is used as a substrate of the semiconductor device is not easily contaminated, or the electrostatic chuck which can be widely used in the manufacturing process of the semiconductor device. The thickness of the carrier substrate is not particularly limited, and is, for example, preferably 300 μm to 100 mm, more preferably 300 μm to 10 mm. The surface of the carrier substrate can have a release layer. The mold release layer is preferably a low surface energy layer containing a fluorine atom and/or a ruthenium atom, and preferably contains a material having a fluorine atom and/or a ruthenium atom. The fluorine content of the release layer is preferably from 30% by mass to 80% by mass, more preferably from 40% by mass to 76% by mass, even more preferably from 60% by mass to 75% by mass.

As the element wafer, a known one can be used without limitation, and examples thereof include a tantalum substrate, a compound semiconductor substrate, and the like. Specific examples of the compound semiconductor substrate include a SiC substrate, a SiGe substrate, a ZnS substrate, a ZnSe substrate, a GaAs substrate, an InP substrate, and a GaN substrate. A mechanical structure or circuit may be formed in the surface of the component wafer. Examples of the component wafer in which the mechanical structure or the circuit is formed include, for example, a micro electro mechanical system (MEMS), a power element, an image sensor, a micro sensor, and a light emitting diode (Light Emitting Diode). LED), optical components, interposers, embedded components, micro-components, and the like. The component wafer preferably has a structure such as a metal bank. According to the present invention, even in the case of an element wafer having a structure on the surface, the dummy wafer can be stably performed, and the dummy wafer with the element wafer can be easily released. The height of the structure is not particularly limited, and is, for example, preferably 1 μm to 150 μm, and more preferably 5 μm to 100 μm.

After the dummy composition is applied as a layer on the support, it is dried and solidified, and the obtained pseudo-adhesive film is mechanically peeled off from the support, whereby a single pseudo-adhesive film (film) can be obtained. ). The drying conditions are different depending on the type of the composition or the film thickness of the dummy film. For example, it is preferably 60 ° C to 180 ° C for 10 seconds to 600 seconds. The drying temperature is more preferably from 80 ° C to 150 ° C, and still more preferably from 100 ° C to 120 ° C. The drying time is more preferably from 30 seconds to 300 seconds, and still more preferably from 40 seconds to 180 seconds. Drying can be carried out in two stages and the temperature is increased stepwise. Further, when a release film is used as the support, the pseudo-adhesive film may be directly left without being peeled off from the support to form a pseudo-adhesive film (laminate) having a release film. By continuing these processes, a roll of long film can be obtained. The length of the long film is not particularly limited, and the lower limit is, for example, preferably 5,000 mm or more, and more preferably 1000 mm or more. The upper limit is, for example, preferably 500,000 mm or less, more preferably 200,000 mm or less. Further, a release film (substrate) may be bonded to both surfaces of the dummy film to form a pseudo-adhesive film (layered body) having a release film on both sides. By attaching the release film to one side or both surfaces of the dummy film, it is possible to prevent the occurrence of scratches on the surface of the dummy film and adhesion during storage. The release film can be peeled off and removed at the time of use. Further, when the element wafer or the carrier substrate is used as the support, the dummy film may be directly left without being peeled off from the support.

In the present invention, the ratio A of the fluorine atom of the film is preferably from 5.0% to 35%, more preferably from 10% to 30%. According to this aspect, a pseudo-adhesion film excellent in peelability can be obtained. In the present invention, the ratio B of the fluorine atom of the film is preferably from 1% to 20%, more preferably from 1% to 15%. According to this aspect, the peeling interface can be easily controlled to the surface of the film which is opposite to the support.

<Fake film> Next, the dummy film of the present invention will be described with reference to Fig. 1 . As shown in FIG. 1, the pseudo-adhesive film of the present invention is a pseudo-adhesion film containing a compound having a fluorine atom, and the film 11 is a single-layer film, and an irradiation area of 1400 μm ́700 μm on the surface of the pseudo-adhesive film is irradiated. The ratio of the presence of fluorine atoms obtained by X-ray photoelectron spectroscopy on the surface of the pseudo-adhesive film measured by the monochromatic AlKα ray at an emission angle of 45°, is presumably in one of the surfaces a of the film 11. The ratio A1 of the existence of the fluorine atom and the existence ratio B1 of the fluorine atom in the surface b on the side opposite to the surface a of the pseudo-adhesion film satisfy the relationship of the following formula (11), and the existence ratio A1 of the fluorine atom is 5 %~40%. A1/B1≧1.3 (11) A1 is a ratio A1 in which the fluorine atoms in the surface a of the film are abbreviated, and B1 is a ratio B1 of the fluorine atoms in the surface b of the pseudo-attachment film. In the pseudo-adhesion film of the present invention, the ratio A1 of the fluorine atom existence ratio to the fluorine atom B1 satisfies the relationship of the above formula (11), so that the carrier substrate and the element wafer can be peeled off on the surface a side of the dummy film. Further, since the ratio A1 of the fluorine atoms in the surface a is 5% to 40%, the carrier substrate can be peeled off from the element wafer by a smaller peeling force.

In the pseudo-adhesive film of the present invention, it is preferable that the ratio B1 of the existence ratio of the fluorine atom to the fluorine atom B1 satisfies the relationship of the following formula (12), and the ratio A1 of the fluorine atom is from 10% to 30%. A1/B1≧1.5 Formula (12) A1 is a ratio A1 of the existence of fluorine atoms in the surface a of the pseudo-attachment film, and B1 is a ratio B1 of the existence of fluorine atoms in the surface b of the pseudo-attachment film.

In the present invention, the ratio A of the fluorine atom of the film is preferably from 5% to 35%, more preferably from 10% to 30%. According to this aspect, a pseudo-adhesion film excellent in peelability can be obtained. In the present invention, the ratio B of the fluorine atom of the film is preferably from 1% to 20%, more preferably from 1% to 15%. According to this aspect, the peeling interface can be easily controlled to the surface of the film which is opposite to the support. The pseudo adhesive film of the present invention can be produced by the method for producing a pseudo adhesive film of the present invention.

The pseudo-adhesive film of the present invention preferably has an average film thickness of from 0.1 μm to 500 μm. The lower limit is preferably 1 μm or more. The upper limit is preferably 200 μm or less, more preferably 100 μm or less.

In the pseudo-attachment film of the present invention, the compound having a fluorine atom is preferably a compound having an oleophilic group and a fluorine atom. The details of the compound having a fluorine atom are exemplified in the composition for the subsequent use of the composition, and the preferred range is also the same. The pseudo-adhesive film of the present invention preferably contains a compound having a fluorine atom in a proportion of 0.03 mass% or more and less than 0.5 mass% in the total solid content of the pseudo-adhesive film, more preferably 0.04% by mass to 0.4% by mass, and furthermore It is preferably 0.05% by mass to 0.2% by mass.

In the dummy film of the present invention, the dummy film preferably contains at least one selected from the group consisting of a binder and a radical polymerizable compound. More preferably, the binder contains an elastomer. The details of the binder can be exemplified in the composition of the pseudo-construction composition, and the preferred range is also the same. In the case where the pseudo-adhesive film of the present invention contains a binder, it is preferable to contain a binder in a ratio of 50.00% by mass to 99.99% by mass, more preferably 70.00% by mass to 99.99% by mass, based on the total solid content of the pseudo-adhesive film. It is particularly preferably from 88.00% by mass to 99.99% by mass. Further, when an elastomer is used as the binder, the elastomer is preferably contained in an amount of from 50.00% by mass to 99.99% by mass, more preferably from 70.00% by mass to 99.99% by mass, based on the total solid content of the pseudo-adhesive film. It is particularly preferably from 88.00% by mass to 99.99% by mass. In the case where the pseudo-adhesive film of the present invention contains a radical polymerizable compound, it is preferred to contain a radical polymerizable compound in a ratio of from 1% by mass to 50% by mass based on the total solid content of the pseudo-adhesive film. It is preferably 1% by mass to 30% by mass, particularly preferably 5% by mass to 30% by mass. The pseudo-adhesive film of the present invention may further contain other additives such as an antioxidant. The details of these may be exemplified in the composition of the pseudo-construction composition, and the preferred ranges are also the same.

<Laminated body> Next, the laminated body of the present invention will be described. The laminate of the present invention has a pseudo-adhesive film or the pseudo-adhesive film obtained by the above-described production method of the present invention, and a substrate provided on one or both sides of the pseudo-adhesive film. Examples of the substrate include a release film, a component wafer, and a carrier substrate.

For example, a pseudo-adhesive film with a release film can be produced by using a release film as a substrate. A pseudo-adhesive film with a release film can be produced using the manufacturing method of the pseudo-adhesion film of the present invention. Further, a release film can be produced by attaching it to one side or both sides of the pseudo-adhesive film of the present invention.

Further, an adhesive substrate can be produced by using a carrier substrate or a component wafer as a substrate. The subsequent substrate can be produced by using the method for producing a pseudo-adhesive film of the present invention. Further, the pseudo-adhesive film of the present invention may be formed by laminating it on a substrate. For example, a method in which a dummy film is placed in a vacuum laminator, a dummy film is placed on a substrate by the apparatus, and a dummy film is brought into contact with the substrate under vacuum, and the film is pressed by a roller or the like to be false. The film is then fixed (laminated) to the substrate. Further, the dummy film to be fixed to the substrate may be cut into a desired shape such as a circular shape.

<Laminated body with element wafer> Next, a laminated body of the element-equipped wafer of the present invention will be described. The laminated body with a component wafer of the present invention has the dummy film of the present invention between the carrier substrate and the component wafer, and the one side of the film is in surface contact with the component surface of the component wafer, and the other surface and the carrier The surface of the substrate is in contact. It is assumed that the film is a single layer film as described, and does not have a release layer or the like. Thereby, the amount of processing for forming the laminated body can be increased.

The carrier substrate and the element wafer can be exemplified. The film thickness of the element wafer before the mechanical or chemical treatment is preferably 500 μm or more, more preferably 600 μm or more, and still more preferably 700 μm or more. The upper limit is, for example, preferably 2000 μm or less, more preferably 1500 μm or less. The film thickness of the element wafer which has been subjected to mechanical or chemical treatment and is thinned is, for example, preferably less than 500 μm, more preferably 400 μm or less, still more preferably 300 μm or less. The lower limit is, for example, preferably 1 μm or more, and more preferably 5 μm or more.

The layered body with a device wafer of the present invention can be produced by subjecting the surface of the adhesive substrate to a surface on the side of the film to be heated and pressure bonded to the element wafer or the carrier substrate. The heating and pressure bonding conditions are preferably, for example, a temperature of 100 ° C to 200 ° C, a pressure of 0.01 MPa to 1 MPa, and a time of 1 minute to 15 minutes. Further, the dummy film of the present invention may be disposed between a carrier substrate and an element wafer, and may be produced by heating and pressure bonding.

<Manufacturing Method of Semiconductor Device> <<First Embodiment>> Hereinafter, an embodiment of a method of manufacturing a semiconductor device will be described with reference to FIGS. 2(A) to 2(E). Furthermore, the present invention is not limited to the following embodiments. 2(A) to 2(E) are schematic cross-sectional views (Fig. 2(A), Fig. 2(B)) for explaining a false connection of a carrier substrate and an element wafer, respectively, showing a pseudo-subsequent to a carrier base. The state in which the component wafer is thinned (Fig. 2(C)), the state in which the carrier substrate and the component wafer are peeled off (Fig. 2(D)), and the state in which the dummy film is removed from the device wafer ( Fig. 2 (E)) is a schematic cross-sectional view.

As shown in FIG. 2(A), an adhesive substrate 100 having the dummy film 11 of the present invention on the carrier substrate 12 is prepared. In this embodiment, the surface a of the pseudo-adhesion film is disposed on the side of the carrier substrate 12. The adhesive substrate 100 can be produced by disposing a film-like pseudo-adhesive film on a carrier substrate so as to be disposed on the carrier substrate 12 so that the surface a of the dummy film is disposed on the carrier substrate 12 side. The element wafer 60 is formed by providing a plurality of element wafers 62 on the surface 61a of the ruthenium substrate 61. The thickness of the ruthenium substrate 61 is preferably, for example, 200 μm to 1200 μm. The element wafer 62 is preferably, for example, a metal structure, and has a height of preferably 10 μm to 100 μm. In the process of forming the dummy adhesive film 11, a step of cleaning the back surface of the carrier substrate 12 or the element wafer 60 by a solvent or the like may be provided. Specifically, by removing the residue of the dummy film attached to the end surface and the back surface of the carrier substrate 12 or the element wafer 60 by using a solvent that dissolves the dummy film, contamination of the device can be prevented, and the thinned element crystal can be reduced. Total Thickness Variation (TTV). The solvent used in the step of washing the back surface of the carrier substrate 12 or the element wafer 60 with a solvent can be used.

Then, as shown in FIG. 2(B), the adhesive substrate 100 is pressed against the component wafer 60, whereby the carrier substrate 12 and the component wafer 60 are subsequently printed. It is preferable that the film 11 is completely covered with the element wafer 62. When the height of the element wafer is X μm and the thickness of the dummy film is Y μm, it is preferable to satisfy the relationship of "X+100≧Y>X". It is effective that the film 11 completely covers the element wafer 62 in order to further reduce the TTV (Total Thickness Variation) of the thin element wafer (that is, when the flatness of the thin element wafer is further improved). In other words, when the element wafer is made thinner, the plurality of element wafers 62 are protected by the dummy film 11, so that the uneven shape can be substantially eliminated in the contact surface with the carrier substrate 12. Therefore, even if the thickness is reduced in the state of being supported as described above, the shape derived from the plurality of element wafers 62 is reduced and transferred to the back surface 61b1 of the thin element wafer, and as a result, the finally obtained thin type member can be further reduced. Wafer TTV.

Then, as shown in FIG. 2(C), the back surface 61b of the ruthenium substrate 61 is subjected to mechanical or chemical treatment (not particularly limited, for example, a thin film treatment such as sliding or chemical mechanical polishing (CMP), Chemical Vapor Deposition (CVD) or Physical Vapor Deposition (PVD) treatment under high temperature and vacuum, treatment with chemicals such as organic solvents, acidic treatment solutions or alkaline treatment solutions As shown in FIG. 2(C), the thickness of the ruthenium substrate 61 is reduced as shown in FIG. 2(C) (for example, the average thickness is preferably less than 500 μm, more preferably, the plating treatment, the actinic ray irradiation, the heating and the cooling treatment) The thin component wafer 60a is obtained from 1 μm to 200 μm).

After the element wafer is made thinner, a step of cleaning the dummy adhesive film which is outside the area of the substrate surface of the element wafer by the solvent may be provided in a stage before the processing under high temperature and vacuum. Specifically, after the element wafer is made thinner, the excess pseudo-adhesion film is removed by using a solvent that dissolves the dummy film, thereby preventing the pseudo-adhesion film caused by directly performing the high-temperature vacuum treatment on the dummy adhesive film. Deformation and deterioration. The solvent used in the step of cleaning the pseudo-adhesion film which exceeds the area of the substrate surface of the carrier substrate or the substrate surface of the element wafer by the solvent can be used as the solvent used for the cleaning step. The solvent contained in the composition. That is, in the present invention, the area of the film surface of the dummy film is preferably smaller than the area of the substrate surface of the carrier substrate. Further, in the present invention, when the diameter of the substrate surface of the carrier substrate is C μm, the diameter of the substrate surface of the element wafer is D μm, and the diameter of the film surface of the dummy film is T μm. It is better to satisfy (C-200) ≧T≧D. Further, when the diameter of the substrate surface of the carrier substrate is C μm, the diameter of the substrate surface of the element wafer is D μm, and the diameter of the film surface of the dummy film on the side in contact with the carrier substrate is set. when set to T _D μm diameter of the membrane surface is T _C μm, and then the prosthesis film in contact with the element side wafer, satisfies _{(C-200) ≧ T C} > T D ≧ D. With such a configuration, it is possible to further suppress deformation and deterioration of the pseudo-adhesive film caused by directly performing the treatment under high temperature and vacuum on the dummy adhesive film. In addition, the area of the film surface of the pseudo-adhesion film refers to the area when viewed from a direction perpendicular to the carrier substrate, and the unevenness of the film surface is not considered. The substrate surface of the component wafer is also the same. That is, the substrate surface of the element wafer described here corresponds to, for example, the surface 61a of FIG. The diameter of the film surface or the like of the dummy film is also considered in the same manner. In addition, the diameter T of the film surface of the pseudo-adhesion film means that the diameter of the film surface on the side in contact with the carrier substrate of the pseudo-adhesion film is T _C μm, and the surface of the dummy film is in contact with the element wafer. When the diameter of the film surface is T _D μm, T = (T _C + T _D )/2. The diameter of the substrate surface of the carrier substrate and the diameter of the substrate surface of the element wafer refer to the diameter of the surface on the side in contact with the dummy film. In addition, although the carrier base material and the like are defined as "diameter", the carrier base material or the like is not necessarily a circular shape (a perfect circle) in a mathematical sense, and may be substantially circular. In the case of not being a perfect circle, the diameter when converting into a perfect circle of the same area is referred to as the diameter. Further, as a mechanical or chemical treatment, after the thinning treatment, a through hole (not shown) that penetrates the back surface 61b1 of the thin element wafer 60a and is formed in the through hole may be formed.矽through electrode (not shown). The heat treatment may be performed during the period after the carrier substrate 12 and the element wafer 60 are false and until the peeling. As an example of the heat treatment, heat treatment is performed in a mechanical or chemical treatment. The maximum reaching temperature in the heat treatment is preferably from 80 ° C to 400 ° C, more preferably from 130 ° C to 400 ° C, still more preferably from 180 ° C to 350 ° C. The highest reaching temperature in the heat treatment is preferably set to a temperature lower than the decomposition temperature of the pseudo-film. The heat treatment is preferably 30 seconds to 30 minutes at the highest temperature of arrival, more preferably 1 minute to 10 minutes at the highest temperature.

Then, as shown in FIG. 2(D), the carrier substrate 12 is detached from the thin element wafer 60a. The method of the detachment is not particularly limited, and it is preferable that the end portion of the thin-type element wafer 60a is pulled up in a direction perpendicular to the thin-type element wafer 60a and peeled off without any treatment. In this embodiment, since the surface a of the dummy film is disposed on the side of the carrier substrate 12, as shown in FIG. 2(D), the interface between the carrier substrate 12 and the dummy film 11 is peeled off. In the case where the surface b of the dummy film is placed on the carrier substrate 12 side, the surface of the surface of the dummy film, that is, the thin element wafer 60a and the dummy film 11 are used. The interface is peeled off.

The dummy adhesive film 11 is brought into contact with a peeling liquid to be described later, and then, if necessary, the thin component wafer 60a is slid relative to the carrier substrate 12, and the end portion of the thin component wafer 60a is perpendicular to the component wafer. The direction is pulled up and peeled off.

<Peeling Liquid> Hereinafter, the peeling liquid will be described in detail. As the peeling liquid, water and a solvent (organic solvent) can be used. Further, as the peeling liquid, an organic solvent in which the pseudo-adhesion film 11 is dissolved is preferable. Examples of the organic solvent include aliphatic hydrocarbons (hexane, heptane, Isopar E, H, G (manufactured by Esso Chemical Co., Ltd.), limonene, p-menthane, and anthracene. Alkane, decane, dodecane, decahydronaphthalene, etc., aromatic hydrocarbons (toluene, xylene, anisole, mesitylene, ethylbenzene, propylbenzene, cumene, n-butylbenzene, Dibutylbenzene, isobutylbenzene, tert-butylbenzene, pentylbenzene, isopentylbenzene, (2,2-dimethylpropyl)benzene, 1-phenylhexane, 1-phenylglycol Alkane, 1-phenyloctane, 1-phenyldecane, 1-phenyldecane, cyclopropylbenzene, cyclohexylbenzene, 2-ethyltoluene, 1,2-diethylbenzene, o-iso Propyltoluene, indane, 1,2,3,4-tetrahydronaphthalene, 3-ethyltoluene, m-isopropyltoluene, 1,3-diisopropylbenzene, 4-ethyltoluene, 1, 4-diethylbenzene, p-isopropyltoluene, 1,4-diisopropylbenzene, 4-tert-butyltoluene, 1,4-di-t-butylbenzene, 1,3-diethyl Benzobenzene, 1,2,3-trimethylbenzene, 1,2,4-trimethylbenzene, 4-tert-butyl-o-xylene, 1,2,4-triethylbenzene, 1,3 , 5-triethylbenzene, 1,3,5-triisopropylbenzene, 5-position Butyl-m-xylene, 3,5-di-t-butyltoluene, 1,2,3,5-tetramethylbenzene, 1,2,4,5-tetramethylbenzene, pentamethylbenzene, etc. ), a halogenated hydrocarbon (dichloromethane, dichloroethane, trichloroethylene, monochlorobenzene, etc.), a polar solvent. Examples of the polar solvent include alcohols (methanol, ethanol, propanol, isopropanol, 1-butanol, 1-pentanol, 1-hexanol, 1-heptanol, 1-octanol, 2-octanol). , 2-ethyl-1-hexanol, 1-nonanol, 1-nonanol, benzyl alcohol, ethylene glycol monomethyl ether, 2-ethoxyethanol, diethylene glycol monoethyl ether, diethylene glycol Monohexyl ether, triethylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether, polyethylene glycol monomethyl ether, polypropylene glycol, tetraethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monobenzyl Ether, ethylene glycol monophenyl ether, propylene glycol monophenyl ether, methylphenylmethanol, n-pentanol, methylpentanol, etc.), ketones (acetone, methyl ethyl ketone, ethyl butyl ketone, Methyl isobutyl ketone, cyclohexanone, etc., esters (ethyl acetate, propyl acetate, butyl acetate, amyl acetate, benzyl acetate, methyl lactate, butyl lactate, ethylene glycol monobutyl) Ether acetate, propylene glycol monomethyl ether acetate, diethylene glycol acetate, diethyl phthalate, butyl acetonate, etc.), other (triethyl phosphate, trimethyl phenol) Phosphate, N-phenylethanolamine, N-phenyldiethyl Amine, N- methyl-diethanolamine, N- ethyldiethanolamine, 4- (2-hydroxyethyl) morpholine, N, N- dimethylacetamide, N- methylpyrrolidone, etc.) and the like.

Further, from the viewpoint of peelability, the peeling liquid may contain a base, an acid, and a surfactant. When these components are blended, the blending amount is preferably from 0.1% by mass to 5.0% by mass based on the stripping solution. Further, from the viewpoint of the releasability, it is also preferred to mix two or more organic solvents and water, two or more kinds of bases, an acid, and a surfactant.

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

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

As the surfactant, an anionic, cationic, nonionic or zwitterionic surfactant can be used. In this case, the content of the surfactant is preferably from 1% by mass to 20% by mass, and more preferably from 1% by mass to 10% by mass based on the total amount of the aqueous alkaline solution. When the content of the surfactant is within the above range, the peeling property of the dummy film 11 and the thin element wafer 60a tends to be further improved.

The anionic surfactant is not particularly limited, and examples thereof include fatty acid salts, rosinates, hydroxyalkanesulfonates, alkanesulfonates, dialkylsulfosuccinates, and linear alkanes. Alkylbenzenesulfonate, branched alkylbenzenesulfonate, alkylnaphthalenesulfonate, alkyldiphenylether (di)sulfonate, alkylphenoxypolyoxyethylene alkylsulfonate Acid salts, polyoxyethylene alkyl sulfophenyl ether salts, sodium N-alkyl-N-oleyl taurate, N-alkyl sulfosuccinate monoamine disodium salt, petroleum Sulfonates, sulfated castor oil, sulfated tallow oil, sulfate esters of fatty acid alkyl esters, alkyl sulfate salts, polyoxyethylene alkyl ether sulfate salts, fatty acid monoglyceride sulfate salts , polyoxyethylene alkyl phenyl ether sulfate salts, polyoxyethylene styryl phenyl ether sulfate salts, alkyl phosphate salts, polyoxyethylene alkyl ether phosphate salts, polyoxyethylene Alkyl phenyl ether phosphate salts, partial saponifications of styrene-maleic anhydride copolymers, partial soaps of olefin-maleic anhydride copolymers Species, naphthalene sulfonate formaldehyde condensates and the like. Among them, alkylbenzenesulfonates, alkylnaphthalenesulfonates, and alkyldiphenylether (di)sulfonates are particularly preferably used.

The cationic surfactant is not particularly limited, and those known in the art can be used. For example, an alkylamine salt, a quaternary ammonium salt, an alkyl imidazolium salt, a polyoxyethylene alkylamine salt, and a polyethylene polyamine derivative are mentioned.

The nonionic surfactant is not particularly limited, and examples thereof include a polyethylene glycol-based higher alcohol ethylene oxide adduct, an alkylphenol ethylene oxide adduct, and an alkyl naphthol epoxy B. Alkane adduct, phenol ethylene oxide adduct, naphthol ethylene oxide adduct, fatty acid ethylene oxide adduct, polyol fatty acid ester ethylene oxide adduct, higher alkylamine Ethylene oxide adduct, fatty acid decylamine ethylene oxide adduct, ethylene oxide adduct of fats and oils, polypropylene glycol ethylene oxide adduct, dimethyl methoxy alkane-ethylene oxide Block copolymer, dimethyloxane-(propylene oxide-ethylene oxide) block copolymer, fatty acid ester of glycerol of polyol type, fatty acid ester of pentaerythritol, sorbitol and sorbitol A fatty acid ester of an anhydride, a fatty acid ester of sucrose, an alkyl ether of a polyhydric alcohol, a fatty acid decylamine of an alkanolamine, or the like. Among them, those having an aromatic ring and an ethylene oxide chain are preferred, and an alkyl substituted or unsubstituted phenol ethylene oxide adduct or an alkyl substituted or unsubstituted naphthol epoxy is preferred. Ethane adduct.

The zwitterionic surfactant is not particularly limited, and examples thereof include an amine oxide system such as an alkylamine oxide such as an alkyl dimethylamine oxide, a betaine system such as an alkylbetaine, or an alkylamine fatty acid sodium. In particular, an alkyl dimethyl amine oxide which may have a substituent, an alkylcarboxybetaine which may have a substituent, and an alkyl sulfobetaine which may have a substituent may be preferably used. Specifically, a compound represented by the formula (2) of Paragraph No. [0256] of JP-A-2008-203359, and a formula of Paragraph No. [0028] of JP-A-2008-276166 can be used. I), a compound represented by the formula (II), the formula (VI), and a compound shown in paragraphs [0022] to [0029] of JP-A-2009-47927.

Further, an additive such as an antifoaming agent and a hard water softening agent may be contained as needed.

Further, as shown in FIG. 2(E), the thin element wafer can be obtained by removing the dummy adhesive film 11 from the thin element wafer 60a. The method of removing the film 11 may be, for example, a method in which a pseudo-adhesive film is peeled off (mechanically peeled off) in a film state, a method in which a pseudo-adhesion film is swollen by a peeling liquid, and a method of peeling off is performed; A method of removing and removing the peeling liquid; a method of dissolving and removing the pseudo-adhesive film in the peeling liquid; and a method of decomposing and vaporizing the pseudo-adhesive film by irradiation with actinic rays, radiation, or heat. A method of peeling off the pseudo-adhesive film in a film state can be preferably used; a method in which the pseudo adhesive film is dissolved in an aqueous solution or an organic solvent to be dissolved and removed. As the organic solvent, the organic solvent described in the above-mentioned peeling liquid can be used. From the viewpoint of reducing the amount of use of the solvent, it is preferred to remove it in a film state. Further, from the viewpoint of reducing damage on the surface of the element wafer, it is preferably dissolved and removed. In order to remove in a film state, it is preferable that the peel strength B of the element wafer surface 61a and the dummy film 11 satisfy the following formula (2). B≦4 N/cm ... (2)

When the peeling strength of the interface between the carrier substrate 12 and the dummy adhesive film 11 is A, and the peeling strength of the surface 61a of the element wafer and the dummy film 11 is B, the formula (1) is simultaneously satisfied. (2), when the carrier base material 12 is peeled off from the thin component wafer 60a, the end portion of the thin component wafer 60a is pulled up in a direction perpendicular to the component wafer without any treatment. The peeling is performed, and the dummy film 11 on the element wafer surface 61a can be removed in a film state. After the carrier substrate 12 is detached from the thin component wafer 60a, various known processes are performed on the thin component wafer 60a as needed to manufacture a semiconductor device having the thin component wafer 60a.

Further, when the residue of the film or the like adheres to the carrier substrate, the carrier substrate can be regenerated by removing the residue. Examples of the method for removing the residue include a physical removal method by blowing a brush, an ultrasonic wave, an ice particle, or an aerosol; a method of dissolving and dissolving in an aqueous solution or an organic solvent to dissolve and remove; A chemical removal method such as a method of decomposing and vaporizing radiation, radiation, or heat, and a conventionally known cleaning method can be used depending on the carrier substrate. For example, in the case of using a tantalum substrate as a carrier substrate, a previously known cleaning method of a tantalum wafer can be used, for example, as an aqueous solution or an organic solvent which can be used for chemical removal, and examples thereof include a strong acid and a strong alkali. The strong oxidizing agent or a mixture thereof may specifically be an acid such as sulfuric acid, hydrochloric acid, hydrofluoric acid, nitric acid or an organic acid; an alkali such as tetramethylammonium, ammonia or an organic base; or an oxidizing agent such as hydrogen peroxide; A mixture of ammonia and hydrogen peroxide, a mixture of hydrochloric acid and hydrogen peroxide water, a mixture of sulfuric acid and hydrogen peroxide water, a mixture of hydrofluoric acid and hydrogen peroxide water, a mixture of hydrofluoric acid and ammonium fluoride, and the like.

From the viewpoint of the adhesion in the case of using the regenerated carrier substrate, it is preferred to use a cleaning liquid. The cleaning solution preferably contains an acid (strong acid) having a pKa of less than 0 and hydrogen peroxide. The acid having a pKa of less than 0 may be selected from inorganic acids such as hydrogen iodide, perchloric acid, hydrogen bromide, hydrogen chloride, nitric acid, sulfuric acid, or the like, or an organic acid such as an alkylsulfonic acid or an arylsulfonic acid. From the viewpoint of the cleaning property of the pseudo-adhesive film on the carrier substrate, a mineral acid is preferred, and sulfuric acid is preferred.

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

<<Second Embodiment>> A second embodiment of a semiconductor manufacturing method in which a step of manufacturing a laminated body is carried out will be described with reference to Figs. 3(A) to 3(E). The same portions as those in the first embodiment are denoted by the same reference numerals, and their description will be omitted. 3(A) to 3(E) are schematic cross-sectional views (Fig. 3(A), Fig. 3(B)) for explaining the false connection of the carrier substrate and the element wafer, respectively, showing the pseudo-subsequent to the carrier base. The state in which the component wafer is thinned (Fig. 3(C)), the state in which the carrier substrate and the component wafer are peeled off (Fig. 3(D)), and the state in which the dummy film is removed from the component wafer ( Fig. 3 (E)) is a schematic cross-sectional view. In this embodiment, as shown in FIG. 3(A), the dummy film 11a is formed on the surface 61a of the element wafer, which is different from the first embodiment. In this embodiment, the surface b of the dummy film is disposed on the element wafer 60 side. As a method of forming a dummy film on the surface 61a of the element wafer so that the surface b of the dummy film is disposed on the surface of the element wafer 60, the dummy wafer of the present invention can be exemplified on the element wafer 60. A method in which a composition is applied as a layer and dried to form a pseudo-adhesive film. In addition, a film-shaped dummy film can be placed on the element wafer and laminated by disposing the surface b of the dummy film on the element wafer 60 side. Then, as shown in FIG. 3(B), the carrier substrate 12 is pressed against the component wafer 60, thereby causing the carrier substrate 12 and the component wafer 60 to be false. Then, as shown in FIG. 3(C), the back surface 61b of the ruthenium substrate 61 is mechanically or chemically treated to reduce the thickness of the ruthenium substrate 61, and the thin element wafer 60a is obtained. Then, as shown in FIG. 3(D), the carrier substrate 12 is detached from the thin element wafer 60a. In this embodiment, since the surface a of the dummy film is disposed on the side of the carrier substrate 12, as shown in FIG. 3(D), the interface between the carrier substrate 12 and the dummy film 11 is peeled off. Further, as shown in FIG. 3(E), the thin element wafer can be obtained by removing the dummy adhesive film 11 from the thin element wafer 60a. [Examples]

Hereinafter, the present invention will be specifically described by way of examples, and the present invention is not limited to the following examples, without departing from the spirit of the invention. In addition, unless otherwise indicated, "part" and "%" are the quality standards.

[Test Example 1] <Preparation of Compositions by Default> The following components were mixed to prepare a pseudo-construction composition. - Compound having a fluorine atom: the types described in Table 1, the parts by mass shown in Table 1, the binders: the types described in Table 1, and the mass parts shown in Table 1 · Irganox 1010 (manufactured by BASF): 5 parts by mass of Sumilizer TP-D (manufactured by Sumitomo Chemical Co., Ltd.): 5 parts by mass of solvent: the solvent described in Table 1, Parts of mass shown in Table 1

[Table 1]

The compounds described in Table 1 are as follows. [Compound having a fluorine atom] (A-1): Megafac F-553 (oligomer containing a fluorine group, a hydrophilic group, a lipophilic group, or a liquid compound (viscosity at 25 ° C is 1 mPa· s~100,000 mPa·s range), 10% thermal mass reduction temperature=247°C, Mw=0.2 million or more and less than 20,000, manufactured by Diane Health (DIC)) (A-2): Megafac F -554 (oligomer containing fluorine group or lipophilic group, liquid compound (viscosity at 25 ° C in the range of 1 mPa·s to 100,000 mPa·s), 10% thermal mass reduction temperature = 267 ° C, Mw = 0.20 or more and less than 20,000, manufactured by Diane Health (DIC)) (A-3): Megafac F-556 (oligomer containing fluorine group, hydrophilic group, lipophilic group, liquid compound ( Viscosity at 25 ° C is in the range of 1 mPa·s to 100,000 mPa·s), 10% thermal mass reduction temperature = 277 ° C, Mw = 0.2 million or more and less than 20,000, manufactured by Di Ai Sheng (DIC) Co., Ltd. (A- 4): Megafac F-557 (oligomer containing fluorine group, hydrophilic group, lipophilic group, liquid compound (viscosity at 25 ° C of 1 mPa·s to 100,000 mPa·s) Circumference), 10% thermal mass reduction temperature = 299 ° C, Mw = 0.2 million or more and less than 20,000, manufactured by Di AI (DIC) (A-5): Megafac F-559 (containing fluorine-based Hydrophilic group/lipophilic group oligomer, liquid compound (viscosity at 25 ° C in the range of 1 mPa·s to 100,000 mPa·s), 10% thermal mass reduction temperature = 286 ° C, Mw = 20,000 or more Less than 50,000, manufactured by Diane Health (DIC)) (A-6): Ftergent 710FL (oligomer containing fluorine group, hydrophilic group, lipophilic group, liquid compound (viscosity at 25 ° C) It is in the range of 1 mPa·s to 100,000 mPa·s, manufactured by NEOS (A-7): Ftergent 730LM (oligomer containing fluorine group, hydrophilic group, lipophilic group) Compounds, liquid compounds (viscosity at 25 ° C in the range of 1 mPa·s to 100,000 mPa·s), manufactured by NEOS (A-8): Surflon S243 (containing fluorine) Ethylene oxide adduct, liquid compound containing no lipophilic group, manufactured by AGC Seimi Chemical Co., Ltd.) [Binder] (B-1): Match Septon 2002 (hydrogenated polystyrene elastomer, styrene content = 30% by mass, unsaturated double bond amount = less than 0.5 mmol/g, 5% thermal mass reduction temperature = 350 ° C or more and less than 400 ° C, Mw=50,000 or more and less than 100,000, hardness (type A durometer)=80, manufactured by Kuraray (share)) (B-2): Septon 2104 (hydrogenated polystyrene elastic) Body, styrene content = 65 mass%, unsaturated double bond amount = less than 0.5 mmol / g, 5% thermal mass reduction temperature = 400 ° C or more and less than 450 ° C, Mw = 50,000 or more and less than 100,000, hardness ( Type A durometer) = 98, manufactured by Kuraray Co., Ltd.) (B-3): Tuftec P2000 (hydrogenated polystyrene elastomer, styrene content = 67% by mass, Unsaturated double bond amount = 0.5 mmol / g or more and less than 5 mmol / g, 5% thermal mass reduction temperature = 400 ° C or more and less than 450 ° C, Mw = 50,000 or more and less than 100,000, hardness (type A hardness tester) =90 or more, manufactured by Asahi Kasei Co., Ltd.) (B-4): Durimide registered trademark 284 (polyimide manufactured by Fujifilm) B-5): ZEONEX 480R (cycloolefin polymer manufactured by ZEON) (B-6): PCZ300 (polycarbonate manufactured by Mitsubishi Gas Chemical Co., Ltd.) Unsaturated double bond amount It is a value calculated by NMR (nuclear magnetic resonance) measurement. The mass reduction temperature is a value measured by a thermogravimetric measuring apparatus under the condition of a nitrogen gas flow and a temperature rise at 25 ° C /min at 25 ° C.

<Manufacturing of Test Piece> The dummy composition was spin-coated on a tantalum wafer (first substrate), dried at 110 ° C for 2 minutes, and further dried at 190 ° C for 4 minutes. A laminate having a pseudo-adhesion film having a thickness of 60 μm was produced on the (first substrate). Hereinafter, the surface (air side surface) on the opposite side to the first base material of the false adhesive film is also referred to as an A surface. Further, the surface on the first substrate side of the dummy film is also referred to as a B surface. The test piece was produced by pressure-bonding the surface of the laminated body on the side of the film with the ruthenium wafer (second base material) under vacuum at 190 ° C and 0.11 MPa for 3 minutes.

<<Measurement of the ratio of the presence of fluorine atoms in the film>> The first substrate, the pseudo-adhesion film, and the second substrate of the obtained test piece were separated, and the A of the pseudo-adhesive film was measured by X-ray photoelectron spectroscopy. The ratio of the presence of fluorine atoms on the surface and the B side. The measuring apparatus used PHI Quantera SXM (manufactured by ULVAC PHI) to irradiate 25 W of monochromated AlKα rays on the analysis area of 1400 μm ́700 μm of the pseudo-adhesive film and to detect at an exit angle of 45°. On the other hand, the ratio of the presence of fluorine atoms on the A side and the B side of the film was measured. The measurement temperature is room temperature (20 ° C to 25 ° C), and the measurement pressure is 10 ^-8 Pa or less.

<<Evaluation of Peelability>> The test piece produced under the conditions described in the following table was stretched in the vertical direction of the dummy film under conditions of 250 mm/min to confirm the peelability. A: Maximum peeling force is less than 15 N, peelable B: Maximum peeling force is 15 N or more and less than 25 N, peelable C: Maximum peeling force is 25 N or more and less than 40 N, peelable D: Maximum peeling force is 50 N or more or damaged wafer

<<Evaluation of Peeling Interface>> The peeling test was performed 10 times, and the number of peeling of the A side and the number of peeling of the B side were measured.

[Table 2]

According to the results, the peeling properties of Examples 1 to 16 were excellent. Further, peeling can be performed on the side A of the dummy film, and the peeling interface is stabilized. On the other hand, Comparative Example 1 and Comparative Example 2 were inferior in peelability. Further, in Comparative Example 3 to Comparative Example 5, the A surface of the dummy film was peeled off, and the B surface was peeled off, and the peeling interface was unstable.

[Test Example 2] <Preparation of Compositions by Default> The following components were mixed to prepare a pseudo-construction composition. - Compounds having a fluorine atom: the types described in Table 3, the parts by mass shown in Table 3, the binders: the types described in Table 3, and the mass parts shown in Table 3, Irganox 1010 (manufactured by BASF): 5 parts by mass of Sumilizer TP-D (manufactured by Sumitomo Chemical Co., Ltd.): 5 parts by mass of solvent: the solvent described in Table 3, Parts of mass shown in Table 3

[table 3]

The compounds described in the table are as follows. [Compound having a fluorine atom] (A-4): the same as (A-4) described in Table 1 [Binders] (B-1) to (B-3): as described in Table 1 ( B-1) to (B-3) are the same (B-7): Septon 4033 (hydrogenated polystyrene elastomer, styrene content = 30% by mass, unsaturated double bond amount = less than 0.5) Mmol/g, 5% thermal mass reduction temperature = 400 ° C or more and less than 400 ° C, hardness (type A durometer) = 76, manufactured by Kuraray (stock)) (B-8): Septon (Septon) 4044 (hydrogenated polystyrene elastomer, styrene content = 30% by mass, unsaturated double bond amount = less than 0.5 mmol/g, 5% thermal mass reduction temperature = 400 ° C or more and less than 450 ° C, Kuraray ( Kuraray) (B-9): Kraton G1650 (hydrogenated polystyrene elastomer, styrene content = 30% by mass, unsaturated double bond amount = less than 0.5 mmol/g, 5 % Thermal mass reduction temperature = 400 ° C or more and less than 450 ° C, hardness (Type A durometer) = 70, manufactured by Kraton (B-10): Septon 8104 (hydrogenated polystyrene) Resilience , styrene content = 60% by mass, unsaturated double bond amount = less than 0.5 mmol / g, 5% thermal mass reduction temperature = 350 ° C or more and less than 400 ° C, hardness (type A durometer) = 98, Kuraray ( Kuraray) (B-11): Kraton A1535 (hydrogenated polystyrene elastomer, styrene content = 58% by mass, unsaturated double bond amount = less than 0.5 mmol/g, 5 % thermal mass reduction temperature = 400 ° C or more and less than 450 ° C, hardness (type A durometer) = 83, manufactured by Kraton

<Manufacture of Test Piece> The dummy composition was spin-coated on a tantalum wafer (first substrate) having a diameter of 100 mm and a thickness of 525 μm, and dried at 110 ° C for 2 minutes, and further 190 After drying at ° C for 4 minutes, a laminate having a pseudo-adhesion film having a thickness of 60 μm was produced on the tantalum wafer (first substrate). Hereinafter, the surface (air side surface) on the opposite side to the first base material of the false adhesive film is also referred to as an A surface. Further, the surface on the first substrate side of the dummy film is also referred to as a B surface. The tantalum wafer (second substrate) having a diameter of 100 mm and a thickness of 525 μm was pressure-bonded to the laminate on the surface of the laminate with a pressure of 190 ° C and a pressure of 0.11 MPa under vacuum for 3 minutes. And make a test piece.

<<Measurement of the ratio of the presence of fluorine atoms in the film>> The first substrate, the pseudo-adhesion film, and the second substrate of the obtained test piece were separated, and the A of the pseudo-adhesive film was measured by X-ray photoelectron spectroscopy. The ratio of the presence of fluorine atoms on the surface and the B side. The measuring apparatus used PHI Quantera SXM (manufactured by ULVAC PHI) to irradiate 25 W of monochromated AlKα rays on the analysis area of 1400 μm ́700 μm of the pseudo-adhesive film and to detect at an exit angle of 45°. On the other hand, the ratio of the presence of fluorine atoms on the A side and the B side of the film was measured. The measurement temperature is room temperature (20 ° C to 25 ° C), and the measurement pressure is 10 ^-8 Pa or less.

<<Evaluation of Peelability>> The test piece produced under the conditions described in the following table was stretched in the vertical direction of the dummy film under conditions of 250 mm/min to confirm the peelability. A: Maximum peeling force is less than 15 N, peelable B: Maximum peeling force is 15 N or more and less than 25 N, peelable C: Maximum peeling force is 25 N or more and less than 40 N, peelable D: Maximum peeling force is 50 N or more or damaged wafer

<<Evaluation of Peeling Interface>> The peeling test was performed 10 times, and the number of peeling of the A side and the number of peeling of the B side were measured.

<Flat Polishing Property> The first base material of the produced test piece was polished to a thickness of 35 μm. The first substrate to be polished was visually confirmed, and the presence or absence of a depression having a diameter of 1 mm or more was confirmed. A: The depression is not visible at all. B: Although a slight depression is generated, it is tolerable. C: A large number of depressions are generated and cannot be tolerated.

<Wafer Warpage> The first base material of the produced test piece was polished to a thickness of 35 μm, and then the temperature rise rate and the temperature drop rate were set to 10 using FLX-2320 manufactured by KLA-Tencor Co., Ltd. After heating at room temperature to 200 ° C at ° C / min, it was cooled to room temperature, and the Bow (bending) value was measured. A: Bow value is 40 μm or less B: Bow value is more than 40 μm and less than 80 μm C: Bow value is 80 μm or more

[Table 4] According to the results, the peelability of Examples 17 to 30 was excellent. Further, the side A of the dummy film can be peeled off, and the peeling interface is stabilized. Further, the flatness is excellent, and the warpage of the wafer can be suppressed. Further, in Examples 17 to 26 in which the elastomer A and the elastomer B were used as the elastomer, the flatness of the flatness was particularly excellent.

[Test Example 3] <Preparation of Compositions by Default> The following components were mixed to prepare a pseudo-construction composition. (Fake composition of the composition) - Compound having a fluorine atom: the types described in Table 5, the parts by mass shown in Table 5, the binders: the types described in Table 5, and the types shown in Table 5. Parts by mass and radically polymerizable compound: the types described in Table 5, and the mass parts shown in Table 5, 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 described in Table 5, and the mass parts shown in Table 5.

[table 5]

The compounds described in Table 5 are as follows. [Compound having a fluorine atom] (A-1): same as (A-1) of Table 1 [Binder] (B-2): same as (B-2) of Table 1 (B-12): Match Septon V9827 (hydrogenated polystyrene elastomer, styrene content = 30% by mass, 5% thermal mass reduction temperature = 400 ° C or more and less than 450 ° C, hardness (type A durometer) = 78, cola Kuraray (manufactured by Kuraray Co., Ltd.) [radical polymerizable compound] (C-1): NK ester M-40G (manufactured by Shin-Nakamura Chemical Co., Ltd., monofunctional methacrylate, the following structure) 14] (C-2): NK ester 4G (manufactured by Shin-Nakamura Chemical Co., Ltd., difunctional methacrylate, the following structure) [Chem. 15] (C-3): NK ester A-9300 (manufactured by Shin-Nakamura Chemical Co., Ltd., trifunctional acrylate, the following structure) [Chem. 16] (C-4): triallyl isocyanurate (manufactured by Tokyo Chemical Industry Co., Ltd., trifunctional allylic compound) [Chem. 17] (C-5): NK ester A-TMMT (manufactured by Shin-Nakamura Chemical Co., Ltd., tetrafunctional acrylate) [Chem. 18] (C-6): NK ester A-DPH (manufactured by Shin-Nakamura Chemical Industry Co., Ltd., hexafunctional acrylate) [Chem. 19] (C-7): NK ester A-BPE-4 (manufactured by Shin-Nakamura Chemical Industry Co., Ltd., difunctional acrylate) [Chem. 20]

<Manufacturing of Test Piece> The dummy composition was spin-coated on a tantalum wafer (first substrate) having a diameter of 100 mm and a thickness of 525 μm, and dried at 110 ° C for 2 minutes, and further 150 After drying at ° C for 4 minutes, a laminate having a pseudo-adhesion film having a thickness of 60 μm was produced on the tantalum wafer (first substrate). Hereinafter, the surface (air side surface) on the opposite side to the first base material of the false adhesive film is also referred to as an A surface. Further, the surface on the first substrate side of the dummy film is also referred to as a B surface. The surface of the laminated body on the side of the pseudo-adhesive film and the crucible wafer (second substrate) having a diameter of 100 mm and a thickness of 525 μm were pressure-bonded for 3 minutes under vacuum at a pressure of 220 ° C and 0.11 MPa. And make a test piece.

<<Measurement of the ratio of the presence of fluorine atoms in the film>> The first substrate, the pseudo-adhesion film, and the second substrate of the obtained test piece were separated, and the A of the pseudo-adhesive film was measured by X-ray photoelectron spectroscopy. The ratio of the presence of fluorine atoms on the surface and the B side. The measuring apparatus used PHI Quantera SXM (manufactured by ULVAC PHI) to irradiate 25 W of monochromated AlKα rays on the analysis area of 1400 μm ́700 μm of the pseudo-adhesive film and to detect at an exit angle of 45°. On the other hand, the ratio of the presence of fluorine atoms on the A side and the B side of the film was measured. The measurement temperature is room temperature (20 ° C to 25 ° C), and the measurement pressure is 10 ^-8 Pa or less.

<<Evaluation of Peelability>> The test piece produced under the conditions described in the following table was stretched in the vertical direction of the dummy film under conditions of 250 mm/min to confirm the peelability. A: Maximum peeling force is less than 15 N, peelable B: Maximum peeling force is 15 N or more and less than 25 N, peelable C: Maximum peeling force is 25 N or more and less than 40 N, peelable D: Maximum peeling force is 50 N or more or damaged wafer

<<Evaluation of Peeling Interface>> The peeling test was performed 10 times, and the number of peeling of the A side and the number of peeling of the B side were measured.

<Flat Polishing Property> The first base material of the produced test piece was polished to a thickness of 35 μm. The first substrate to be polished was visually confirmed, and the presence or absence of a depression having a diameter of 1 mm or more was confirmed. A: The depression is not visible at all. B: Although a slight depression is generated, it is tolerable. C: A large number of depressions are generated and cannot be tolerated.

<Wafer Warpage> The first base material of the produced test piece was polished to a thickness of 35 μm, and then the temperature rise rate and the temperature drop rate were set to 10 using FLX-2320 manufactured by KLA-Tencor Co., Ltd. After heating to room temperature from room temperature to 200 ° C, it was cooled to room temperature and the Bow value was measured. A: Bow value is 40 μm or less B: Bow value is more than 40 μm and less than 80 μm C: Bow value is 80 μm or more

[Table 6] According to the results, the peelability of the examples was excellent. In addition, the peeling interface is stable. Further, the flatness is excellent, and the warpage of the wafer can be suppressed.

[Test Example 4] <Production of test piece> A 12-inch diameter twin was subjected to edge trimming treatment with a plurality of bumps and a width of 500 μm and a depth of 100 μm. On the surface of a circle (1吋2.54 cm), 15 mL was added in 30 seconds while rotating at 50 rpm using a wafer bonding apparatus (manufactured by Tokyo Electron and Synapse V). The composition of the pseudo-construction used in Examples 1 to 40 was used. The number of revolutions was increased to 600 rpm for 30 seconds, and then, while rotating the crucible wafer, mesitylene was supplied to the outer peripheral portion of the crucible wafer and the back surface of the crucible wafer for 40 seconds, and was cleaned and attached to the outer peripheral portion of the crucible wafer. And the fake backside of the wafer is followed by a composition. Using a hot plate, the film was heated at 110 ° C for 3 minutes and further heated at 190 ° C for 3 minutes to form a pseudo-adhesion film on the surface of the tantalum wafer. Next, the surface on which the pseudo-adhesive film side was formed and the other piece 12 were pressed under vacuum at 190 ° C and 0.11 MPa by a wafer bonding apparatus (manufactured by Tokyo Electron Co., Ltd., Synapse V). The tantalum wafer (carrier substrate) was crimped for 3 minutes to obtain a laminate. Further, the thickness of the dummy film at this time was 40 μm. Next, the previously used tantalum wafer side of the laminate was polished to a thickness of 35 μm using a back grinder DFG8540 (manufactured by DISCO) to obtain a thinned laminated body. . The thinned germanium wafer of the laminate has a diameter of 299 mm.

<End-face treatment after thinning> The carrier substrate was placed on the lower surface, and the thinned laminated body was 300 by a wafer bonding apparatus (manufactured by Tokyo Electron Co., Ltd., Synapse V). Rotate at rpm and add 15 mL of mesitylene to the position of 20 mm from the end of the tantalum wafer in 10 seconds. Then, the number of revolutions was increased to 1000 rpm, and 45 mL of mesitylene was added dropwise over 30 seconds. Then, the surface of the crucible wafer was dried by rotating it for 20 seconds while maintaining the number of revolutions at 1000 rpm. The obtained laminated body was observed from the direction perpendicular to the tantalum wafer having a diameter of 12 Å provided with a plurality of protrusions by an optical microscope, and as a result, it was confirmed that the diameter of the substrate surface of the pseudo-adhesive film was larger than that of the carrier base. The substrate surface of the material has a diameter of less than 250 μm. Further, the diameter of the film surface on the side in contact with the carrier substrate of the film is larger than the diameter of the film surface on the side in contact with the element wafer.

11, 11a‧‧‧ false film
12‧‧‧ Carrier substrate
60‧‧‧Component Wafer
60a‧‧‧ Thin component wafer
61‧‧‧矽 substrate
61a‧‧‧ surface
61b‧‧‧Back
61b1‧‧‧back
62‧‧‧Component wafer
100‧‧‧Adhesive substrate
a, b‧‧‧ surface

Fig. 1 is a schematic view showing a false adhesive film of the present invention. 2(A) to 2(E) are schematic views showing a first embodiment of a method of manufacturing a semiconductor device. 3(A) to 3(E) are schematic diagrams showing a second embodiment of a method of manufacturing a semiconductor device.

11‧‧‧ False follow-up film

a, b‧‧‧ surface

Claims (32)

A method for producing a pseudo-adhesive film comprising the steps of coating a dummy layer with a composition and drying it on a support, the pseudo-conducting composition containing a compound having a fluorine atom, with respect to the false Membrane, the use of the surface of the pseudo-adhesive film measured by irradiating 25 W of monochromated AlKα rays to an analysis area of 1400 μm ́ 700 μm on the surface of the pseudo-adhesive film and detecting at an exit angle of 45° The ratio of the presence of fluorine atoms obtained by ray photoelectron spectroscopy, the ratio A of the fluorine atoms in the surface of the pseudo-adhesion film on the opposite side to the support, and the support side of the pseudo-adhesion film The ratio B of the fluorine atoms in the surface satisfies the relationship of the following formula (1), and the ratio A of the fluorine atoms is 5% to 40%, and A/B ≧ 1.3 (1) is a false The ratio A of the fluorine atoms in the surface of the film opposite to the support is A, and B is the ratio B of the fluorine atoms in the surface of the support side of the pseudo-attachment film. The method for producing a pseudo-adhesive film according to the first aspect of the invention, wherein the ratio ratio A of the fluorine atom of the pseudo-adhesion film to the fluorine atom satisfies the following formula (2) Relationship, and the existence ratio A of the fluorine atom is 10% to 30%, A/B≧1.5 (2) A is the existence ratio of fluorine atoms in the surface of the pseudo-attachment film opposite to the support A B is the ratio B of the presence of fluorine atoms in the surface of the support side of the film. The method for producing a pseudo-adhesive film according to the first or second aspect of the invention, wherein the compound having a fluorine atom contains a lipophilic group. The method for producing a pseudo-adhesive film according to the first or second aspect of the invention, wherein the composition for false smear comprises at least one selected from the group consisting of a binder and a radical polymerizable compound. The method for producing a pseudo-adhesive film according to claim 4, wherein the binder is a block copolymer. The method for producing a pseudo-adhesive film according to claim 4, wherein the binder is a styrene block copolymer having a single terminal or a styrene block at both ends. The method for producing a pseudo-adhesive film according to claim 4, wherein the binder is a hydride of a block copolymer. The method for producing a pseudo-adhesive film according to claim 4, wherein the binder is an elastomer. The method for producing a pseudo-adhesive film according to claim 8, wherein the elastomer contains a repeating unit derived from styrene. The method for producing a pseudo-adhesive film according to claim 8, wherein the elastomer is a hydride. The method for producing a pseudo-adhesive film according to claim 8, wherein the elastomer is a styrene block copolymer having a single terminal or a styrene block at both ends. The method for producing a pseudo-adhesive film according to claim 8, wherein the elastomer contains an elastomer A and an elastomer B, and the elastomer A is 10 mass% or more and 50 mass in all the repeating units. The ratio below % contains a repeating unit derived from styrene containing a repeating unit derived from styrene in a ratio of more than 50% by mass and 95% by mass or less in all the repeating units. The method for producing a pseudo-adhesive film according to claim 12, wherein the mass ratio of the elastomer A to the elastomer B is 5:95 to 95:5. The method for producing a pseudo-adhesive film according to the invention of claim 4, wherein the radical polymerizable compound is a compound having two or more radical polymerizable groups. The method for producing a pseudo-adhesive film according to claim 4, wherein the radically polymerizable compound has at least one of partial structures represented by the following (P-1) to (P-4); * in the formula is a link key, . The method for producing a pseudo-adhesive film according to claim 4, wherein the radical polymerizable compound is selected from trimethylolpropane tri(meth)acrylate, isocyanuric acid ethylene oxide. Modified di(meth)acrylate, isocyanuric acid ethylene oxide modified tri(meth)acrylate, triallyl isocyanurate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra (A) Acrylate, dimethylolpropane tetra(meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa(meth) acrylate, and tetramethylol methane tetra(meth) acrylate At least one of them. The method for producing a pseudo-adhesive film according to the first or second aspect of the invention, wherein the composition of the pseudo-adhesive composition is 0.03 mass% or more and less than the total solid content of the composition for the pseudo-adhesive composition. The ratio of 0.5% by mass contains the compound having a fluorine atom. The method for producing a pseudo-adhesive film according to the first or second aspect of the invention, wherein the pseudo-adhesive film has an average film thickness of 0.1 μm to 500 μm. A pseudo-attachment film containing a compound having a fluorine atom, the pseudo-adhesion film being a single-layer film, and irradiating 25 W of monochromated AlKα with respect to an analysis area of 1400 μm ́700 μm on the surface of the pseudo-adhesion film The ratio of the presence of fluorine atoms on the surface of the pseudo-adhesive film measured by the X-ray photoelectron spectroscopy measured at an emission angle of 45°, and the presence of fluorine atoms in one surface a of the pseudo-adhesion film The ratio A1 of the ratio of the fluorine atoms in the surface b on the side opposite to the surface a of the pseudo-adhesion film satisfies the relationship of the following formula (11), and the existence ratio A1 of the fluorine atom is 5% to 40%, A1/B1≧1.3 (11) A1 is a ratio A1 in which the fluorine atoms in the surface a of the film are abbreviated, and B1 is a ratio B1 of the fluorine atoms in the surface b of the pseudo-film. The pseudo-adhesive film according to claim 19, wherein the ratio A1 of the existence ratio of the fluorine atom of the pseudo-adhesion film to the fluorine atom satisfies the relationship of the following formula (12), and The fluorine atom is present in a ratio A1 of 10% to 30%, and A1/B1≧1.5 is a formula (12). A1 is a ratio A1 of a fluorine atom in the surface a of the pseudo-adhesion film, and B1 is a surface of the pseudo-attachment film b. The ratio of the presence of fluorine atoms in B1 is B1. The pseudo-attachment film according to claim 19, wherein the compound having a fluorine atom contains a lipophilic group. The pseudo-adhesive film according to claim 19, wherein the pseudo-adhesive film contains at least one selected from the group consisting of a binder and a radical polymerizable compound. The pseudo-adhesive film according to claim 19, wherein the pseudo-adhesive film is contained in a ratio of 0.03 mass% or more and less than 0.5 mass% in the total solid content of the pseudo adhesive film. A compound having a fluorine atom. A laminate comprising: a pseudo-adhesive film obtained by the production method according to claim 1 or 2, and a substrate provided on one side or both sides of the pseudo-adhesion film. A laminated body with a component wafer having a dummy film as described in claim 1 or 2 between the carrier substrate and the component wafer, one side of the dummy film and the The elements of the component wafer are in surface contact and the other side is in contact with the surface of the carrier substrate. The laminated body with a component wafer according to claim 25, wherein the area of the film surface of the dummy film is smaller than the area of the substrate surface of the carrier substrate. The laminated body with a component wafer according to claim 25, wherein when the diameter of the substrate surface of the carrier substrate is C μm, the diameter of the substrate surface of the component wafer is set to D μm. When the diameter of the film surface of the dummy film is set to T μm, (C-200) ≧T≧D is satisfied. The laminated body with a component wafer according to claim 25, wherein when the diameter of the substrate surface of the carrier substrate is C μm, the diameter of the substrate surface of the component wafer is set to D μm. The diameter of the film surface on the side in contact with the carrier substrate of the dummy film is T _C μm, and when the diameter of the film surface on the side of the contact film on the surface of the dummy film is T _D μm, it satisfies (C- 200) ≧T _C >T _D ≧D. A pseudo-concomitant composition containing a compound having a fluorine atom and containing the compound having a fluorine atom in a proportion of 0.03 mass% or more and less than 0.5 mass% in the total solid content of the pseudo-concomitant composition. The composition according to claim 29, wherein the compound having a fluorine atom contains a lipophilic group. The composition according to claim 29 or 30, which further comprises at least one selected from the group consisting of a binder and a radical polymerizable compound. The composition according to claim 31, wherein the binder is an elastomer.