KR101884256B1 - Temporary bonding film, laminate, composition for temporary bonding, and method and kit for manufacturing device - Google Patents

Abstract

It is possible to stably adhere the device wafer to the device wafer when mechanically or chemically treating the device wafer and to easily release adherence of the device wafer to the device wafer, , A composition for adhesion, a method of manufacturing a device, and a kit.
The adhesive film has a bonding area and a releasing area on the surface of the bonding area. The bonding area has a mass reduction rate of 1% by mass or less at 400 ° C when the temperature is raised at 25 ° C / 10 ° C / The solubility in N-methylpyrrolidone is less than 1 g / 100 g Solvent.

Description

TECHNICAL FIELD [0001] The present invention relates to a bonding film, a laminate, a composition for adhesion, a device manufacturing method, and a kit (TEMPORARY BONDING FILM, LAMINATE, COMPOSITION FOR TEMPORARY BONDING, AND METHOD AND KIT FOR MANUFACTURING DEVICE)

The present invention relates to an adhesive film, a laminate, a composition for adhering, a method of manufacturing a device, and a kit. More particularly, the present invention relates to an adhesive film, a laminate, a composition for bonding, a method of manufacturing a device, and a kit, which can be preferably used for manufacturing various devices such as semiconductor devices.

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

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

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

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

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

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

In order to solve the above problems, the device wafer and the supporting substrate (carrier substrate) before thinning are temporarily fixed (adhered) by an adhesive, and the back surface of the device wafer is ground to be thinned. Is known.

For example, Patent Document 1 discloses a method for manufacturing a semiconductor device, which includes a step of temporarily fixing a device wafer to a support member with a temporarily fixing film comprising a specific polyimide resin interposed between the support member and the device wafer, A step of subjecting the device wafer to predetermined processing, a step of bringing the organic solvent into contact with the temporary film to dissolve a part or all of the temporary film, and to separate the processed device wafer from the supporting member, A method of manufacturing a semiconductor device having a step of disposing a semiconductor device is disclosed.

On the other hand, Patent Document 2 discloses an invention relating to a semiconductor element fixing adhesive (an adhesive for die bonding) for bonding semiconductor elements or a semiconductor element to a support substrate. (A1) a polyimide resin having a glass transition temperature of 60 占 폚 or less and a weight average molecular weight of 10,000 to 100,000, and (A2) a resin component in an amount of 20% by mass in N-methyl-2-pyrrolidone (B) a thermoplastic component (B) containing a thermoplastic resin (A) containing a polyimide resin having a viscosity at 25 ° C of at least 10 poise at 25 ° C and an epoxy resin (B1) and a bismaleimide resin Is formed into a sheet shape.

Patent Document 1: JP-A-2014-29999 Patent Document 2: JP-A-2012-241134

In the case where the surface of the device wafer and the supporting substrate are adhered to each other, an adhering force between the surface of the device wafer and the supporting substrate is required to have a constant strength, There is a demand for a property of easily releasing the adhesion state of the substrate.

Patent Document 1 discloses that a film for temporary fixation is released from a device wafer by contacting an organic solvent with a temporary film using a film which is soluble in an organic solvent. However, according to the investigations of the present inventors, it has been found that the temporary fixing film disclosed in Patent Document 1 is inferior in tolerance.

In the device manufacturing process, various chemicals may be used. For example, when the device wafer is thinned by a wet process, an etchant is used. Therefore, in the manufacturing process of the device, there is a demand for an improvement in tolerance of the adhesive film which may be exposed to various chemicals.

Further, in the device manufacturing process, recently, a device may be provided for processing at a higher temperature. Therefore, in order to cope with various manufacturing processes, further improvement of the heat resistance is demanded in the adhesive film.

In addition, the invention disclosed in Patent Document 2 is an invention relating to an adhesive for fixing a semiconductor element used for bonding semiconductor elements or a semiconductor element and a support substrate, and does not adhere the device wafer and the support substrate to each other. As a result, the semiconductor element fixing adhesive of Patent Document 2 does not have such a property as to release adhesion between the device wafer and the support substrate.

SUMMARY OF THE INVENTION The present invention has been made in view of the above background and an object of the present invention is to provide a device wafer which can stably adhere to a device wafer when mechanically or chemically treating the device wafer, A laminate, a composition for adhesion, a method of manufacturing a device, and a kit.

Means for Solving the Problems As a result of intensive studies to solve the above problems, the inventors of the present invention have found that when the temperature rise at 25 占 폚 at 10 占 폚 / min, the mass reduction rate at 400 占 폚 is 1% by mass or less and N-methylpyrrolidone Is not more than 1 g / 100 g Solvent, and the adhesion layer having a release area on the surface of the adhesion area can stably adhere the device wafer and can easily release adhesion to the device wafer And has excellent tolerance, and based on these findings, the present invention has been accomplished. The present invention provides the following.

≪ 1 > The adhesive sheet according to any one of < 1 >, wherein the adhesive region has a releasing region on the surface of the adhesive region and the adhesive region has a mass reduction rate of 1% by mass or less at 400 deg. A solubility in N-methylpyrrolidone of 1 g / 100 g Solvent or less.

≪ 2 > The bonding region is formed by a resin composition comprising a resin containing a heterocyclic ring containing at least one member selected from a polyimide resin, a polyamideimide resin, a polybenzimidazole resin and a polybenzoxazole resin and a maleimide resin, 1 >.

<3> The resin composition according to <3>, wherein the heterocyclic ring-containing resin is at least one selected from the group consisting of γ-butyrolactone, cyclopentanone, N-methylpyrrolidone, cyclohexanone, glycol ether, dimethylsulfoxide and tetramethylurea Is a polyimide resin having a solubility of not less than 10 g / 100 g Solvent at 25 캜 with respect to a solvent of the following formula (1).

<4> The adhesion film according to <2> or <3>, wherein the maleimide resin is a bismaleimide resin.

<5> The adhesive film according to any one of <1> to <4>, wherein 50 to 100% by mass of the crosslinking component contained in the adhesive region is a maleimide resin.

<6> The adhesion film according to any one of <1> to <5>, wherein the adhesion region further contains a thermal polymerization initiator.

<7> The adhesive layer according to <6>, wherein the thermal polymerization initiator has a half-life temperature for one minute of 130 to 300 ° C.

<8> The adhesion film according to <6> or <7>, wherein the thermal polymerization initiator is an organic peroxide.

<9> The adhesive layer according to any one of <1> to <8>, wherein the release region comprises a compound containing at least one selected from a fluorine atom and a silicon atom.

<10> The adhesive film according to any one of <1> to <9>, wherein the releasing region contains a fluorine-based silane coupling agent.

&Lt; 11 > A laminate having a device wafer on a surface on a release-region side of a self-adhesive film according to any one of <1> to <10>.

<12> A resin composition containing a heterocyclic ring-containing resin containing at least one member selected from a polyimide resin, a polyamideimide resin, a polybenzimidazole resin and a polybenzoxazole resin, a crosslinking component and a solvent, And 50 to 100 mass% is a maleimide resin.

The heterocyclic ring-containing resin may be at least one selected from the group consisting of γ-butyrolactone, cyclopentanone, N-methylpyrrolidone, cyclohexanone, glycol ether, dimethyl sulfoxide and tetramethylurea Is a polyimide resin having a solubility of not less than 10 g / 100 g Solvent at 25 캜 with respect to a solvent of the composition.

&Lt; 14 > The composition according to < 12 >, wherein the maleimide resin is a bismaleimide resin.

<15> The adhesive composition according to any one of <12> to <14>, further comprising a thermal polymerization initiator.

The thermosetting polymerization initiator has a half-life temperature for one minute of 130 to 300 ° C.

The thermosetting polymerization initiator is an organic peroxide.

<18> The adhesive composition according to any one of <12> to <17>, further comprising a releasing component.

<19> The adhesive bonding composition according to <18>, wherein the releasing component comprises a compound containing at least one selected from a fluorine atom and a silicon atom.

<20> The adhesive composition according to <18> or <19>, wherein the releasing component is a fluorine-based silane coupling agent.

&Lt; 21 > A method for manufacturing a device, which comprises a step of applying the adhesive composition according to any one of <12> to <20>.

<22> A kit for forming an adhesion film according to any one of <1> to <10>, which comprises a composition for adhesion as described in any one of <12> to <20>, a release mold A kit comprising a composition for forming a region.

According to the present invention, when performing a mechanical or chemical treatment on a device wafer, it is possible to stably adhere the device wafer, to easily release the adhesion to the device wafer, An adhesive film can be provided. In addition, it becomes possible to provide a laminate, a composition for adhesion, a device manufacturing method, and a kit.

1A, 1B, and 1C are schematic cross-sectional views illustrating the adhesion of a support substrate and a device wafer, respectively, a schematic cross-sectional view showing a device wafer adhered by a support substrate, and FIGS. Is a schematic cross-sectional view showing a state in which a device wafer to which an adhesive is adhered is thinned.

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

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

The term "active ray" or "radiation" in the present specification means, for example, visible ray, ultraviolet ray, far ultraviolet ray, electron ray, X ray and the like.

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

As used herein, the term "exposure" means not only exposure by deep ultraviolet rays such as mercury lamps, ultraviolet rays, and excimer lasers, X-rays, EUV light, etc., but also drawing by particle beams such as electron beams and ion beams It means.

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

In the present specification, the weight average molecular weight and the number average molecular weight are defined as polystyrene reduced values by Gel Permeation Chromatography (GPC) measurement. In this specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) can be measured by using, for example, HLC-8220 (manufactured by TOSOH CORPORATION) as a column, TSKgel Super AWM- , 6.0 mm ID x 15 cm) can be obtained by using 10 mmol / L lithium bromide NMP (N-methylpyrrolidinone) solution as an eluent.

As used herein, "monomer" and "monomer" are synonyms. The monomer in the present invention is distinguished from an oligomer and a polymer, and refers to a compound having a weight average molecular weight of 2,000 or less.

The polymer compound in the present invention means a compound having a weight average molecular weight of more than 2000.

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

<Adhesive film>

The adhesion film of the present invention has an adhesion region and a release region on the surface of the adhesion region, and the adhesion region has a mass reduction rate of 1% by mass or less at 400 占 폚 when the temperature is raised at 25 占 폚 to 10 占 폚 / , The solubility in N-methylpyrrolidone at 25 占 폚 is 1 g / 100 g Solvent or less.

Since the adhesive film of the present invention has a release region on the surface of the adhesive region, the device wafer is laminated on the surface of the release region of the adhesive film, and the device wafer in the adhesive film is laminated By disposing the supporting substrate on the side opposite to the side of the device wafer while appropriately protecting the device wafer having a structure such as a bump or the like, the adhesive film can be simply peeled off from the device wafer after mechanically or chemically treating the device wafer It can peel off.

In addition, since the mass reduction rate at 400 ° C when the temperature is raised at 25 ° C at 10 ° C / minute is not more than 1% by mass, the adhesion region is excellent in heat resistance, and even in the case where the process is performed at a high temperature, It can be adhered stably. Further, since the adhesive film is hardly thermally deteriorated, the adhesive film can be easily peeled off from the device wafer by mechanical peeling or the like even after the high temperature process.

Since the device wafer and supporting substrate in the present invention can be peeled off by mechanical peeling, the solubility of the adhesive region in N-methylpyrrolidone at 25 캜 can be made to be 1 g / 100 g Solvent or less, Is excellent. Therefore, even when a chemical such as an etching solution adheres to the adhesive film during the processing of the device wafer, for example, the device wafer can stably adhere to the adhesive film.

As described above, even when various treatments such as high-temperature treatment and chemical treatment are performed on the device wafer, the adhesive film of the present invention can stably adhere to the device wafer and can be easily peeled off from the device after treatment have.

Further, in the present invention, the mass reduction rate is a value measured by the calorimeter apparatus (TGA) under the above-described temperature elevation condition under a nitrogen stream.

In the present invention, the solubility is measured by repeating the operation of adding a certain amount of the sample to 100 g of the solvent while stirring to confirm the solubility and, when completely dissolved, adding the sample in a predetermined amount with stirring, Deg.] C for 1 hour, the solubility was defined as the amount immediately before the sample was no longer dissolved.

The adhesive film of the present invention has an adhesive area and a release area on the surface of the adhesive area.

The adhesive film of the present invention has a mass reduction rate of 1% by mass or less, preferably 0.90% by mass or less, and preferably 0.8% by mass or less, at 400 ° C when the adhesive region is heated from 25 ° C to 10 ° C / More preferably 0.7 mass% or less, particularly preferably 0.6 mass% or less, and most preferably 0.5 mass% or less. With this range, even when the wafer is subjected to a high-temperature process up to 400 ° C, the device wafer can be stably bonded. Further, since the adherent film is hardly thermally deteriorated, the adherent film can be easily peeled off from the device wafer by mechanical peeling or the like even after the high temperature process.

The adhesive film of the present invention has a solubility of 1 g / 100 g Solvent or less, preferably not more than 0.8 g / 100 g Solvent, and not more than 0.5 g / 100 g Solvent, at 25 ° C in N-methylpyrrolidone More preferably 0.1 g / 100 g Solvent or less. According to this aspect, even when the chemical solution used during the manufacturing process of the device is in contact with the adhesive film, the device wafer can be adhered stably.

In the adhesion film of the present invention, the adhesion region and the release region may exist as independent adhesive layers and release layers, respectively, and the boundary between the adhesion region and the release region may not be clear. As an example of a mode in which the boundary between the adhesive region and the releasing region is not clear, there is an embodiment in which the releasing component is localized on the surface layer in the adhesive layer to form the releasing region. The adhesive region may be composed of two or more kinds of adhesive layers, and the release region may be composed of two or more release layers.

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

<< Adhesion area >>

The adhesive film of the present invention has an adhesive area. The bonding area is to bond the device wafer and the supporting substrate.

The adhesion region has a mass reduction rate of 1 mass% or less at 400 占 폚 when heated at 25 占 폚 at 10 占 폚 / min and solubility in N-methylpyrrolidone at 25 占 폚 is 1 g / Is used.

The average thickness of the adhesive region is preferably 0.1 to 500 占 퐉, more preferably 0.5 to 500 占 퐉, still more preferably 0.5 to 50 占 퐉, and particularly preferably 0.5 to 10 占 퐉. When the adhesive film of the present invention is applied to a device wafer having a structure on the surface, it is preferable that the average thickness of the adhesive region is thicker than the height of the structure of the device wafer described later.

When the adhesive film of the present invention is a laminate structure formed by laminating layers constituting the releasing regions on the surface layer of the adhesive layer, the average thickness of the layers constituting the adhesive regions is preferably 1 to 50 占 퐉, More preferably 20 mu m.

In the case where the adhesive film of the present invention is an embodiment in which the release component is localized on the surface layer in the adhesive layer to form the release region, the average thickness of the adhesive region is preferably 1 to 50 탆, more preferably 2 to 20 탆.

In the present invention, the average thickness of the adhesive region is defined as an average value of five points measured by ellipsometry.

The adhesive region can be preferably used as far as it can attain the above mass reduction rate and solubility, but preferably includes the resin component A described later and a maleimide resin. When the adhesive region includes a resin component A and a maleimide resin to be described later, the resin component A can be interposed between the three-dimensionally crosslinked maleimide resin, and an adhesive region excellent in heat resistance and tolerance can be easily obtained.

<<< Resin Component A >>>

In the present invention, as the resin component A that can be included in the bonding region, any resin may be used as long as it satisfies the above-described mass reduction rate and solubility. In the present invention, it is assumed that the resin component A does not include a maleimide resin.

As the resin component A, for example, a resin containing a heterocyclic ring (preferably a polyimide resin, a polyamideimide resin, a polybenzimidazole resin, a polybenzoxazole resin), a terpene resin, a terpene phenol resin, Hydrogenated terpene resin, hydrogenated terpene phenol resin, rosin, rosin ester, hydrogenated rosin, hydrogenated rosin ester, polymerized rosin, polymerized rosin ester, modified rosin, rosin modified phenol resin, alkylphenol resin, aliphatic petroleum resin, aromatic petroleum (For example, methylpentene copolymer), a cycloolefin copolymer (for example, a norbornene copolymer such as a norbornene copolymer), a hydrogenated petroleum resin, a modified petroleum resin, an alicyclic petroleum resin, a coumarone petroleum resin, Copolymers, dicyclopentadiene copolymers, tetracyclododecene copolymers), novolak resins, phenol resins, epoxy resins, melamine resins, ureas (EPDM rubber), polyvinyl chloride resin, polystyrene resin, polystyrene copolymer resin (for example, acrylonitrile-butadiene-styrene copolymer resin, (ABS resin), acrylonitrile styrene copolymer (AS resin), methyl methacrylate-styrene copolymer resin (MS resin)), polyacetic acid vinyl resin, tetrafluoroethylene resin (PTFE resin), copolymer of tetrafluoroethylene and perfluoroalkoxyethylene (PFA resin), tetrafluoroethylene / hexafluoropropylene copolymer (FEP resin), ethylene-TFE copolymer resin, polyvinylidene fluoride (PVDF resin), polychlorotrifluoroethylene (PCTFE resin), ethylene-chlorotrifluoroethylene resin (CTFE resin), TFE-perfluorodimethyldi Polyvinylidene fluoride resin, polyvinylidene fluoride resin, polyvinylidene fluoride resin, polyvinylidene fluoride resin, polyvinylidene fluoride resin, polyvinylidene fluoride resin, polyvinylidene fluoride resin, Synthetic resins such as polyolefin resins, polyphenylene sulfide resins, polysulfone resins, polyethersulfone resins, polyarylate resins and polyether ketone resins, and natural resins such as natural rubber.

Among them, a polyimide resin, a polyamideimide resin, a polybenzimidazole resin, a polybenzoxazole resin, a polycarbonate resin, a polyether sulfone resin and a polyester resin are preferable, and a polyimide resin, a polyamideimide resin, A polybenzimidazole resin and a polybenzoxazole resin are more preferable, and a polyimide resin or a polyamideimide resin is more preferable, and a polyimide resin is particularly preferable. Since these resins are excellent in heat resistance, the mass reduction rate is easily achieved.

The polyimide resin is preferably at least one solvent selected from the group consisting of? -Butyrolactone, cyclopentanone, N-methylpyrrolidone, cyclohexanone, glycol ether, dimethyl sulfoxide and tetramethylurea Is a polyimide resin having a solubility of 10 g / 100 g or more at 25 캜. According to this embodiment, the adhesive region can be formed by a coating method.

<<<< Polyimide resin >>>>

As the polyimide resin, those obtained by condensation reaction of tetracarboxylic acid dianhydride and diamine by a known method can be used.

As a known method, for example, a method of dehydrating and ring closure of a polyamic acid obtained by mixing tetracarboxylic dianhydride and diamine at approximately equimolar mixing in an organic solvent at a reaction temperature of 80 ° C or lower can be given. Here, approximately equimolar means that the molar ratio of tetracarboxylic acid dianhydride to diamine is in the vicinity of 1: 1. If necessary, the composition ratio of the tetracarboxylic dianhydride and the diamine may be adjusted so that the total amount of the diamine is 0.5 to 2.0 moles relative to 1.0 moles of the tetracarboxylic dianhydride in total. The weight average molecular weight of the polyimide resin can be adjusted by adjusting the composition ratio of tetracarboxylic dianhydride and diamine within the above range.

Examples of the tetracarboxylic acid dianhydride include, but are not limited to, pyromellitic dianhydride, 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, 2,2', 3,3'- Bis (2,3-dicarboxyphenyl) propane dianhydride, 1,1-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2- Bis (3,4-dicarboxyphenyl) ethane dianhydride, bis (2,3-dicarboxyphenyl) methane dianhydride, bis (3,4 (3,4-dicarboxyphenyl) sulfone dianhydride, 3,4,9,10-perylene tetracarboxylic acid dianhydride, bis (3,4-dicarboxyphenyl) ether Dianhydride, benzene-1,2,3,4-tetracarboxylic acid dianhydride, 3,4,3 ', 4'-benzophenone tetracarboxylic acid dianhydride, 2,3,2', 3'-benzophenone tetracarboxylic acid dianhydride Water, 2,3,3 ', 4'-benzophenone tetracarboxylic acid imine Water, 1,2,5,6-naphthalenetetracarboxylic acid dianhydride, 1,4,5,8-naphthalenetetracarboxylic acid dianhydride, 2,3,6,7-naphthalenetetracarboxylic acid dianhydride, 1,2,4- 5-naphthalenetetracarboxylic acid dianhydride, 2,6-dichloronaphthalene-1,4,5,8-tetracarboxylic acid dianhydride, 2,7-dichloronaphthalene-1,4,5,8-tetracarboxylic acid dianhydride, 2,3,6,7-tetrachloronaphthalene-1,4,5,8-tetracarboxylic acid dianhydride, phenanthrene-1,8,9,10-tetracarboxylic acid dianhydride, pyrazine-2,3,5,6 -Tetracarboxylic acid dianhydride, thiophene-2,3,5,6-tetracarboxylic acid dianhydride, 2,3,3 ', 4'-biphenyltetracarboxylic acid dianhydride, 3,4,3', 4'- (3,4-dicarboxyphenyl) dimethylsilane dianhydride, bis (3,4-dicarboxyphenyl) diisocyanate dianhydride, 2,3,4'- Methylphenylsilane dianhydride, bis (3,4-dicarboxyphenyl) diphenylsilane (3,4-dicarboxyphenyldimethylsilyl) benzene dianhydride, 1,3-bis (3,4-dicarboxyphenyl) -1,1,3,3-tetramethyl di Cyclohexane dianhydride, p-phenylene bis (trimellitate anhydride), ethylene tetracarboxylic acid dianhydride, 1,2,3,4-butane tetracarboxylic acid dianhydride, decahydronaphthalene-1,4,5,8 -Tetracarboxylic acid dianhydride, 4,8-dimethyl-1,2,3,5,6,7-hexahydronaphthalene-1,2,5,6-tetracarboxylic acid dianhydride, cyclopentane- Tetracarboxylic acid dianhydride, pyrrolidine-2,3,4,5-tetracarboxylic acid dianhydride, 1,2,3,4-cyclobutante tetracarboxylic acid dianhydride, bis (exo- bicyclo [2 , 2,1 heptane-2,3-dicarboxylic acid dianhydride, bicyclo- [2,2,2] -oct-7-ene-2,3,5,6-tetracarboxylic acid dianhydride, 2,2 Bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2'-bis [4- (3,4-dicarboxyphenyl) (3,4-dicarboxyphenyl) phenyl] hexa (2,2-bis [4- (3,4-dicarboxyphenoxy) diphenyl sulfide dianhydride, 1,4-bis (2-hydroxyhexafluoroisopropyl) benzene bis (trimellitic anhydride) (2-hydroxyhexafluoroisopropyl) benzene bis (trimellitic anhydride), 5- (2,5-dioxotetrahydrofuryl) -3-methyl- Hexene-1,2-dicarboxylic acid dianhydride, tetrahydrofuran-2,3,4,5-tetracarboxylic dianhydride, 4,4'-oxydiphthalic dianhydride, 1,2- (ethylene) bis (Tetramethylene anhydride), 1,5- (pentamethylene) bis (trimellitate anhydride), 1,3- (tetramethylene anhydride), 1,4- Water), 1,6- (hexamethylene) bis (trimellitate anhydride) 1,7- (heptamethylene) bis (trimellitate anhydride) 1,8- (octamethylene) bis (trimellitate anhydride) , 1,12- (nonamethylene) bis (trimellitate anhydride), 1,10- (decamethylene) bis (trimellitate anhydride), 1,12- (Trimellitate anhydride), 1,18- (octadecamethylene) bis (trimellitate anhydride), and the like. These may be used singly or in combination of two or more kinds. . Among them, 3,4,3 ', 4'-benzophenonetetracarboxylic dianhydride, 2,3,2', 3'-benzophenonetetracarboxylic dianhydride, 2,3,3 ', 4'-benzophenonetetra Carboxylic acid dianhydride is preferable, and 3,4,3 ', 4'-benzophenonetracarboxylic acid dianhydride is more preferable.

The diamine is not particularly limited, and examples thereof include o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 3,3'-diaminodiphenylether, 3,4'- Aminodiphenylether, 4,4'-diaminodiphenylether, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, bis (4-amino- (4-amino-3,5-diisopropylphenyl) methane, 3,3'-diaminodiphenyldifluoromethane, 3,4'-diaminodiphenyl Diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfone, 4,4'-diamino Diphenyl sulfone, 3,3'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl ketone, 4'-diaminodiphenyl ketone, 4,4'-di Aminophenyl ketone, 3- (4-aminophenyl) -1,1,3-trimethyl-5-aminoindene, 2,2-bis Bis (3-aminophenyl) hexafluoropropane, 2,2- (3-aminophenyl) propane, Bis (4-aminophenoxy) benzene, 1,4-bis (4-aminophenyl) (3-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 3,3 ' 2, 4 '- (1,4-phenylenebis (1-methylethylidene)) bisaniline, 4,4' Bis (4- (3-aminophenoxy) phenyl) hexafluoropropane, 2,2-bis (4- 4-aminophenoxy) phenyl) hexafluoropropane, bis (4- (3-aminophenoxy) phenyl) sulfide, (4-aminophenoxy) phenyl) sulfone, bis (4- (4-aminophenoxy) (Aminomethyl) cyclohexane, 2,2-bis (4-aminophenoxy) aminophenoxy, 2,2-bis Phenyl) propane, polyoxypropylene diamine, 4,9-dioxadecane-1,12-diamine, 4,9,14-trioxaheptadecane-1,17-diamine, Amino ethane, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8 Diaminodecane, 1,1-diaminododecane, 1,1-diaminododecane, 1,1-diaminododecane, 1,1-diaminododecane, 1,3-bis (3-aminopropyl) tetramethyldisiloxane, and the like.

Among these diamines, it is preferable to use at least one selected from the group consisting of 3- (4-aminophenyl) -1,1,3-trimethyl-5-aminoindene, 1,3-bis (3-aminopropyl) tetramethyldisiloxane, Diamine, 1,6-diaminohexane, and 4,9,14-tri (4-aminophenoxyphenyl) propane, 4,9-dioxadecane- Oxaheptadecane-1,17-diamine, and more preferably at least one selected from the group consisting of 3- (4-aminophenyl) -1,1,3-trimethyl-5-aminoindene Do.

Examples of the solvent used in the reaction of the tetracarboxylic acid dianhydride with diamine include N, N-dimethylacetamide, N-methyl-2-pyrrolidone and N, N-dimethylformamide. 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 占 폚, more preferably less than 90 占 폚. Imidization of polyamic acid is typically performed by heat treatment under an inert atmosphere (typically, a vacuum or a nitrogen atmosphere). The heat treatment temperature is preferably 150 占 폚 or higher, more preferably 180 to 450 占 폚.

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

In the present invention, the polyimide resin is at least one selected from the group consisting of? -Butyrolactone, cyclopentanone, N-methylpyrrolidone, cyclohexanone, glycol ether, dimethylsulfoxide and tetramethylurea A polyimide resin having a solubility of not less than 10 g / 100 g Solvent at 25 캜 for a solvent of a species is preferable.

The polyimide resin having such a solubility can be obtained, for example, by reacting 3,4,3 ', 4'-benzophenonetetracarboxylic dianhydride with 3- (4-aminophenyl) -1,1,3- And polyimide resins obtained by reacting a polyimide resin with an aminoindine. This polyimide resin is particularly excellent in heat resistance.

As the polyimide resin, a commercially available product may be used. (All manufactured by Fuji Photo Film Co., Ltd.), GPT-LT (manufactured by Gunpo Aigaku Co., Ltd.), SOXR-S, SOXR-M, SOXR-U, SOXR- Manufactured by KODOSHI KOGYO CO., LTD.).

<<<< Polyamideimide Resin >>>>

As the polyamideimide resin, for example, those obtained by reacting an acid component such as a polycarboxylic acid or a derivative thereof with a diamine or diisocyanate in a polar solvent can be used.

Examples of the polar solvent include N-methyl-2-pyrrolidone (NMP) and N, N'-dimethylacetamide. The above reaction can be carried out by stirring while heating at a predetermined temperature (usually about 60 to 200 ° C).

Examples of the acid component used for preparing the polyamideimide resin include trimellitic acid, trimellitic acid anhydride, trimellitic acid chloride; Pyromellitic acid (benzene-1,2,4,5-tetracarboxylic acid), biphenyltetracarboxylic acid, biphenylsulfone tetracarboxylic acid, benzophenonetetracarboxylic acid, biphenyl ether tetracarboxylic acid, ethylene glycol bevel trimellitate, Tetracarboxylic acids such as propylene glycol bistrimellitate and acid anhydrides or acid chlorides thereof; But are not limited to, oxalic acid, adipic acid, malonic acid, sebacic acid, azelaic acid, dodecane dicarboxylic acid, dicarboxy polybutadiene, dicarboxy poly (acrylonitrile- butadiene), dicarboxy poly Aliphatic dicarboxylic acids such as dienes; Cycloaliphatic dicarboxylic acids such as 1,4-cyclohexane dicarboxylic acid, 1,3-cyclohexane dicarboxylic acid, 4,4'-dicyclohexylmethane dicarboxylic acid and dimeric acid; Aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, diphenylsulfon dicarboxylic acid, diphenyl ethadecarboxylic acid and naphthalenedicarboxylic acid.

These acidic components may be used alone or in combination of two or more. Of these, trimellitic anhydride is preferable from the viewpoints of reactivity, heat resistance, solubility and the like.

As the diamine or diisocyanate used in the production of the polyamideimide resin,

Aliphatic diamines such as ethylene diamine, propylene diamine, and hexamethylene diamine; and diisocyanates thereof; Alicyclic diamines such as 1,4-cyclohexane diamine, 1,3-cyclohexane diamine, isophorone diamine, 4,4'-dicyclohexyl methane diamine, and their diisocyanates Nate; m-phenylenediamine, p-phenylenediamine, 4,4'-diaminodiphenylmethane, 4'-diaminodiphenyl ether, 4,4'-diaminodiphenylsulfone, benzidine, o Aromatic diamines such as tolylidine, 2,4-tolylene diamine, 2,6-tolylene diamine and xylylenediamine, and diisocyanates thereof.

These may be used alone or in combination of two or more. Among them, 4,4'-diaminodiphenylmethane and its diisocyanate, 2,4-tolylene diamine and its diisocyanate, o (4'-diaminodiphenylmethane and its isocyanate) from the viewpoints of heat resistance, mechanical properties, solubility, Tolidine and its diisocyanate, isophoronediamine and its diisocyanate, p-phenylenediamine and diisocyanates thereof are preferable, and p-phenylenediamine is particularly preferable .

The number average molecular weight (Mn) of the polyamideimide resin is preferably 5,000 to 100,000. More preferably 10,000 to 50,000.

When the number average molecular weight (Mn) of the polyamideimide resin is 5,000 or more, durability is good. When the number average molecular weight (Mn) of the polyamideimide resin is 100,000 or less, the solution viscosity is low, and the adhesive region is easily coated.

As the polyamideimide resin, a commercially available product may be used. For example, Durimide (registered trademark) 10 or 32 (manufactured by Fuji Photo Film Co., Ltd.), Viromax (registered trademark) 13NX (Toyobo Co.), or Rika Coat (manufactured by Shin Nippon Rika KK).

<<<< Polybenzimidazole Resin >>>>

As the polybenzimidazole resin, for example, those obtained by reacting an aromatic tetraamine with a dicarboxylic acid component can be used.

The aromatic tetraamines include, for example, 1,2,4,5-tetraaminobenzene, 1,2,5,6-tetraaminonaphthalate, 2,3,6,7-tetraaminonaphthalate, 3,3 ' , 4,4'-tetraminodiphenylmethane, 3,3 ', 4,4'-tetraminodiphenyl ether, 3,3', 4,4'-tetramonodiphenyl-2,2-propane , 3,3 ', 4,4'-tetramino diphenyl thioether, and 3,3', 4,4'-tetramino diphenyl sulfone. A preferred aromatic tetraamine is 3,3 ', 4,4'-tetraaminobiphenyl.

The dicarboxylic acid component includes, for example, isophthalic acid, terephthalic acid, 4,4'-biphenyldicarboxylic acid, 1,4-naphthalenedicarboxylic acid, diphenic acid (2,2'- biphenyldicarboxylic acid), phenylindene dicarboxylic acid , 1,6-naphthalene dicarboxylic acid, 2,6-naphthalene dicarboxylic acid, 4,4'-diphenyl thioether dicarboxylic acid, 4,4'-diphenyl sulfone dicarboxylic acid, 4,4'- Carboxylic acid.

The dicarboxylic acid component is preferably introduced at a ratio of about 1 mole of the dicarboxylic acid component per mole of the aromatic tetraamine. In addition, the optimum ratio of the reactants in the polymerization system is easily determined by those skilled in the art.

Examples of the polybenzimidazole resin include poly-2,2 '- (m-phenylene) -5,5'-bibenzimidazole, poly-2,2' - (biphenylene- -Bibenzimidazole, poly-2,2 '- (biphenylene-4' '' ') - 5,5'-bibenzimidazole, , 1 ", 3" trimethyl phosphorous mono-3 "5" -p-phenylene-5,5'-bibenzimidazole, 2,2 '- (m- Benzimidazole / 2,2- (1 ", 1 ", 3" -trimethyl phosphorous monoren) 5 &quot;, 3 " , 2 '- (m-phenylene) -5,5'-bibenzimidazole / 2,2'-biphenylene-2' '' - 5,5'-bibenzimidazole copolymer, poly -2,2 '- (furylene-2 ", 5") -5,5'-bibenzimidazole, poly-2,2' - (m-phenylene) -5,5'- , Poly-2,2 '- (naphthalene-2 &quot;, 6 ") - 5,5'-bibenzimidazole, Bibenzimidazole, poly-2,2'-amylene-5,5'-bibenzimidazole, poly-2,2'-octamethylene-5,5'-bibenzimidazole, '- (m-phenylene) -da Polyimides such as imidazobenzene, poly-2,2'-cyclohexenyl-5,5'-bibenzimidazole, poly-2,2'- (m-phenylene) -5,5'- ) Ether, poly-2,2'- (m-phenylene) -5,5'-di (benzimidazole) sulfide, poly- (Benzimidazole) sulfone, poly-2,2'- (m-phenylene) -5,5'-di (benzimidazole) methane, , 5'-di (benzimidazole) propane, and poly-ethylene-1,2,2,2 "- (m-phenylene) -5,5" -dibenzimidazole) ethylene- .

As the polybenzimidazole resin, commercially available products may be used. For example, MRS0810H (manufactured by PBI).

<<<< Polybenzoxazole Resin >>>>

The polybenzoxazole resin is obtained by dissolving a bisaminophenol compound and a polyhydroxyamide synthesized from a dicarboxylic acid derivative in a solvent and subjecting to a dehydration ring-closure reaction.

Examples of bisaminophenol compounds include 2,4-diaminoresorcinol, 4,6-diaminoresorcinol, 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, Bis (4-amino-3-hydroxyphenyl) hexafluoropropane, 2,2-bis Hydroxyphenyl) propane, 3,3'-diamino-4,4'-dihydroxydiphenylsulfone, 4,4'-diamino-3,3'-dihydroxydiphenylsulfone, Dihydroxybiphenyl, 4,9'-diamino-3,3'-dihydroxybiphenyl, 9,9-bis (4 - ((4- Phenyl) fluorene, 9,9-bis (4- (3-hydroxyphenoxy) phenyl) fluorene, 9,9- (4-amino-3-hydroxyphenyl) fluorene, 1,1'-binaphthyl-3,3'- Diamino-2,2'-diol, bis (2 - ((4- (3-amino-4-hydroxyphenoxy)) - 1,1'-binaphthyl, bis 3,3'-diamino-4,4'-dihydroxydiphenyl ether, 4,4'-diamino-3,3'-dihydroxydiphenyl ether, 2,2-bis (3- 2-trifluoromethylphenyl) propane, 2,2-bis (4-amino-3-hydroxy-2-trifluoromethylphenyl) propane, Amino-3-hydroxy-5-trifluoromethylphenyl) propane, 2,2-bis (3- Amino-3-hydroxy-6-trifluoromethylphenyl) propane, 2,2-bis (3- Amino-3-hydroxy-2-trifluoromethylphenyl) hexafluoropropane, 2,2-bis (4-amino- Bis (4-amino-3-hydroxy-5-trifluoromethylphenyl) hexafluoropropane, 2,2- Bis (4-amino-4-hydroxy-6-trifluoromethylphenyl) hexafluoropropane, 2,2- 3-hydroxy-6-trifluoromethylphenyl) hexafluoropropane, 3,3'-diamino-4,4'-dihydroxy-2,2'-bis (trifluoromethyl) 4,4'-diamino-3,3'-dihydroxy-2,2'-bis (trifluoromethyl) biphenyl, 3,3'- , 5'-bis (trifluoromethyl) biphenyl, 4,4'-diamino-3,3'-dihydroxy-5,5'-bis (trifluoromethyl) Diamino-4,4'-dihydroxy-6,6'-bis (trifluoromethyl) biphenyl, 4,4'-diamino-3 , 3'-dihydroxy-6,6'-bis (trifluoromethyl) biphenyl, and the like.

Examples of dicarboxylic acid derivatives include isophthalic acid, terephthalic acid, 4,4'-biphenyldicarboxylic acid, 3,4'-biphenyldicarboxylic acid, 3,3'-biphenyldicarboxylic acid, 2,6- Naphthalene dicarboxylic acid, 4,4'-sulfonyl bisbenzoic acid, 3,4'-sulfonyl bisbenzoic acid, 3,3'-sulfonyl bisbenzoic acid, 4,4'-oxybisbenzoic acid, 3,4'- (3-carboxyphenyl) propane, 2,2-bis (4-carboxyphenyl) propane, 2,2- Bis (4-carboxyphenoxy) biphenyl, 4,4'-bis (3-carboxyphenyl) hexafluoropropane, Carboxyphenoxy) biphenyl, 3,3'-bis (4-carboxyphenoxy) biphenyl, 3,4'-bis Bis (4-carboxyphenoxy) -p-terphenyl, 4,4'-bis (4-carboxyphenoxy) biphenyl, Pe (4-carboxyphenoxy) -p-terphenyl, 3,3'-bis (4-carboxyphenoxy) -Bis (3-carboxyphenoxy) -m-terphenyl, 3,3'-bis (4-carboxyphenoxy) Terphenyl, 4,4'-bis (3-carboxyphenoxy) -m-terphenyl, 3,4'-bis (3-carboxyphenoxy) (3-carboxyphenoxy) -m-terphenyl, 2, 3'-bis (3-carboxyphenoxy) Bis (trifluoromethyl) -4,4'-biphenyldicarboxylic acid, 2,2'-bis (trifluoromethyl) -4,4'-biphenyldicarboxylic acid, 3,3'- (Trifluoromethyl) -3,3'-biphenyldicarboxylic acid, 2,2'-dimethyl-4,4'-biphenyldicarboxylic acid, 3,3'-dimethyl-4,4'- Dicarboxylic acid, 2,2'-dimethyl-3,3'-biphenyldicarboxylic acid, 3-fluoroisophthalic acid, 2-fluoroisophthalic acid, 2-fluoroterephthalic acid, Dicarbon selected from the group consisting of 1-hydroxybenzotriazole, 1-hydroxybenzothiazole, 1-hydroxybenzotriazole, 2-hydroxybenzotriazole, 2-hydroxybenzotriazole, , p-nitrophenol, and the like, and the like.

Commercially available polybenzoxazole resins may be used. For example, CRC-8800 (manufactured by Sumitomo Bakelite Co., Ltd.).

The adhesive region preferably contains the resin component A in an amount of 1 to 99 mass%, more preferably 10 to 90 mass%, and more preferably 25 to 75 mass% with respect to the total solid content (amount excluding the solvent) Is particularly preferable.

The adhesive film preferably contains the resin component A in an amount of 1 to 99 mass%, more preferably 10 to 90 mass%, and more preferably 25 to 75 mass%, based on the total solid content (amount excluding the solvent) % By mass is particularly preferable.

The resin component A may be a single kind or two or more kinds. When the number of the resin component A is two or more, the sum is preferably in the above range.

<<< Crosslinking Component >>>

In the present invention, it is preferable that the adhesive region includes a maleimide resin as a cross-linking component. As the maleimide resin, any material may be used as long as the product after curing satisfies the mass reduction rate and solubility.

In the present invention, the compound having a maleimide group and the crosslinked product obtained by crosslinking such a compound are all referred to as maleimide resins. The crosslinked product is preferably a three-dimensional crosslinked product using a compound having a maleimide group. The compound having a maleimide group may be either a monomer or a polymer.

In the present invention, a bismaleimide resin is preferable as the maleimide resin.

The bismaleimide resin is more preferably at least one selected from a bismaleimide resin represented by the following general formula (III) and a novolac-type maleimide resin represented by the following general formula (IV).

[Chemical Formula 1]

In the general formula (III), R represents an aromatic ring or a divalent organic group containing a straight-chain, branched-chain or cyclic aliphatic hydrocarbon group.

R is preferably a divalent group composed of a benzene group, a toluene group, a xylene group, a naphthalene group, or a linear, branched or cyclic saturated hydrocarbon group, or a combination thereof.

R is preferably a divalent group represented by the following formula (v), (vi) or (vii).

(2)

(3)

In the general formula (IV), s represents an integer of 0 to 20.

In the present invention, the maleimide resin may be those described in paragraphs 0020 to 0023 of JP-A No. 2003-321608.

Examples of commercially available products of the maleimide resin include BMI-1000, 2000, 3000, 4000, 5000, 5100, 7000 (bismaleimide resin, manufactured by Daiwa Kasei Kogyo Co., Ltd.), BANI-X (bismaleimide resin, Shin Nakamura Kagaku Co., -M (Shin Nakamura Kagaku Co., Ltd., bismaleimide resin), and the like.

The adhesion region preferably contains the maleimide resin in an amount of 1 to 99 mass%, more preferably 10 to 90 mass%, and more preferably 25 to 75 mass% with respect to the total solid content (amount excluding the solvent) Is particularly preferable. When the content of the maleimide resin is within the above range, the heat resistance of the adhesive region can be further improved.

The adhesive film preferably contains 1 to 99 mass%, more preferably 10 to 90 mass%, and more preferably 25 to 75 mass% of the maleimide resin with respect to the total solid content (amount excluding the solvent) % By mass is particularly preferable.

The maleimide resin preferably contains 10 to 100 mass%, more preferably 20 to 100 mass%, more preferably 50 to 100 mass%, and most preferably 80 to 100 mass% of the total mass of the cross- Particularly preferably 100% by mass. Most preferably, the crosslinking component is composed substantially of maleimide resin alone. The content of the cross-linking component other than the maleimide resin is preferably 1% by mass or less, more preferably 0.5% by mass or less, and more preferably 0.1% by mass or less, By mass or less is particularly preferable. According to this embodiment, the heat resistance of the adhesive region can be further improved.

The bonding region of the present invention may contain a crosslinking component (other crosslinking component) other than the maleimide resin. As other crosslinking components, known compounds which are compounds having two or more polymerizable groups and can be polymerized by the action of an actinic ray, radiation, light, heat, radical or acid can be used. Examples of the polymerizable group include a group having an ethylenic unsaturated bond and an epoxy group. As the ethylenically unsaturated bond group, a vinyl group, an acrylic group, a methacrylic group and an allyl group are preferable.

Examples of the compound having a group having an ethylenically unsaturated bond include (meth) acrylamide compounds having 3 to 35 carbon atoms, (meth) acrylate compounds having 4 to 35 carbon atoms, aromatic vinyl compounds having 6 to 35 carbon atoms, 20 vinyl ether compounds, and the like.

Examples of the compound having an epoxy group include glycidyl ethers of bisphenol A type (or AD type, S type, and F type), glycidyl ethers of hydrogenated bisphenol A type, and glycidyl ethers of ethylene oxide adduct bisphenol A type Glycidyl ethers of propylene oxide adduct bisphenol A type, glycidyl ethers of phenol novolac resins, glycidyl ethers of cresol novolak resins, glycidyl ethers of bisphenol A novolak resin, (Or tetrafunctional) glycidyl ethers of a naphthalene resin, glycidyl ethers of a dicyclopentadienephenol resin, diallyl bisphenol A diglycidyl ether A polycondensation product of allylated bisphenol A and epichlorohydrin, a glycidyl ester of dimeric acid, a glycidyl amine of trifunctional (or tetrafunctional) type, a glycidyl amine of naphthalene resin, etc. .

In the present invention, a compound having an epoxy group as a crosslinking component may be contained. However, since the heat resistance can be further improved, the content of the compound having an epoxy group in 100 parts by mass of the crosslinking component may be 10% And more preferably 5% by mass or less, and may be substantially free of any other impurities. For example, the content of the epoxy group-containing compound is preferably 1% by mass or less, more preferably 0.5% by mass or less, particularly preferably 0.1% by mass or less, desirable.

<<< Thermal polymerization initiator >>>

The adhesive region of the present invention preferably further contains a thermal polymerization initiator. As the thermal polymerization initiator, known ones can be used.

As the preferable thermal polymerization initiator, a compound having a half-life temperature for one minute of 130 占 폚 to 300 占 폚, preferably 150 占 폚 to 260 占 폚 may be preferably used. According to this embodiment, the heat resistance of the adhesive region can be further improved.

The one-minute half-life temperature of the thermal polymerization initiator is a temperature at which the thermal polymerization initiator is decomposed and its remaining amount (mass) is reduced to 1/2. One-minute half-life temperature of the thermal polymerization initiator is, for example, by preparing a thermal polymerization initiator in benzene to 0.1mol / l, is heated to a temperature Ti (absolute temperature) of a number of points, and the half-life of t _{1 /} in each temperature Ti _2, by measuring the _T1, by the Int _{1/2, T1,} from the plots, and the obtained straight line with respect to 1 / Ti, obtain the temperature at which the half-life is one minute, it can be determined.

The thermal polymerization initiator is preferably a compound (thermal radical generator) that generates radicals by the energy of heat and initiates or promotes the reaction of the crosslinking component such as maleimide resin.

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

Specific examples of the thermal radical generator include the compounds described in paragraphs 0074 to 0118 of JP-A No. 2008-63554.

Commercially available products include organic peroxides such as pericumyl D, percumyl H, percumyl ND, percumyl P, peroyl IB, peroyl IP, peroyl L, peroyl NPP, peroyl SA, Peroyl OPP, peryl 355, perbutyl D, perbutyl ND, perbutyl NHP, perbutyl PV, perbutyl P, perbutyl Z, perbutyl O, perheyl ND, perheyl O , Perhexil PV, perocta ND, perocta O, nippers BMT, nippers BW, nippers PMB, perhexa HC, perhexa MC, perhexa TMH, perhexa V, perhexa 25B, perhexa 25O, , And the like. As the azo-based compound, V-601 of Wako Co., Ltd. and the like can be mentioned.

The adhesive region preferably contains the thermal polymerization initiator in an amount of 0.5 to 20 mass%, more preferably 1 to 10 mass%, and more preferably 2 to 8 mass%, based on the total solid content (amount excluding the solvent) Is particularly preferable. When the content of the thermal polymerization initiator is within the above range, the heat resistance of the adhesive region can be further improved.

The adhesive film preferably contains the thermal polymerization initiator in an amount of 0.5 to 20 mass%, more preferably 1 to 10 mass%, and more preferably 2 to 8 mass%, based on the total solid content (amount excluding the solvent) % By mass is particularly preferable.

<<< Surfactant >>>

The adhesive region of the adhesive film of the present invention may contain a surfactant. As the surfactant, various surfactants such as a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicone-based surfactant can be used, and a fluorine-based surfactant is preferable.

In the case of forming the adhesive region by the coating method, the liquid property (particularly, fluidity) when prepared as a coating liquid is improved, and the uniformity of the coating thickness and the liquid-storing property can be further improved.

The fluorine-containing surfactant preferably has a fluorine content of 3 to 40% by mass, more preferably 5 to 30% by mass, and further preferably 7 to 25% by mass. The fluorine-based surfactant having a fluorine content within this range is effective in terms of uniformity of the thickness of the coating film and liquidity.

Examples of the fluorine-based surfactant include Megapak F171, Dong F172, Dong F173, Dong F176, Dong F177, Dong F141, Dong F142, Dong F143, Dong F144, Dong R30, Dong F437, Dong F475, Dong F479, Dong F482 (Manufactured by Sumitomo 3M Co., Ltd.), Surflon S-382, SC-101, and SC-101 (manufactured by Sumitomo 3M Limited), F554, F780, and F781 (manufactured by DIC Corporation), Fluorad FC430, (Manufactured by ASAHI GLASS CO., LTD.), PF636, PF656, and SC-103, SC-104, SC-105, SC1068, SC- PF6320, PF6520 and PF7002 (manufactured by OMNOVA).

Examples of the nonionic surfactant include glycerol, trimethylol propane, trimethylol ethane and their ethoxylates and propoxylates (for example, glycerol propoxylate, glycerin ethoxylate and the like), polyoxyethylene lauryl Polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol di-laurate, polyethylene glycol di-stearate , Consumant fatty acid ester (Pluronic L10, L31, L61, L62, 10R5, 17R2, 25R2, Tetronic 304, 701, 704, 901, 904, 150R1, Solspus 20000 ), And the like.

Examples of the cationic surfactant include phthalocyanine derivatives (trade name: EFKA-745, manufactured by Morishita Sangyo Co., Ltd.), organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.) Lt; / RTI &gt; 75, No. 90, No. 95 (manufactured by Kyoeisha Chemical Co., Ltd.) and W001 (manufactured by Yusoh Co., Ltd.).

Examples of the anionic surfactant include W004, W005 and W017 (manufactured by Yusoh Co., Ltd.).

Examples of silicon based surfactants include fluororesins such as "TORAY Silicon DC3PA", "TORAY Silicone SH7PA", "TORAY Silicon DC11PA", "TORAY Silicone SH21PA", "TORAY Silicone SH28PA", "DORAY Silicone SH29PA TSF-4440 "," TSF-4445 "," TSF-4460 "," TSF-4452 "," Tory Silicone SH8400 "and" TSF-4440 "manufactured by Momentive Performance Materials "KF341", "KF6001", and "KF6002" manufactured by Shin-Etsu Silicones Co., Ltd., "BYK307", "BYK323", and "BYK330" manufactured by Big Chemie.

When the adhesive region has a surfactant, the content of the surfactant is preferably 0.001 to 1% by mass, more preferably 0.01 to 0.5% by mass, particularly preferably 0.05 to 0.1% by mass, with respect to the total solid content of the adhesive region Do.

The adhesive film preferably contains the surfactant in an amount of 0.001 to 1 mass%, more preferably 0.01 to 0.5 mass%, more preferably 0.05 to 0.1 mass%, based on the total solids content (amount excluding the solvent) % Is particularly preferable.

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

<<< Antioxidants >>>

The adhesive region of the adhesive film of the present invention may contain an antioxidant from the viewpoint of preventing the adhesive region from becoming low in molecular weight or gelation due to oxidation at the time of heating. As the antioxidant, phenol-based antioxidants, sulfur-based antioxidants, quinone-based antioxidants, nitrogen-based antioxidants and the like can be used.

Examples of the phenolic antioxidant include p-methoxyphenol, 2,6-di-tert-butyl-4-methylphenol, Irganox 1010, Irganox 1330, Irganox 3114, "Irganox 1035" manufactured by Sumitomo Chemical Co., Ltd., "Sumilizer MDP-S" manufactured by Sumitomo Chemical Co., Ltd., and "Sumilizer GA-80"

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

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

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

As the antioxidant, Irganox 1010, Irganox 1330, 3,3'-thiodipropionate distearyl are preferable, Irganox 1010 and Irganox 1330 are more preferable, and Irganox 1010 is particularly preferable.

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

When the adhesive region has an antioxidant, the content of the antioxidant is preferably 0.001 to 10 mass%, more preferably 0.01 to 5 mass%, particularly preferably 0.1 to 1 mass%, based on the total solid content of the adhesive region Do.

The antistatic agent preferably contains the antioxidant in an amount of 0.001 to 10 mass%, more preferably 0.01 to 5 mass%, and more preferably 0.1 to 1 mass%, based on the total solids content (amount excluding the solvent) % Is particularly preferable.

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

<< Release Region >>

The adhesive film of the present invention has a release area on the surface of the adhesive area. The releasing area adjusts the adhesive force between the device wafer and the adhesive area so that the adhesive layer can be easily peeled from the device wafer.

The average thickness of the release region is preferably from 0.001 to 1 mu m, more preferably from 0.01 to 0.5 mu m. In the above-mentioned range, the adhesive film has an appropriate adhesive force, and the adhesive property to the device wafer is good, and the adhesive film can be easily peeled off from the device wafer.

In the case where the adhesive film of the present invention has a laminate structure in which the layers constituting the releasing regions are laminated on the surface layer of the adhesive layer, the average thickness of the layers constituting the releasing regions is preferably from 0.001 to 1 μm, More preferably 0.5 mu m.

When the adhesive film of the present invention is an embodiment in which the releasing component is localized on the surface layer to form the releasing region in the adhesive layer, the average thickness of the releasing region is preferably 0.001 to 1 μm, more preferably 0.01 to 0.5 μm. In this case, the ratio of the average thickness of the adhesive region to the average thickness of the release region is preferably 10 to 1000, more preferably 50 to 500, in the average thickness of the adhesive region / the average thickness of the release region.

In the present invention, the average thickness of the release region is defined as an average value of five points measured by ellipsometry.

The releasing region in the adhesive film of the present invention preferably contains a compound containing at least one selected from a fluorine atom and a silicon atom, and more preferably contains a fluorine-based silane coupling agent.

The fluorine content of the release region is preferably 30 to 80 mass%, more preferably 40 to 76 mass%, and particularly preferably 60 to 75 mass%. The fluorine content is defined as "{(the number of fluorine atoms in one molecule x the mass of fluorine atoms) / the mass of all atoms in one molecule} x 100".

The releasing region preferably contains a compound containing at least one kind selected from a fluorine atom and a silicon atom in an amount of 10 to 100 mass%, more preferably 50 to 100 mass%, with respect to the total solid content of the releasing region Do.

The adhesive film is preferably 10 to 100% by mass, more preferably 50 to 100% by mass, based on the total solid content of the adhesive film, of a compound containing at least one selected from a fluorine atom and a silicon atom.

In the present invention, it is preferable that the releasing region includes a three-dimensional crosslinked material containing fluorine atoms from the viewpoint of heat resistance. Of these, a three-dimensional crosslinked product of a fluorine-containing polyfunctional monomer and oligomer or a three-dimensional crosslinked product of a fluorine-containing silane coupling agent is preferable, and a three-dimensional crosslinked product of a fluorine-containing silane coupling agent is particularly preferable. As the fluorine-containing silane coupling agent, a hydrazene-based silane coupling agent having a low risk for human body and low metal corrosion is preferable, and a fluorine-containing alkoxysilane is particularly preferable. Commercially available products include OptuT DAC-HP and Optun DSX manufactured by Daikin Industries, Ltd. Examples of the halogen-based silane coupling agent include a chlorosilane fluoride compound and the like.

In the present invention, the releasing region may contain a polymer compound having a non-three-dimensional crosslinked structure having fluorine atoms.

The non-three-dimensional crosslinked structure means that the ratio of the crosslinked structure that does not contain a crosslinked structure in the compound or forms a three-dimensional crosslinked structure with respect to the total crosslinked structure in the compound is 5% or less, preferably 1% or less. But it is preferable that it is substantially contained.

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

As the polymer compound having a fluorine atom having a non-three-dimensional cross-linking structure, it is preferably a (meth) acrylic resin containing a perfluoroalkyl group which can be synthesized from a perfluoroalkyl group-containing (meth) acrylic acid ester.

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

(101)

[Chemical Formula 4]

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

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

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

Examples of the divalent aromatic group include a phenylene group, a substituted phenylene group, a naphthalene group and a substituted naphthalene group, and a phenylene group is preferable.

As Y ¹⁰¹ , it is preferable that the Y ¹⁰¹ is an aliphatic group having a bivalent straight-chain structure.

The monovalent organic group having a fluorine atom represented by Rf is not particularly limited, but is preferably a fluorinated alkyl group having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and particularly preferably a fluorinated alkyl group having 1 to 15 carbon atoms desirable. The fluorinated alkyl group is a straight chain {e.g. _{-CF 2 CF 3, -CH 2 (} CF 2) 4 H, -CH 2 (CF 2) 8 CF 3, -CH 2 CH 2 (CF 2) 4 H , etc. }, and even, for example, {branch structure _{-CH (CF 3) 2, -CH} 2 CF (CF 3) 2, -CH (CH 3) CF 2 CF 3, -CH (CH 3) (CF 2) 5 CF ₂ H, etc.), and may have an alicyclic structure (preferably, a 5-membered ring or a 6-membered ring such as a perfluorocyclohexyl group, a perfluorocyclopentyl group, (E.g., -CH ₂ OCH ₂ CF ₂ CF ₃ , -CH ₂ CH ₂ OCH ₂ C ₄ F ₈ H, -CH ₂ CH ₂ OCH ₂ CH ₂ C ₈ F ₁₇ , -CH ₂ CF ₂ OCF ₂ CF ₂ OCF ₂ CF ₂ H, etc.). It may also be a perfluoroalkyl group.

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

Equation (102)

[Chemical Formula 5]

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

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

More specifically, acrylic acid esters such as alkyl acrylates (the number of carbon atoms of the alkyl group is preferably from 1 to 20), (e.g., methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, Amyl acrylate, ethylhexyl acrylate, octyl acrylate, t-octyl acrylate, chloroethyl acrylate, 2,2-dimethylhydroxypropyl acrylate, 5-hydroxypentyl acrylate, trimethylolpropane monoacrylate, (For example, phenyl acrylate and the like), acrylic acid esters (for example, methacrylic acid esters such as methacrylic acid esters, maleic acid esters, maleic acid esters, Methacrylic acid esters such as alkyl methacrylate (the alkyl group preferably has 1 to 20 carbon atoms) (for example, methyl methacrylate Acrylates such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, amyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, chlorobenzyl methacrylate, octyl methacrylate, 4-hydroxybutyl methacrylate, 5-hydroxypentyl methacrylate, 2,2-dimethyl-3-hydroxypropyl methacrylate, trimethylolpropane monomethacrylate, pentaerythritol monomethacrylate (Methacrylic acid, methacrylic acid, methacrylic acid, methacrylic acid, methacrylic acid, methacrylic acid and the like), glycidyl methacrylate, furfuryl methacrylate, tetrahydrofurfuryl methacrylate and the like), aryl methacrylate Etc.), styrenes such as styrene and alkylstyrene (e.g., methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, Butylene styrene, isoprene styrene, isoprene, styrene, butylene, diene, styrene, isobutylene, styrene, , Acetoxymethylstyrene, etc.), alkoxystyrene (e.g., methoxystyrene, 4-methoxy-3-methylstyrene, dimethoxystyrene and the like), halogensilane (e.g., But are not limited to, chlorostyrene, chlorostyrene, dichlorostyrene, dichlorostyrene, trichlorostyrene, tetrachlorostyrene, pentachlorostyrene, bromostyrene, dibromostyrene, iodostyrene, fluorostyrene, 2-bromo-4-trifluoromethylstyrene, 4-fluoro-3-trifluoromethylstyrene, etc.), acrylonitrile, methacrylonitrile acrylic acid, and carboxylic acid Water (e.g., acrylic acid, methacrylic acid, itaconic acid, crotonic acid, incrotonic acid, maleic acid, p-carboxy styrene and metal salts and ammonium salt compounds of these acid groups). In view of releasability, (Meth) acrylic acid esters having 1 to 24 hydrocarbon groups are preferable, and examples thereof include methyl, butyl, 2-ethylhexyl, lauryl, stearyl and glycidyl ester of (meth) acrylic acid. (Meth) acrylates of higher alcohols such as 2-ethylhexyl, lauryl and stearyl, especially acrylates, are preferred.

A commercially available polymer compound having a fluorine atom and a non-three-dimensional cross-linking structure may be used. For example, Teflon (registered trademark) (DuPont), Tefloss (DuPont), Fluon (Asahi Glass Co.), Hyler (SolvaySolexis), Haier (SolvaySolexis), Lumipro (Asahi Glass) Fluorine resins such as Arplose (Asahi Glass Co.), Saitot (Asahi Glass Co.), Sephrill Soft (Central Glass Co.), Sephrill Coat (Central Glass Co.) and Daionin (3M) (DuPont), Pombulin (DaiTokuTech), and DEMNUM (DaiKingo), which are trademarks, such as SILIC (DuPont), SIREL (DuPont), SIFEL Various fluorine oils including perfluoropolyether oils, and fluorine-containing mold release agents such as DieFree FB series (Daikin Kogyu Co., Ltd.) and Megapak series (DIC).

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

The content of the polymer compound having a non-three-dimensional crosslinked structure having a fluorine atom in the releasing region is preferably from 1 to 99% by mass, more preferably from 3 to 95% by mass, based on the total solid content of the releasing region from the viewpoint of good releasability , More preferably 5 to 90 mass%.

The ratio (mass ratio) of the three-dimensional crosslinked material containing a fluorine atom to the polymer compound of a non-three-dimensional crosslinked structure having a fluorine atom in the releasing region is preferably from 5:95 to 50:50, To 40:60 is more preferable, and 15:85 to 30:70 is more preferable.

The polymer compound having a non-three-dimensional crosslinked structure having a fluorine atom may be one kind or two or more kinds. In the case of two or more types, it is preferable that the total is in the above range.

&Lt; Adhesive composition >

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

The adhesive composition of the present invention is a resin composition comprising a resin containing a heterocyclic ring containing at least one member selected from a polyimide resin, a polyamideimide resin, a polybenzimidazole resin and a polybenzoxazole resin, 100% by mass, and a solvent.

By using the adhesive composition of the present invention, it is possible to form an adhesive region in the above-mentioned adhesive film of the present invention.

<< Bicycle-containing resin >>

As the heterocyclic ring-containing resin, at least one selected from a polyimide resin, a polyamideimide resin, a polybenzimidazole resin and a polybenzoxazole resin is used. As specific examples thereof, those described in the section of the adhesive region are suitably used. Among them, a polyimide resin is preferable. The polyimide resin may be at least one selected from the group consisting of γ-butyrolactone, cyclopentanone, N-methylpyrrolidone, cyclohexanone, glycol ether, dimethyl sulfoxide and tetramethylurea A polyimide resin having a solubility of not less than 10 g / 100 g Solvent at 25 캜 is preferable.

The content of the heterocyclic ring-containing resin is preferably from 1 to 99% by mass, more preferably from 10 to 90% by mass, and still more preferably from 25 to 75% by mass, based on the total solids content (amount excluding solvent) Particularly preferred.

<< Crosslinking Component >>

As the crosslinking component, a resin containing 50 to 100% by mass of a maleimide resin is used.

Here, the maleimide resin is preferably a bismaleimide resin. As specific examples of the maleimide resin, those described in the section of the adhesive region are suitably used.

The content of the maleimide resin in the crosslinking component is preferably 80 to 100% by mass of the total crosslinking component. Most preferably, the crosslinking component is composed substantially of maleimide resin alone. The content of the crosslinking component other than the maleimide resin is preferably 1% by mass or less, more preferably 0.5% by mass or less, and particularly preferably 0.1% by mass or less, Do. As the crosslinking component other than the maleimide resin, those described in the section of other crosslinking components of the bonding region are preferably used.

The content of the maleimide resin is preferably from 1 to 99% by mass, more preferably from 10 to 90% by mass, and particularly preferably from 25 to 75% by mass, relative to the total solids content (amount excluding solvent) desirable.

<< Solvent >>

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

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

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

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

N, N-dimethylacetamide, and the like.

Among them, anisole, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, 2-butanone, methylamylketone, limonene, mesitylene, methyl ethyl ketone, PGMEA (1-methoxy- 2-propyl acetate) and the like are preferable, and N-methyl-2-pyrrolidone, N, N-dimethylacetamide, methyl amyl ketone and limonene are preferable.

These solvents are also preferably mixed with two or more kinds in view of improving the application surface shape and the like.

The content of the solvent is preferably such that the solid content concentration of the adhesive composition is from 5 to 60% by mass.

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

<< Thermal polymerization initiator >>

The adhesive composition preferably contains a thermal polymerization initiator. By containing a thermal polymerization initiator, an adhesion film having more excellent heat resistance and tolerance can be formed. As the thermal polymerization initiator, those described in the section of the adhesive region are suitably used, and preferable ranges are also the same.

The content of the thermal polymerization initiator is preferably 0.001 to 1% by mass, more preferably 0.01 to 0.5% by mass, and particularly preferably 0.05 to 0.1% by mass, relative to the total solids content (amount excluding solvent) desirable.

<< Release Component >>

It is preferable that the adhesive composition further contains a releasing component. By containing the releasing component, it is possible to form an adherent film in which the releasing component is localized on the surface layer and the releasing region is unevenly distributed on the surface layer of the adhering region when the adherent composition is applied in film form.

The releasing component is preferably a material containing at least one kind selected from a fluorine atom and a silicon atom. Examples of the material containing at least one kind selected from a fluorine atom and a silicon atom include a polymerizable monomer having a fluorine atom or a silicon atom. A fluorine-based silane coupling agent is more preferable.

<<< Polymerizable monomers having fluorine or silicon atoms >>>

The polymerizable monomer having a fluorine atom or a silicon atom is preferably a radically polymerizable monomer or oligomer containing one or more fluorine atoms or silicon atoms in one molecule and is preferably a polymerizable monomer or oligomer having two or more fluorine atoms in one molecule, And a polymerizable monomer having a group called a luorro group is particularly preferable.

The radical polymerizable monomer or oligomer having a fluorine atom or a silicon atom has a radically polymerizable functional group, and the radical polymerizable functional group is not particularly limited, but is preferably an unsaturated group (an ethylenically unsaturated bonding group or the like).

The radically polymerizable monomer or oligomer having a fluorine atom or a silicon atom preferably has two or more radically polymerizable functional groups, and thus it is preferable that in the manufacturing process of the device, the release from the device wafer It is possible to improve the property.

<<<< Polymerizable monomers with fluorine atoms >>>>

The polymerizable monomer having a fluorine atom can be selected from known monomers, and a monomer having a polymerizable group is preferable, and a fluorinated silane coupling agent is more preferable. Examples of the polymerizable group include a silyl group having a hydroxyl group or a hydrolyzable group (e.g., an alkoxysilyl group or an acyloxysilyl group), a group having a reactive unsaturated double bond (a (meth) acryloyl group, an allyl group, A hydroxyl group, a carboxyl group, an amino group, a carbamoyl group, a mercapto group, a β-ketoester group (eg, Group, hydrosilyl group, silanol group, etc.), acid anhydride, group which may be substituted by nucleophilic agent (active oxygen atom, sulfonic acid ester etc.).

The radically polymerizable monomer having a fluorine atom is preferably a compound represented by the following general formula (1).

General formula (I): Rf {-LY} _n

(Wherein Rf represents a straight or cyclic n-valent group containing at least a carbon atom and a fluorine atom and may include any one of an oxygen atom and a hydrogen atom, and n represents an integer of 2 or more.) L is a single bond Or a divalent linking group, and Y represents a polymerizable group.

In the general formula (I), Y is a polymerizable group, for example, a silyl group having a hydroxyl group or a hydrolyzable group (e.g., an alkoxysilyl group, an acyloxysilyl group, etc.), a group having a reactive unsaturated double bond (Such as a (meth) acryloyl group, an allyl group or a vinyloxy group), a ring-opening polymerization reactive group (an epoxy group, an oxetanyl group, an oxazolyl group or the like), a group having an active hydrogen atom (e.g. a hydroxyl group, , A group capable of being substituted by an acid anhydride or a nucleophilic agent (an active hydrogen atom, a sulfonic acid ester, etc.), and the like are preferable .

More preferably, Y represents a radical polymerizable group, and a group having a reactive unsaturated double bond is more preferable. Specifically, T is preferably a radical polymerizable functional group represented by the following general formula (9).

[Chemical Formula 6]

(In the general formula (9), R ⁹⁰¹ to R ⁹⁰³ each independently represent a hydrogen atom, an alkyl group or an aryl group, and a dotted line represents a bond to a group connected to L.)

The alkyl group is preferably an alkyl group having 1 to 8 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, an octyl group, an isopropyl group, a tert-butyl group, an isopentyl group, Methyl hexyl group, and cyclopentyl group. The aryl group is preferably an aryl group having 6 to 12 carbon atoms, and examples thereof include a phenyl group, a 1-naphthyl group and a 2-naphthyl group. As R ⁹⁰¹ to R ⁹⁰³ , a hydrogen atom or a methyl group is particularly preferable.

L represents a single bond or a divalent linking group. Examples of the divalent linking group include a divalent linking group obtained by combining two or more kinds of a divalent aliphatic group, a divalent aromatic group, -O-, -S-, -CO-, -N (R) -, Provided that R represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.

When L has an alkylene group or an arylene group, the alkylene group and the arylene group are preferably substituted with a halogen atom, and more preferably substituted with a fluorine atom.

Rf represents a straight or cyclic n-valent group which contains at least a carbon atom and a fluorine atom and may contain either an oxygen atom or a hydrogen atom. Rf may be a linear or branched polymer structure having a repeating unit having a fluorine atom.

As such a monomer having a fluorine atom, compounds described in paragraphs 0019 to 0033 of JP-A No. 2011-48358 can also be preferably used, and these contents are incorporated herein by reference.

The radically polymerizable monomer having a fluorine atom is also preferably at least one selected from the compounds represented by the following structural formulas (1), (2), (3), (4) and (5)

CH ₂ = CR ¹ COOR ² R ^f ... The structural formula (1)

(Formula (1) of, R ¹ represents a hydrogen atom, or a methyl group R ² _{is, -C p H 2p -.,} -C (C p H 2p + 1) H-, -CH 2 C (C p . H _{2p + 1)} H-, or -CH ₂ CH ₂ O- represents a R ^f _{is, -C n F 2n +1, -} (CF 2) n H, -C n F 2n + 1 -CF 3, _{- (CF 2) p OC n} H 2n C i F 2i +1, - (CF 2) p OC m H 2m C i F 2i H, -N (C p H 2p + 1) COC n F 2n +1, or represents a _{-N (C p H 2p + 1} ) SO 2 C n F 2n + 1. However, p is an integer of 1 ~ 10, n is an integer of 1 ~ 16, m is an integer of 0 ~ 10, i is Represents an integer from 0 to 16, respectively.)

CF ₂ = CFOR ^g ... Structural formula (2)

(In the structural formula (2), R ^g represents a fluoroalkyl group having 1 to 20 carbon atoms.)

CH ₂ = CHR ^g ... Structural Formula (3)

(In the structural formula (3), R ^g represents a fluoroalkyl group having 1 to 20 carbon atoms.)

CH ₂ = CR ³ COOR ⁵ R ^j R ⁶ OCOCR ⁴ = CH ₂ ... The structural formula (4)

(Structure 4 of, R ³ and R ⁴ represent a hydrogen atom, a methyl group or R ⁵ and R ⁶ _{is, -C q H 2q -.,} -C (C q H 2q + 1) H-, - CH ₂ C (C _q H _{2q + 1} ) H- or -CH ₂ CH ₂ O-, R ^j represents -C _t F _2t , q is an integer of 1 to 10, and t is an integer of 1 to 16 .)

CH ₂ = CHR ⁷ COOCH ₂ (CH ₂ R ^k ) CHOCOCR ⁸ = CH ₂ ... Structural formula (5)

(In the structural formula (5), R ⁷ and R ⁸ represent a hydrogen atom or a methyl group, R ^k is -CyF _{2y +1, and} y is an integer of 1 to 16.)

Examples of the monomer represented by the structural formula (1) include CF ₃ (CF ₂ ) ₅ CH ₂ CH ₂ OCOCH═CH ₂ , CF ₃ CH ₂ OCOCH═CH ₂ , CF ₃ (CF ₂ ) ₄ CH ₂ CH ₂ OCOC _{CH 3) = CH 2, C} 7 F 15 CON (C 2 H 5) CH 2 OCOC (CH 3) = CH 2, CF 3 (CF 2) 7 SO 2 N (CH 2) CH 2 CH 2 OCOCH = CH _{2, CF 2 (CF 2)} 7 SO 2 N (C 3 H 7) CH 2 CH 2 OCOCH = CH 2, C 2 F 5 SO 2 N (C 3 H 7) CH 2 CH 2 OCOC (CH 3) = _{CH 2, (CF 3) 2} CF (CF 2) 6 (CH 2) 3 OCOCH = CH 2, (CF 3) 2 CF (CF 2) 10 (CH 2) 3 OCOC (CH 3) = CH 2, CF _{3 (CF 2) 4 CH (} CH 3) OCOC (CH 3) = CH 2, CF 3 CH 2 OCH 2 CH 2 OCOCH = CH 2, C 2 F 5 (CH 2 CH 2 O) 2 CH 2 OCOCH = CH _{2, (CF 3) 2 CFO} (CH 2) 5 OCOCH = CH 2, CF 3 (CF 2) 4 OCH 2 CH 2 OCOC (CH 3) = CH 2, C 2 F 5 CON (C 2 H 5) CH _{2 OCOCH = CH 2, CF 3} (CF 2) 2 CON (CH 3) CH (CH 3) CH 2 OCOCH = CH 2, H (CF 2) 6 C (C 2 H 5) OCOC (CH 3) = CH _{2, H (CF 2) 8} CH 2 OCOCH = CH 2, H (CF 2) 4 CH 2 OCOCH = CH 2, H (CF 2) CH 2 OCOC (CH 3) = CH 2, CF 3 (CF 2) _{7 SO 2 N (CH 3)} CH 2 CH 2 OCOC (CH 3) = CH 2, CF 3 (CF 2) 7 SO 2 N (CH 3) (CH 2) 10 OCOCH = CH 2, _{C 2 F 5 SO 2 N (} C 2 H 5) CH 2 CH 2 OCOC (CH 3) = CH 2, CF 3 (CF 2) 7 SO 2 N (CH 3) (CH 2) 4 OCOCH = CH 2, C ₂ F ₅ SO ₂ N (C ₂ H ₅ ) C (C ₂ H ₅ ) HCH ₂ OCOCH = CH ₂ . These may be used alone, or two or more kinds may be used in combination.

As the structural formula (2) or alkylated fluoro represented by (3) an olefin, for example _{C 3 F 7 CH = CH 2} , C 4 F 9 CH = CH 2, C 10 F 21 CH = CH 2, C 3 F 7 OCF = CF ₂ , C ₇ F ₁₅ OCF = CF ₂ , and C ₈ F ₁₇ OCF = CF ₂ .

As the monomer represented by the structural formula (4) or (5), for example, _{CH 2 = CHCOOCH 2 (CF 2} ) 3 CH 2 OCOCH = CH 2, CH 2 = CHCOOCH 2 (CF 2) 6 CH 2 OCOCH = CH 2, CH ₂ = CHCOOCH ₂ CH (CH ₂ C ₈ F ₁₇ ) OCOCH = CH ₂ and the like.

As the radically polymerizable monomer or oligomer having a fluorine atom, an oligomer having a repeating unit having a fluorine atom and a repeating unit having a radically polymerizable functional group is also preferably used.

The repeating unit having a fluorine atom is preferably selected from at least one kind of repeating units represented by the following formulas (6), (7) and (10).

(7)

(6) of, R ^1, R ^2, R ^3, and R ⁴ are, each independently represents a hydrogen atom, a halogen atom, a hydroxyl group, or a monovalent organic group for, R ^1, R ^2, R ^3, and R at least one ⁴ is a monovalent organic group having a fluorine atom, or a fluorine atom.

In formula (7), R ⁵ , R ⁶ and R ⁷ each independently represent a hydrogen atom, a halogen atom, a hydroxyl group or a monovalent organic group, Y ¹ represents a single bond or a group represented by -CO-, , -NH-, a divalent aliphatic group, a divalent aromatic group, and combinations thereof. Rf represents a fluorine atom or a monovalent organic group having a fluorine atom.

Equation (10), R ^8, R ^9, R ^10, R ^11, R ^12, R ¹³ are, each independently represents a hydrogen atom, a halogen atom, a hydroxyl group, or one group monovalent organic to, Y ² and Y ³ are , A single bond or a divalent linking group selected from the group consisting of -CO-, -O-, -NH-, a bivalent aliphatic group, a bivalent aromatic group, and combinations thereof. Rf represents a divalent organic group having a fluorine atom.

The monovalent organic group having a fluorine atom in the formulas (6) and (7) is not particularly limited, but is preferably a fluorinated alkyl group having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, Of fluorinated alkyl groups are particularly preferred. The fluorinated alkyl group is a straight-chain (for example, _{-CF 2 CF 3, -CH 2 (} CF 2) 4 H, -CH 2 (CF 2) 8 CF 3, -CH 2 CH 2 (CF 2) 4 H , etc. ) being even, the branch structure (e.g. _{-CH (CF 3) 2, -CH} 2 CF (CF 3) 2, -CH (CH 3) CF 2 CF 3, -CH (CH 3) (CF 2) 5 CF ₂ H and the like), and may have an alicyclic structure (preferably a 5-membered ring or a 6-membered ring such as a perfluorocyclohexyl group, a perfluorocyclopentyl group or an alkyl group substituted with these) (E.g., -CH ₂ OCH ₂ CF ₂ CF ₃ , -CH ₂ CH ₂ OCH ₂ C ₄ F ₈ H, -CH ₂ CH ₂ OCH ₂ CH ₂ C ₈ F ₁₇ , -CH ₂ CF ₂ OCF ₂ CF ₂ OCF ₂ CF ₂ H, etc.). It may also be a perfluoroalkyl group.

The divalent organic group having a fluorine atom in formula (10) is not particularly limited, but is preferably a fluorinated alkylene group having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, a fluorinated alkyl group having 1 to 15 carbon atoms Rhenylene is particularly preferred. A fluorinated alkylene group, a straight-chain (for example, _{-CF 2 CF 2 -, -CH 2} (CF 2) 4 -, -CH 2 (CF 2) 8 CF 2 -, -CH 2 CH 2 (CF 2) ₄ -, etc.), branched structures (for example, -CH (CF ₃ ) CF ₂ -, -CH ₂ CF (CF ₃ ) CF ₂ -, -CH (CH ₃ ) CF ₂ CF ₂ -, -CH _{CH 3) (CF 2) 5} CF 2 - which may have, etc.), and, again alicyclic structure (preferably, for a five-membered ring or 6-membered ring, such as perfluoro cyclohexyl group, perfluoro cyclo pentyl or their (E.g., -CH ₂ OCH ₂ CF ₂ CF ₂ -, -CH ₂ CH ₂ OCH ₂ C ₄ F ₈ -, -CH ₂ CH ₂ OCH ₂ CH ₂ C ₈ F ₁₆ -, -CH ₂ CF ₂ OCF ₂ CF ₂ OCF ₂ CF ₂ -, -CH ₂ CF ₂ OCF ₂ CF ₂ OCF ₂ CF ₂ -, polyperfluoroalkylene ether chain, etc.) do. The perfluoroalkylene group may also be a perfluoroalkylene group.

The monovalent organic group in the formulas (6), (7) and (10) is preferably an organic group consisting of 3 to 10 valent nonmetallic atoms, for example 1 to 60 carbon atoms, 0 to 10 An organic group composed of at least one element selected from the group consisting of nitrogen atom, 0 to 50 oxygen atoms, 1 to 100 hydrogen atoms, and 0 to 20 sulfur atoms .

More specific examples include organic groups having the following structures singly or in combination.

The monovalent organic group may further have a substituent and examples of the substituent which can be introduced include a halogen atom, a hydroxyl group, a carboxyl group, a sulfonate group, a nitro group, a cyano group, an amide group, An alkenyl group, an alkynyl group, an alkynyl group, an aryl group, a substituted oxy group, a substituted sulfonyl group, a substituted carbonyl group, a substituted sulfinyl group, a sulfo group, a phosphono group, a phosphonate group, a silyl group and a heterocyclic group. The organic group may also include an ether bond, an ester bond, and a ureido bond.

The monovalent organic group is preferably an alkyl group, an alkenyl group, an alkynyl group or an aryl group. The alkyl group is preferably an alkyl group having 1 to 8 carbon atoms, and examples thereof include a methyl group, ethyl group, propyl group, octyl group, isopropyl group, t-butyl group, An acyl group, a cyclopentyl group and the like. An alkenyl group and an alkenyl group having 2 to 20 carbon atoms, and examples thereof include a vinyl group, an allyl group, a purene group, a geranyl group and an oleyl group. The alkanyl group is preferably an alkanyl group having 3 to 10 carbon atoms, and examples thereof include an ethynyl group, a propargyl group, and a trimethylsilylethynyl group. The aryl group is preferably an aryl group having 6 to 12 carbon atoms, and examples thereof include a phenyl group, a 1-naphthyl group and a 2-naphthyl group. The heterocyclic group is preferably a heterocyclic group having 2 to 10 carbon atoms, and examples thereof include a furanyl group, a thiophenyl group, and a pyridinyl group.

In the formula (6) in the ^{R 1, R 2, R 3} , and R ^4, Equation ^{(7), R 5, R 6, R} 7, equation ^{(10), R 8, R} 9, R 10, R 11 , R ¹² and R ¹³ is preferably an alkyl group or an aryl group.

The alkyl group is preferably an alkyl group having 1 to 8 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, an octyl group, an isopropyl group, a tert-butyl group, an isopentyl group, Methyl hexyl group, and cyclopentyl group. The aryl group is preferably an aryl group having 6 to 12 carbon atoms, and examples thereof include a phenyl group, a 1-naphthyl group and a 2-naphthyl group. As R ⁹⁰¹ to R ⁹⁰³ , a hydrogen atom or a methyl group is particularly preferable.

Selected from the group consisting of -CO-, -O-, -NH-, a divalent aliphatic group, a divalent aromatic group and combinations thereof represented by Y ¹ in the formula (7) and Y ² and Y ³ in the formula (10) Specific examples of the divalent linking group are as follows. In the following example, the left side is bonded to the main chain and the right side is bonded to Rf.

L1 is an aliphatic group of the -CO-NH-2 -O-CO-NH-2 aliphatic group -O-CO-

L2: -CO-NH-2 aliphatic group -O-CO-

L3: -CO-2 aliphatic group -O-CO-

L4: -CO-O-2 aliphatic group -O-CO-

L5: -valent aliphatic group -O-CO-

L6: -CO-NH-2 aromatic group -O-CO-

L7: -CO-2 aromatic group -O-CO-

L8: -valent aromatic group -O-CO-

L9: an aliphatic group of -CO-O-2, an aliphatic group of -CO-O-2,

L10: an aliphatic group of -CO-O-2, an aliphatic group of -O-CO-2, an -O-

L11 represents an aromatic group of -CO-O-2, -CO-O-2 represents an aliphatic group -O-CO-

L12 represents an aromatic group of -CO-O-2, -O-CO-2 represents an aliphatic group -O-CO-

L13: an aliphatic group of -CO-O-2, an aromatic group of -CO-O-2, -O-CO-

L14: an aliphatic group of -CO-O-2, an aromatic group of -O-CO-2, -O-CO-

L15 is an aromatic group of -CO-O-2, -CO-O-2 is an aromatic group of -O-CO-

L16 represents an aromatic group of -CO-O-2, -O-CO-2 represents an aromatic group, -O-CO-

L17 represents an aromatic group of -CO-O-2, -O-CO-NH-2 represents an aliphatic group -O-CO-

L18 represents an aliphatic group of -CO-O-2, an aliphatic group of -O-CO-NH-2,

L19: An aromatic group-bivalent aliphatic group

L20: an aromatic group-having 2-valent aliphatic group -O-2 valent aliphatic group-

L21: an aromatic group-having 2-valent aliphatic group -O-2 valent aliphatic group -O-

L22: -CO-O-2 Aliphatic group -

L23: -CO-O-2 Aliphatic group -O-

Herein, the divalent aliphatic group means an alkylene group, a substituted alkylene group, an alkenylene group, a substituted alkenylene group, an alkenylene group, a substituted alkenylene group or a polyalkyleneoxy group. Among them, an alkylene group, a substituted alkylene group, an alkenylene group, and a substituted alkenylene group are preferable, and an alkylene group and a substituted alkylene group are more preferable.

The divalent aliphatic group is preferably a chain structure rather than a cyclic structure and more preferably a straight chain structure rather than a branched chain structure. The number of carbon atoms of the divalent aliphatic group is preferably from 1 to 20, more preferably from 1 to 15, still more preferably from 1 to 12, still more preferably from 1 to 10, and even more preferably from 1 to 8 , More preferably 1 to 4 carbon atoms.

Examples of the substituent of the divalent aliphatic group include a halogen atom (F, Cl, Br, I), a hydroxyl group, a carboxy group, an amino group, a cyano group, an aryl group, an alkoxy group, an aryloxy group, An aryloxycarbonyl group, an acyloxy group, a monoalkylamino group, a dialkylamino group, an arylamino group, and a diarylamino group.

Examples of the divalent aromatic group include a phenylene group, a substituted phenylene group, a naphthalene group and a substituted naphthalene group, and a phenylene group is preferable. Examples of the substituent of the divalent aromatic group include an alkyl group in addition to the examples of the substituent of the divalent aliphatic group.

The content of the repeating unit having a fluorine atom is preferably from 2 mol% to 98 mol%, more preferably from 10 mol% to 90 mol%, based on the total repeating units of the fluorine atom-containing radically polymerizable oligomer.

The repeating unit having a radical polymerizable functional group is preferably a repeating unit represented by the following formula (8).

[Chemical Formula 8]

(In the general formula (8), R ⁸⁰¹ to R ⁸⁰³ each independently represent a hydrogen atom, an alkyl group, or a halogen atom, and Y ⁸ represents a single bond or a group represented by -CO-, -O-, -NH -, a divalent aliphatic group, a divalent aromatic group, and a combination thereof, and T represents a structure having a radically polymerizable functional group.

The alkyl group as R ⁸⁰¹ to R ⁸⁰³ is preferably an alkyl group having 1 to 6 carbon atoms.

T is preferably a radical polymerizable functional group represented by the general formula (9).

[Chemical Formula 9]

(In the general formula (9), R ⁹⁰¹ to R ⁹⁰³ each independently represent a hydrogen atom, an alkyl group or an aryl group, and the dotted line represents a bond to a group connected to Y ^8. )

The alkyl group is preferably an alkyl group having 1 to 8 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, an octyl group, an isopropyl group, a tert-butyl group, an isopentyl group, Methyl hexyl group, and cyclopentyl group. The aryl group is preferably an aryl group having 6 to 12 carbon atoms, and examples thereof include a phenyl group, a 1-naphthyl group and a 2-naphthyl group. As R ⁹⁰¹ to R ⁹⁰³ , a hydrogen atom or a methyl group is particularly preferable.

Y ⁸ represents a single bond or a divalent linking group selected from the group consisting of -CO-, -O-, -NH-, a bivalent aliphatic group, a bivalent aromatic group, and combinations thereof. A concrete example of Y ⁸ composed of a combination is shown below. In the following example, the left side is bonded to the main chain and the right side is bonded to the formula (9).

L1 is an aliphatic group of the -CO-NH-2 -O-CO-NH-2 aliphatic group -O-CO-

L2: -CO-NH-2 aliphatic group -O-CO-

L3: -CO-2 aliphatic group -O-CO-

L4: -CO-O-2 aliphatic group -O-CO-

L5: -valent aliphatic group -O-CO-

L6: -CO-NH-2 aromatic group -O-CO-

L7: -CO-2 aromatic group -O-CO-

L8: -valent aromatic group -O-CO-

L9: an aliphatic group of -CO-O-2, an aliphatic group of -CO-O-2,

L10: an aliphatic group of -CO-O-2, an aliphatic group of -O-CO-2, an -O-

L11 represents an aromatic group of -CO-O-2, -CO-O-2 represents an aliphatic group -O-CO-

L12 represents an aromatic group of -CO-O-2, -O-CO-2 represents an aliphatic group -O-CO-

L13: an aliphatic group of -CO-O-2, an aromatic group of -CO-O-2, -O-CO-

L14: an aliphatic group of -CO-O-2, an aromatic group of -O-CO-2, -O-CO-

L15 is an aromatic group of -CO-O-2, -CO-O-2 is an aromatic group of -O-CO-

L16 represents an aromatic group of -CO-O-2, -O-CO-2 represents an aromatic group, -O-CO-

L17 represents an aromatic group of -CO-O-2, -O-CO-NH-2 represents an aliphatic group -O-CO-

L18 represents an aliphatic group of -CO-O-2, an aliphatic group of -O-CO-NH-2,

Herein, the divalent aliphatic group means an alkylene group, a substituted alkylene group, an alkenylene group, a substituted alkenylene group, an alkenylene group, a substituted alkenylene group or a polyalkyleneoxy group. Among them, an alkylene group, a substituted alkylene group, an alkenylene group, and a substituted alkenylene group are preferable, and an alkylene group and a substituted alkylene group are more preferable.

The divalent aliphatic group is preferably a chain structure rather than a cyclic structure and more preferably a straight chain structure rather than a branched chain structure. The number of carbon atoms of the divalent aliphatic group is preferably from 1 to 20, more preferably from 1 to 15, still more preferably from 1 to 12, still more preferably from 1 to 10, and even more preferably from 1 to 8 , More preferably 1 to 4 carbon atoms.

Examples of the substituent of the divalent aliphatic group include a halogen atom (F, Cl, Br, I), a hydroxyl group, a carboxy group, an amino group, a cyano group, an aryl group, an alkoxy group, an aryloxy group, An aryloxycarbonyl group, an acyloxy group, a monoalkylamino group, a dialkylamino group, an arylamino group, and a diarylamino group.

Examples of the divalent aromatic group include a phenylene group, a substituted phenylene group, a naphthalene group and a substituted naphthalene group, and a phenylene group is preferable. Examples of the substituent of the divalent aromatic group include an alkyl group in addition to the examples of the substituent of the divalent aliphatic group.

The content of the repeating unit having a radical polymerizable functional group is preferably from 2 to 98% by mole, more preferably from 10 to 90% by mole, based on the total repeating units of the fluorine atom-containing radically polymerizable oligomer.

The weight average molecular weight of the radically polymerizable oligomer having a fluorine atom in terms of polystyrene as determined by gel permeation chromatography (GPC) is preferably 2,000 to 20,000, more preferably 2,000 to 15,000, and most preferably 2,000 to 10,000 desirable.

The weight average molecular weight of the radically polymerizable oligomer having a fluorine atom in terms of polystyrene by gel permeation chromatography (GPC) is preferably 2000 to 10,000, more preferably 2,000 to 8,000, and most preferably 2,000 to 6,000 desirable.

When the composition for forming a releasable region contains a radically polymerizable monomer or oligomer having a fluorine atom, the content of the radically polymerizable monomer or oligomer having a fluorine atom is not particularly limited, and preferably the composition for forming a releasable region Is preferably 0.01 to 15% by mass relative to the total solid content of the polymer. If it is 0.01% by mass or more, sufficient peeling property can be obtained. If it is 15 mass% or less, sufficient adhesion can be obtained.

The radically polymerizable monomer or oligomer having a fluorine atom may be one type or two or more types. When two or more types of polymerizable monomers are used, the total amount is preferably in the above range.

<<< Radically polymerizable monomers or oligomers with silicon atoms >>>

The radically polymerizable monomer or oligomer having the silicon atom is preferably a silicone monomer or a silicone oligomer. For example, at least one terminal of the polydimethylsiloxane bond may be an ethylene (meth) acryloyl group such as a Unsaturated group, and a compound having a (meth) acryloyl group is preferable.

The number average molecular weight of a radically polymerizable oligomer having a silicon atom in terms of polystyrene determined by gel permeation chromatography is preferably 1,000 to 10,000. When the number average molecular weight of the radically polymerizable oligomer having a silicon atom in terms of polystyrene reduced by gel permeation chromatography is less than 1,000 or 10,000 or more, properties such as peelability due to silicon atoms are difficult to manifest.

As the radically polymerizable monomer having a silicon atom, a compound represented by the general formula (11) or (12) is preferable.

[Chemical formula 10]

(Formula (11) and (12) of, R ¹¹ ~ R ¹⁹ are, each independently, represent a hydrogen atom, alkyl group, alkoxy group, alkoxycarbonyl group, or an aryl group. Z ^11, Z ^12, and Z ¹³ is L ¹¹ , L ¹² and L ¹³ each independently represent a single bond or a divalent linking group, and n and m each independently represent an integer of 0 or more.

In the general formulas (11) and (12), R ¹¹ to R ¹⁹ each independently represent a hydrogen atom, an alkyl group, an alkoxy group, an alkoxycarbonyl group or an aryl group.

The alkyl group may be linear, branched or an alkyl group having 1 to 5 carbon atoms, and specific examples thereof include a methyl group, ethyl group, n-propyl group and isopropyl group. The alkoxy group means -OR ²⁰ , and R ²⁰ represents an alkyl group (preferably an alkyl group having 1 to 5 carbon atoms), and specific examples thereof include a methoxy group, ethoxy group, propoxy group, isopropoxy group, And the like. The alkoxycarbonyl group means -C (= O) R ²¹ , and R ²¹ represents an alkoxy group (preferably an alkoxy group having 1 to 5 carbon atoms), specifically, methoxycarbonyl, ethoxycarbonyl Propylcarbonyl, and the like. Examples of the aryl group include a phenyl group, a tolyl group and a naphthyl group, and they may have a substituent. Examples of the aryl group include a phenylmethyl (benzyl) group, a phenylethyl group, a phenylpropyl group, a phenylbutyl group and a naphthylmethyl group.

L ¹¹ , L ¹² , and L ¹³ each independently represent a single bond or a divalent linking group. The divalent linking group represents a divalent linking group selected from the group consisting of -CO-, -O-, -NH-, a bivalent aliphatic group, a bivalent aromatic group, and combinations thereof.

n and m each independently represent an integer of 0 or more, preferably an integer of 0 to 100, more preferably an integer of 0 to 50.

Z ¹¹ , Z ¹² and Z ¹³ each independently represent a radical polymerizable group, and a functional group represented by any one of the following formulas (i) to (iii) is particularly preferable.

(11)

(Wherein R ¹⁰¹ to R ¹⁰³ each independently represents a hydrogen atom or a monovalent organic group, X ¹⁰¹ represents an oxygen atom, a sulfur atom, or -N (R ¹⁰⁴ ) -, and R ¹⁰⁴ Represents a hydrogen atom or a monovalent organic group.)

In the general formula (I), R ¹⁰¹ to R ¹⁰³ each independently represent a hydrogen atom or a monovalent organic group. R ¹⁰¹ is preferably a hydrogen atom or an alkyl group which may have a substituent, and among them, a hydrogen atom and a methyl group are preferable because of high radical reactivity. R ¹⁰² and R ¹⁰³ are each independently preferably a hydrogen atom, a halogen atom, an amino group, a carboxyl group, an alkoxycarbonyl group, a sulfo group, a nitro group, a cyano group, , An aryl group which may have a substituent, an alkoxy group which may have a substituent, an aryloxy group which may have a substituent, an alkylamino group which may have a substituent, an arylamino group which may have a substituent, , Or an arylsulfonyl group which may have a substituent, and among these, a hydrogen atom, a carboxyl group, an alkoxycarbonyl group, an alkyl group which may have a substituent, and an aryl group which may have a substituent are preferable because of high radical reactivity.

X ¹⁰¹ represents an oxygen atom, a sulfur atom, or -N (R ¹⁰⁴ ) -, and R ¹⁰⁴ represents a hydrogen atom or a monovalent organic group. As the monovalent organic group, an alkyl group which may have a substituent may, for example, be mentioned. It is preferable that R ¹⁰⁴ is a hydrogen atom, a methyl group, an ethyl group, or an isopropyl group because of high radical reactivity.

Examples of the substituent which can be introduced include alkyl groups, alkenyl groups, alkynyl groups, aryl groups, alkoxy groups, aryloxy groups, halogen atoms, amino groups, alkylamino groups, arylamino groups, carboxyl groups, alkoxycarbonyl groups, sulfo groups, A cyano group, an amide group, an alkylsulfonyl group, and an arylsulfonyl group.

[Chemical Formula 12]

(Wherein R ²⁰¹ to R ²⁰⁵ each independently represents a hydrogen atom or a monovalent organic group, Y ²⁰¹ represents an oxygen atom, a sulfur atom, or -N (R ²⁰⁶ ) - R ²⁰⁶ represents a hydrogen atom or a monovalent organic group.)

In formula (ii), ^R201 to ^R205 each independently represent a hydrogen atom or a monovalent organic group. R ²⁰¹ to R ²⁰⁵ each independently represent a hydrogen atom, a halogen atom, an amino group, a carboxyl group, an alkoxycarbonyl group, a sulfo group, a nitro group, a cyano group, an alkyl group which may have a substituent, An aryloxy group which may have a substituent, an aryloxy group which may have a substituent, an alkylamino group which may have a substituent, an arylamino group which may have a substituent, an alkylsulfonyl group which may have a substituent, , And more preferably an aryl group which may have a hydrogen atom, a carboxyl group, an alkoxycarbonyl group, an alkyl group which may have a substituent, or a substituent.

The substituent which can be introduced includes the same substituents as those described in the general formula (i).

Y ²⁰¹ represents an oxygen atom, a sulfur atom, or -N (R ²⁰⁶ ) -. R ²⁰⁶ is synonymous with R ^{104 in} formula (i), and preferred examples are also the same.

[Chemical Formula 13]

(In the general formula (iii), R ³⁰¹ to R ³⁰³ each independently represent a hydrogen atom or a monovalent organic group, and Z ³⁰¹ represents an oxygen atom, a sulfur atom, -N (R ³⁰⁴ ) R ³⁰⁴ is the same as R ^{104 in the} general formula (i).)

In formula (iii), R ³⁰¹ to R ³⁰³ each independently represent a hydrogen atom or a monovalent organic group. R ³⁰¹ is preferably a hydrogen atom or an alkyl group which may have a substituent, and among them, a hydrogen atom or a methyl group is more preferable because of high radical reactivity. R ³⁰² and R ³⁰³ each independently represent a hydrogen atom, a halogen atom, an amino group, a carboxyl group, an alkoxycarbonyl group, a sulfo group, a nitro group, a cyano group, an alkyl group which may have a substituent, An aryloxy group which may have a substituent, an aryloxy group which may have a substituent, an alkylamino group which may have a substituent, an arylamino group which may have a substituent, an alkylsulfonyl group which may have a substituent, or a substituent , And more preferably an aryl group which may have a hydrogen atom, a carboxyl group, an alkoxycarbonyl group, an alkyl group which may have a substituent, or an aryl group which may have a substituent, from the viewpoint of high radical reactivity.

The substituent which can be introduced includes the same substituents as those described in the general formula (i). Z ³⁰¹ represents an oxygen atom, a sulfur atom, -N (R ³⁰⁴ ) - or a phenylene group which may have a substituent. R ³⁰⁴ is the same as R ^{104 in the} general formula (i), and examples of the monovalent organic group include an alkyl group which may have a substituent. Among them, the methyl group, the ethyl group and the isopropyl group have a high radical reactivity .

When the composition for forming a releasable region has a radically polymerizable monomer or oligomer having a silicon atom, the content of the radically polymerizable monomer or oligomer having a silicon atom is preferably from 0.01 to 15% by mass, . If it is 0.01% by mass or more, sufficient peeling property can be obtained. If it is 15 mass% or less, sufficient adhesion can be obtained.

The radically polymerizable monomer or oligomer having a silicon atom may be only one kind or two or more kinds. When two or more types of radically polymerizable monomers or oligomers having a silicon atom are contained, the total amount is preferably in the above range.

Examples of the radically polymerizable monomer having a fluorine atom or a silicon atom include RS-75, RS-72-K, RS-76-E, RS-72-K manufactured by DIC Corporation, X-22-164AS, X-22-164A, X-22-164B and X-22-164B manufactured by Shin-Etsu Chemical Co., Ltd., fluorine-based silane coupling agents, 22-164C, X-22-164E, EBECRYL 350, EBECRYL 1360 manufactured by Daicel-Cytech Corporation, TEGORad 2700 and UV-3500B (manufactured by BYK) manufactured by Degussa.

As the material having a fluorine atom or a silicon atom, in addition to the above, heptadecafluoro-1,1,2,2-tetrahydrodecyl) trichlorosilane, (fluoro) alkylphosphonate, parylene fluoride, Silicon acrylate copolymers, copolymers of tetrafluoroethylene and 2,2-bis-trifluoromethyl-4,5-difluoro-1,3-dioxole, polymers having pendant perfluoroalkoxy groups, And fluorinated ethylene-propylene copolymers.

The content of the releasing component is preferably 0.01 to 10% by mass, more preferably 0.05 to 5% by mass, and particularly preferably 0.1 to 1% by mass, based on the total solids content (amount excluding solvent) Do.

<< Surfactant >>

The adhesive composition preferably further contains a surfactant. As the surfactant, those described in the section of the adhesive region are suitably used, and the preferred range is also the same.

The content of the surfactant is preferably 0.001 to 1% by mass, more preferably 0.01 to 0.5% by mass, particularly preferably 0.05 to 0.1% by mass, with respect to the total solid content (amount excluding the solvent) Do.

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

<< Antioxidants >>

The adhesive composition preferably further contains an antioxidant. As the antioxidant, those described in the section of the adhesive region are preferably used, and the preferable range is also the same.

The content of the antioxidant is preferably 0.001 to 10% by mass, more preferably 0.01 to 5% by mass, and particularly preferably 0.1 to 1% by mass, based on the total solids content (amount excluding solvent) Do.

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

<< Plasticizer >>

The adhesive composition preferably includes a plasticizer in order to enhance the deformability at high temperatures and to improve the flatness of adhesion.

As the plasticizer, phthalic acid ester, fatty acid ester, aromatic polycarboxylic acid ester, polyester and the like can be used.

Examples of the phthalic ester include DMP, DEP, DBP, # 10, BBP, DOP, DINP, DIDP (available from Daihachi Chemical), PL-200, DOIP Manufactured by Shin-Nippon Rika KK).

Examples of the fatty acid ester include butyl stearate, Unistar M-9676, Unistar M-2222SL, Unistar H-476, Unistar H-476D, Panaset 800B, Panaset 875, Panaset 810 DIBA, DBA, DOA, DINA, DIDA, DOS, BXA, DOZ, DESU (available from Daihachi Chemical).

Examples of the aromatic polycarboxylic acid ester include TOTM (Daihachi Kagaku), Monoisizer W-705 (Daihachi Kagaku), UL-80 and UL-100 (manufactured by ADEKA).

Examples of the polyester include Polysizer TD-1720, Polysizer S-2002, Polysizer S-2010 (manufactured by DIC) and BAA-15 (manufactured by Daihachi Kagaku).

Among the above plasticizers, DIDP, DIDA, TOTM, Unistar M-2222SL and Polysizer TD-1720 are preferable, DIDA and TOTM are more preferable, and TOTM is particularly preferable.

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

From the viewpoint of preventing sublimation during heating, the molecular weight of the plasticizer is preferably 250 DEG C or more at a weight reduction of 1 mass% when measured under a constant rate of 20 DEG C / min under a nitrogen stream, and more preferably 270 DEG C or more Particularly preferably 300 DEG C or higher. The upper limit is not specifically defined, but can be set to, for example, 500 ° C or lower.

The content of the plasticizer is preferably 1 to 50.0 mass%, more preferably 5 to 20.0 mass%, with respect to the total mass of the adhesive composition.

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

<< Other additives >>

The adhesive composition for adhesion according to the present invention may be compounded with various additives such as a curing agent, a curing catalyst, a filler, an ultraviolet absorber, an anti-aggregation agent, and the like insofar as the effect of the present invention is not impaired . When these additives are compounded, the total amount of these additives is preferably 3% by mass or less of the solid content of the adhesive composition.

The adhesive region of the adhesive film of the present invention can be obtained by subjecting the above-mentioned adhesive composition to a heat treatment using a conventionally known spin coating method, a spraying method, a roller coating method, a float coating method, a doctor coating method, Applying it on a support substrate, and then drying it. Of these, the spin coating method, the spray method and the screen printing method are preferable, and the spin coating method and the spraying method are more preferable, and the spin coating method is particularly preferable.

&Lt; Composition for forming a heterogeneous region &

Next, the composition for forming a releasing region will be described.

The composition for forming a releasable region preferably contains a releasable component and a solvent.

<< Release Component >>

The releasing component is preferably a material containing at least one kind selected from a fluorine atom and a silicon atom. Examples of the material containing at least one kind selected from a fluorine atom and a silicon atom include a polymerizable monomer having a fluorine atom or a silicon atom. A fluorine-based silane coupling agent is more preferable. By the fluorine-based silane coupling agent, the layer of the releasing region can be firmly formed on the surface of the adhesion region. This makes it difficult for the solvent to penetrate the interface between the adhesive layer and the release layer, thereby forming an adhesion film having excellent tolerance. The details of the releasing component are the same as those described in the section on the releasing component of the above-mentioned pressure-sensitive adhesive composition, and the preferable range is also the same.

The content of the releasing component is preferably from 5 to 100% by mass, more preferably from 50 to 100% by mass, further preferably from 90 to 100% by mass, based on the total solid content of the composition for forming a releasable region from the viewpoint of good releasability Do.

<< Solvent >>

As the solvent, any known one can be used as long as it can form a release region, and the same solvent as the solvent for the above-mentioned pressure-sensitive adhesive composition can be used. In addition, perfluoroalkane can be used. Among them, N-methyl-2-pyrrolidone, 2-butanone, methylamylketone, limonene, 1-methoxy-2-propyl acetate, perfluoroalkane and methyl ethyl ketone are preferable, 2-pyrrolidone, 2-butanone, methyl amyl ketone, limonene and 1-methoxy-2-propyl acetate are more preferable.

These solvents are also preferably mixed with two or more kinds in view of improving the application surface shape and the like.

<< Other ingredients >>

In addition to the above-mentioned components, the composition for forming a releasable region may contain various compounds according to the purpose insofar as the effect of the present invention is not impaired. For example, a thermal polymerization initiator, a sensitizing dye, a chain transfer agent, an antioxidant, and a surfactant can be preferably used. These may be those described in the above for the adhesive composition.

The solid content concentration of the composition for forming a releasable region is preferably from 3 to 40% by mass, more preferably from 5 to 40% by mass.

The releasing region is formed by applying the above-described composition for forming a releasing region onto a supporting substrate by using a conventionally known spin coating method, a spraying method, a roller coating method, a float coating method, a doctor coating method, a dipping method, Followed by drying. Of these, the spin coating method, the spray method and the screen printing method are preferable, and the spin coating method and the spraying method are more preferable, and the spin coating method is particularly preferable.

<Kit>

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

The kit of the present invention includes the above-described composition for peeling adhesion, the above-mentioned composition for releasing area including a releasing component and a solvent.

The adhesive film of the present invention can be produced by sequentially applying an adhesive composition and a composition for forming a release area on a support substrate.

The adhesive film of the present invention can also be produced by sequentially applying a composition for forming a releasing area and a composition for adhesion to a device wafer.

The composition, the preferable range, etc. of each of the adhesive composition and the composition for forming a releasable area are the same as those described above.

<Laminate>

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

The laminate of the present invention is formed by laminating device wafers on the surface of the release region of the adhesive film of the present invention described above.

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

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

The device wafer preferably has a structure such as a metal bank. The adhesive film of the present invention can stably adhere to a device wafer having a structure on the surface and can easily release adherence to the device wafer. The height of the structure is not particularly limited, but is preferably 5 to 100 占 퐉, for example.

The thickness of the device wafer before mechanical or chemical treatment is preferably 500 탆 or more, more preferably 600 탆 or more, and more preferably 700 탆 or more.

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

In the laminate of the present invention, it is preferable that a supporting substrate is disposed on the surface of the adherent film opposite to the laminated surface of the device wafer.

The material of the support substrate is not particularly limited, and examples thereof include a silicon substrate, a glass substrate, a metal substrate, and a compound semiconductor substrate. Among them, a silicon substrate is preferable in view of the fact that a silicon substrate typically used as a substrate of a semiconductor device is not easily contaminated, and an electrostatic chuck generally used in a semiconductor device manufacturing process can be used.

The thickness of the supporting substrate is not particularly limited, but is preferably 300 占 퐉 to 5 mm, for example.

&Lt; Device Manufacturing Method >

Next, a method of manufacturing the device of the present invention will be described.

The method of manufacturing a device of the present invention includes a step of applying the above-described adhesive composition of the present invention. Hereinafter, the method of manufacturing the device of the present invention will be described in more detail.

&Lt; Support substrate - Adhesion film - Production of device wafer laminate &gt;

Supporting Substrate-Adhesive Film-Device A wafer laminate (hereinafter also referred to as a laminate) can be produced by any one of the following methods (1) to (4).

(1) The adhesive composition of the present invention is applied to a supporting substrate and heated (baked) to form a layer of an adhesive region. Examples of the application method of the adhesive composition include conventionally known methods such as spin coating, spraying, roller coating, float coating, doctor coating, and dipping.

Subsequently, the aforementioned composition for forming a mold release region is applied on the layer of the adhesion region and heated (baked) to form a layer of the mold release region to form the adhesion film of the present invention. Examples of the application method of the composition for forming a release-type region include conventionally known methods such as a spin coating method, a spraying method, a roller coating method, a float coating method, a doctor coating method and a dipping method.

Subsequently, a device wafer is pressed and adhered to a surface of the adherent film opposite to the surface on which the support substrate is disposed (that is, the surface of the adherent film on the side of the release layer), thereby producing a laminate. The pressure bonding conditions are, for example, a temperature of 100 to 200 DEG C, a pressure of 0.01 to 1 MPa, and a time of 1 to 15 minutes.

(2) The composition for forming a mold release region is applied to a device wafer and heated (baked) to form a mold release region.

Subsequently, the adhesive composition of the present invention is coated on the layer of the releasing area and heated (baked) to form a layer of the adhesive area to form the adhesive film of the present invention.

Subsequently, the supporting substrate is pressed and adhered to a surface of the adherent film opposite to the surface on which the device wafer is arranged (i.e., the surface of the adherent film on the adhered area side), thereby producing a laminate. The pressure bonding conditions are preferably the above-described conditions.

(3) The adhesive composition of the present invention containing a releasing component is applied to the surface of either the support substrate or the device wafer and heated (baked) to form an adhesive layer, Thereby forming a film.

Subsequently, a support substrate or a device wafer is pressure-adhered to the surface of the adhesive film to produce a laminate. The pressure bonding conditions are preferably the above-described conditions.

(4) The composition for forming a mold release region is applied to a device wafer and heated (baked) to form a layer of a mold release region on the device wafer.

Subsequently, the above-mentioned adhesive composition for adhesion of the present invention is applied to the support substrate and heated (baked) to form a layer of the adhesive region on the support substrate.

Subsequently, the release region on the device wafer and the adhesion region on the support substrate are pressure-bonded to form an adhesion film, and a laminate is produced. The pressure bonding conditions are preferably the above-described conditions.

Hereinafter, a method of manufacturing a device wafer that has undergone a process of manufacturing a laminate by the method shown in (4) will be described with reference to FIG.

1A, 1B and 1C are schematic cross-sectional views illustrating the adhesion of a support substrate and a device wafer, respectively, a schematic cross-sectional view showing a device wafer adhered by a support substrate, and a device wafer Is a schematic sectional view showing a state of being thinned.

1A, a device wafer 60 is formed by providing a plurality of device chips 62 on a surface 61a of a silicon substrate 61. As shown in FIG. In addition, a release region 71 is provided on the surface of the device wafer 60 on the side of the structure 63.

The device wafer 60 preferably has a film thickness of 500 탆 or more on average. The structure 63 is called a device chip or a bump, and the average height is preferably in the range of 5 to 100 mu m.

As shown in Fig. 1A, an adhesive supporting body 100 comprising an adhesive region 11 provided on a supporting substrate 12 is prepared. The adhesive support 100 is obtained by applying the adhesive composition of the present invention to a support substrate 12 (for example, a glass substrate) by using a conventionally known spin coating method, a spraying method, a roller coating method, a float coating method, a doctor coating method, ), And then drying it.

Next, adhering of the adhesive support 100 to the device wafer 60, thinning of the device wafer 60, and peeling of the adhesive support 100 from the device wafer will be described below .

The surface of the release region 71 provided on the device wafer is pressed against the adhesive region 11 of the adhesive support 100. [ As a result, as shown in Fig. 1B, the release film 71 and the adhesion area 11 are adhered to each other to form the adhesion film 80 having the release area 71 and the adhesion area 11.

Subsequently, the back surface 61b of the silicon substrate 61 is subjected to a mechanical or chemical treatment (not particularly limited, for example, a thinning treatment such as gliding or chemical mechanical polishing (CMP), a high temperature / A plating process, an actinic ray irradiation, a heating / cooling process, and the like) are performed to form the silicon substrate 61, as shown in Fig. 1C, (For example, it is preferable that the average thickness is less than 500 占 퐉 and more preferably 1 to 200 占 퐉) to obtain a thin device wafer 60a.

As a mechanical or chemical treatment, a through hole (not shown) passing through the silicon substrate is formed from the back surface 61c of the thin device wafer 60a after the thinning treatment, and a silicon penetration electrode (Not shown) may be formed. Concretely, the maximum attained temperature in the heat treatment is preferably 130 ° C to 400 ° C, more preferably 180 ° C to 350 ° C. The maximum reaching temperature in the heat treatment becomes lower than the softening point of the adhesion region. The heat treatment is preferably heating for 30 seconds to 30 minutes at the maximum attained temperature, and more preferably for 1 minute to 10 minutes at the maximum attained temperature.

Subsequently, the adhesion film 80 is peeled from the surface 61a of the thin device wafer 60a.

It is preferable that the adhesive film 80 is peeled off by physical action such as peeling. That is, it is preferable to slide the thin device wafer 60a to the adhesive supporting member 100 or peel the thin device wafer 60a from the adhesive supporting member 100. [ By this method, the adhesion film 80 can be peeled from the surface 61a of the thin device wafer 60a.

After removing the adhesive film 80 from the thin device wafer 60a, the surface 61a of the thin device wafer 60a may be treated with a peeling liquid or the like, if necessary. As the peeling solution, for example, the peeling solution described in paragraphs 0203 to 0212 of Japanese Laid-Open Patent Publication No. 2014-80570 can be used. The adhesive film 80 of the present invention is not necessarily required to be treated with a peeling liquid or the like. The adhesive film 80 can be removed from the surface 61a of the thin device wafer 60a without causing peeling residue or the like only by the mechanical peeling.

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

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

In the above-described embodiment, the silicon substrate is taken as an example of the member to be processed. However, the silicon substrate is not limited to the silicon substrate, but may be any member that can be provided for mechanical or chemical treatment in the manufacturing method of the device. Examples of the compound semiconductor substrate include SiC substrate, SiGe substrate, ZnS substrate, ZnSe substrate, GaAs substrate, InP substrate, GaN substrate, and the like.

In the above-described embodiment, the thinning treatment of the silicon substrate and the forming process of the silicon through electrode are exemplified as the mechanical or chemical treatment for the silicon substrate supported by the supporting substrate. However, the present invention is not limited to these, And any process necessary for the manufacturing method of the device.

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

Example

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

(Example 1)

&Lt; Formation of Adhesion Zone &

Composition 1 for forming an adhesion area having the composition shown in Table 1 was applied to a 4-inch Si wafer by a spin coater (Opticoat MS-A100, manufactured by Mikasa, 1200 rpm, 30 seconds) Baked to form a wafer 1 provided with an adhesion area of 5 mu m in thickness.

&Lt; Formation of Dislocation Region &

The composition 1 for forming a mold releasing region having the composition shown in Table 2 was applied to the adhesion area of the wafer 1 by a spin coater (Opticoat MS-A100, manufactured by Mikasa, 1200 rpm, 30 seconds) Lt; 0 &gt; C for 3 minutes to form a 0.1-μm-thick release region on the adhesion region, thereby forming a wafer 1 provided with an adhesion film.

&Lt; Preparation of test piece &

A test piece was produced by thermocompression bonding the wafer 1 and a 4-inch Si wafer (wafer 2) on the surface of which nothing was applied.

[pressure]

The surface of the wafer 1 having the adhesion film and the surface of the wafer 2 not coated with the wafer 2 were brought into contact with each other, and pressure bonding was performed at 190 DEG C and 0.20 MPa for 3 minutes.

[Bake]

After pressure bonding, it was heated at 280 占 폚 for 30 minutes.

(Examples 2 to 32 and 35)

In Example 1, a bonding region and a releasing region were formed by the combination shown in Table 3 for the composition for forming an adhesive region and the composition for forming a releasable region, respectively, to prepare a test piece provided with an adhesive film in the same manner as in Example 1. [

(Example 33)

A composition prepared by mixing 99 mass% of the composition for forming the adhesion area 19 and 1 mass% of the composition 1 for forming a mold release area was applied on a 4 inch Si wafer by a spin coater (Opticoat MS-A100, 1200 rpm, 30 sec. The wafer 1 was baked at 120 ° C for 3 minutes and at 250 ° C for 3 minutes to form a wafer 1 having an adhesion area of 5 μm in thickness and a test piece provided with an adhesion film was prepared in the same manner as in Example 1.

(Example 34)

A composition prepared by mixing 99 mass% of the composition for forming an adhesive region 19 and 1 mass% of the composition 2 for forming a releasable region was applied to a 4 inch Si wafer by a spin coater (Opticoat MS-A100, 1200 rpm, 30 seconds by Mikasa) The wafer 1 was baked at 120 ° C for 3 minutes and at 250 ° C for 3 minutes to form a wafer 1 having an adhesion area of 5 μm in thickness and a test piece provided with an adhesion film was prepared in the same manner as in Example 1.

(Comparative Example 1)

In the same manner as in Example 1 except that the release-type-region-forming composition 1 was not used in Example 1, a test piece provided with an adherent film was produced.

(Comparative Example 2)

In the same manner as in Example 1 except that the composition 1 for forming an adhesive region was not used in Example 1, a test piece provided with an adhesive film was produced.

(Comparative Examples 3 to 7)

A test piece provided with an adhesive film was prepared in the same manner as in Example 1 except that Comparative Compositions 1 to 7 were used instead of the adhesive layer forming composition 1 in Example 1.

<Adhesiveness>

The shear adhesive strength of the prepared test piece was measured by tensile tester (manufactured by IMADA) in the direction along the surface of the adhesive film at a rate of 50 mm / min and evaluated according to the following criteria. In the following evaluation criteria, 2 to 5 are practical, and 3 to 5 are preferable.

5: Adhesion of 80 N or more

4: Adhesion of 60N or more and less than 80N

3: Adhesion of 40N or more and less than 60N

2: Adhesion between 20N and less than 40N

1: Adhesion less than 20N

<Peelability>

The fabricated test piece was subjected to tensile measurement at a rate of 50 mm / min in a direction perpendicular to the surface of the adherent film, and evaluated by the following criteria. In the following evaluation criteria, 2 to 5 are practical, and 3 to 5 are preferable.

5: can be peeled off with a force of less than 3N, and no residue is visually observed on the surface of the wafer 2

4: can be peeled off with a force of 3N or more and less than 5N, and no residue is visually observed on the surface of the wafer 2

3: It can be peeled off with a force of 3N or more but less than 5N, but a residue is visually observed on the surface of the wafer 2

2: Peeling can be performed with a force of 5 N or more and 7 N or less, but the residue of the wafer 2 is visually observed on the surface of the wafer 2

1: The wafer is damaged in the process of peeling.

<Tolerance>

The prepared test pieces were placed in a glass container filled with N-methyl-2-pyrrolidone at 25 占 폚 and ultrasonic waves were applied for 15 minutes using an ultrasonic washing machine. The samples were observed and evaluated according to the following criteria. In the following evaluation criteria, 2 to 5 are practical, and 3 to 5 are preferable.

5: There is no peeling of the wafer, and the surface of the adhesive film after peeling is not affected by the solvent

4: No peeling of the wafer, but a range of less than 1 mm from the side of the peeled adhesive film that was in contact with the solvent was invaded by the solvent

3: There is no peeling of the wafer, but a range of 1 mm or more and less than 5 mm from the side of the peeled adhesive film that was in contact with the solvent is invaded by the solvent

2: No peeling of the wafer, but a range of 5 mm or more from the side of the peeled adhesive film that was in contact with the solvent was invaded by the solvent

1: Wafer peeled off

<Boyd>

In forming the wafer 1, the adhesive layers of Examples 1 to 35 and Comparative Examples 1 to 9 were formed without changing the 4-inch glass wafer instead of the 4-inch Si wafer, and were bonded to a 4-inch Si wafer . The obtained sample was heated in an oven at 400 DEG C for 3 hours in a nitrogen atmosphere. Thereafter, the adhesive layer was visually observed from the glass wafer side of the sample, and evaluated by the following criteria. In the following evaluation criteria, 2 to 5 are practical, and 3 to 5 are preferable.

The void is a void generated at the interface between the adhesive layer and the glass.

5: No visible voids

4: Less than 5 voids

3: 5 or more and less than 10 voids

2: More than 10 voids and less than 15 voids

1: More than 15 voids

[Table 1]

The compounds shown in Table 1 are as follows.

[Resin component]

B-1: Durimide (R) 284

(FUJIFILM, solvent-soluble polyimide resin)

B-2: Durimide (R) 10

(FUJIFILM, solvent-soluble polyamide-imide resin)

B-3: GPT-LT (Ganagoguchi, solvent-soluble polyimide resin)

B-4: Rika coat (polyamide-imide resin, manufactured by Shin-Nihon Rikagaku Co., Ltd.)

B-5: BIROMAX (R) 13NX

(Toyo Bosje, polyamideimide resin)

B-6: MRS0810H

(PBI, polybenzimidazole resin)

B-7: CRC-8800 (made by Sumitomo Bakelite, polybenzoxazole resin)

B-8: Ultrason E6020 (manufactured by BASF, polyethersulfone resin)

B-9: PCZ-500 (manufactured by MGC, polycarbonate resin)

[Crosslinking component]

C-1: BMI-1000 (manufactured by Daiwa Kasei Kogyo Co., bismaleimide resin)

C-2: BMI-2000 (manufactured by Daiwa Kasei Kogyo Co., bismaleimide resin)

C-3: BMI-3000 (manufactured by Daiwa Kasei Kogyo Co., bismaleimide resin)

C-4: BMI-4000 (manufactured by Daiwa Kasei Kogyo Co., bismaleimide resin)

C-5: BMI-5000 (manufactured by Daiwa Kasei Kogyo Co., bismaleimide resin)

C-6: BMI-7000 (manufactured by Daiwa Kasei Kogyo Co., bismaleimide resin)

C-7: BANI-X (Shin-Nakamura Kagaku Co., bismaleimide resin)

C-8: BANI-M (Shin-Nakamura Kagaku Co., bismaleimide resin)

C-9: A-9300 (available from Shin-Nakamura Chemical Co., Ltd., acrylate resin)

[Thermal polymerization initiator]

D-1: Percumyl H (Nitrate, organic peroxide, 1 minute half-life temperature 254 ° C)

D-2: Percumyl P (Nitrate emulsion, organic peroxide, 1 minute half-life temperature 232.5 ℃)

D-3: Perbutyl Z (Nitrate, organic peroxide, 1 minute half-life temperature of 166.8 캜)

D-4: Nippers BW (Nichi tung, organic peroxide, 1 minute half-life temperature 130.0 ℃)

D-5: V-601 (Wako, azo initiator, 1 minute half-life temperature 120 캜)

Comparative compositions 1 to 8 in Table 1 were prepared by the following methods.

Comparative Composition 1: A composition of Example 1 of Japanese Laid-Open Patent Publication No. 2014-29999 was prepared

Comparative Composition 2: A composition of Example 2 of JP-A-2014-29999 was prepared

Comparative Composition 3: A composition of Example 3 of JP-A-2014-29999 was prepared

Comparative Composition 4: A composition of Example 4 of JP-A-2014-29999 was prepared

Comparative Composition 5: The composition of Example 5 of Japanese Laid-Open Patent Publication No. 2014-29999 was prepared

COMPARATIVE COMPOSITION 6: A composition of Example 6 of JP-A-2014-29999 was prepared

Comparative Composition 7: In the adhesion-improving composition 1, the crosslinking component C-1 was not contained

The mass reduction rate at 400 deg. C in Table 1 was measured by the following method.

&Lt; 400 占 폚 mass reduction rate>

2-3 mg of the sample was heated on an aluminum pan to 400 DEG C under a constant temperature raising condition of 10 DEG C / min at an initial temperature of 25 DEG C under a nitrogen stream of 60 mL / min on a thermogravimetric analyzer Q500 (manufactured by TA) Lt; 0 &gt; C, the residual mass was measured.

The solubility in Table 1 was measured by the following method.

<Solubility>

To 100 g of N-methyl-2-pyrrolidone, a certain amount of the sample was added with stirring to confirm the solubility. When completely dissolved, the sample was further stirred and added in a constant amount, and the solubility was defined as the amount immediately before the sample was not dissolved when the solution was finally stirred at 25 ° C for 1 hour.

[Table 2]

The compounds described in Table 2 are as follows.

[Release Component]

A-1: Optol DSX (a fluorine-based silane coupling agent manufactured by Daikin Industries, Ltd.)

A-2: RS-72-K (manufactured by DIC, fluorine-based compound)

A-3: RS-76-E (a fluorine-based compound manufactured by DIC Corporation)

A-4: UV-3500B (manufactured by BYK, a silicone compound)

A-5: (heptadecafluoro-1,1,2,2-tetrahydrodecyl) trichlorosilane (manufactured by TCI)

A-6: CHEMINOX FHP-2-OH (fluorine-based compound manufactured by UNIMATEC)

A-7: TEFLON (registered trademark) AF (a fluorine-based compound manufactured by Mitsui DuPont Fluorochemical Co., Ltd.)

A-8: CYTOP (fluorine-based compound, manufactured by Asahi Glass Co., Ltd.)

A-9: KP541 (a silicone compound manufactured by Shin-Etsu Chemical Co., Ltd.)

A-10: Dyneon THV (manufactured by 3M, fluorine-based compound)

Among them, A-1 to A-4 indicate that the release layer constitutes a three-dimensional cross-linked body.

[solvent]

S-1: Perfluorohexane (manufactured by Wako Pure Chemical Industries, Ltd.)

S-2: 1-Methoxy-2-propyl acetate

S-3: CT-Solv 180 (AGC)

S-4: methyl ethyl ketone

[Table 3]

From the results, it was found that the adhesive films of Examples 1 to 35 exhibited satisfactory adhesiveness, peelability and tolerance. Also, voids were few.

On the other hand, Comparative Examples 1 to 9 were below the practical level in at least one of adhesion, peelability and tolerance.

11 Adhesion Zone
60 device wafer
60a thin device wafer
61 silicon substrate
61a surface of a silicon substrate
61b The back surface of the silicon substrate
61c back surface of thin device wafer
62 device chip
63 Structure
71 Release area
80 is a bonding layer
100 adhesive backing

Claims (24)

An adhesive region, and a release region on the surface of the adhesive region,
The adhesion region has a mass reduction rate of 1 mass% or less at 400 占 폚 when the temperature is raised at 25 占 폚 at 10 占 폚 / min, a solubility in N-methylpyrrolidone at 25 占 폚 of 1 g / ,
Wherein the adhesive region is formed of a resin containing a heterocyclic ring-containing resin containing at least one member selected from a polyimide resin, a polyamideimide resin, a polybenzimidazole resin and a polybenzoxazole resin,
Wherein the crosslinking component contains a maleimide resin and contains 5% by mass or less of a compound having an epoxy group in the crosslinking component,
Wherein the releasing region comprises a compound containing at least one selected from a fluorine atom and a silicon atom. The method according to claim 1,
Wherein the maleimide resin is represented by the following general formula (III).

[In the formula (III), R represents an aromatic ring or a divalent organic group containing a straight-chain, branched-chain or cyclic aliphatic hydrocarbon group.] The method according to claim 1,
Wherein the heterocyclic ring-containing resin is at least one kind of solvent selected from gamma -butyrolactone, cyclopentanone, N-methylpyrrolidone, cyclohexanone, glycol ether, dimethylsulfoxide and tetramethylurea Is a polyimide resin having a solubility of not less than 10 g / 100 g Solvent at 25 캜. The method according to claim 1 or 3,
Wherein the maleimide resin is a bismaleimide resin. The method according to any one of claims 1 to 3,
Wherein 50 to 100% by mass of the crosslinking component contained in the adhesive region is the maleimide resin. The method according to any one of claims 1 to 3,
Wherein the adhesive region further contains a thermal polymerization initiator. The method of claim 6,
Wherein the thermal polymerization initiator has a half-life temperature for one minute of 130 to 300 占 폚. The method of claim 6,
Wherein the thermal polymerization initiator is an organic peroxide. The method according to any one of claims 1 to 3,
Wherein the adhesive region further contains a thermal polymerization initiator having a half-life temperature for one minute of from 150 ° C to 260 ° C. The method according to any one of claims 1 to 3,
Wherein the releasing region contains a fluorine-based silane coupling agent. A laminate having a device wafer on the surface of the release agent region side of the adhesive film according to any one of claims 1 to 3. A resin containing at least one selected from a polyimide resin, a polyamideimide resin, a polybenzimidazole resin and a polybenzoxazole resin,
A crosslinking component,
A solvent,
Wherein 50 to 100% by mass of the crosslinking component is a maleimide resin,
A composition for adhering to form an adhesive region according to claim 1. The method of claim 12,
Wherein the heterocyclic ring-containing resin is at least one kind of solvent selected from the group consisting of? -Butyrolactone, cyclopentanone, N-methylpyrrolidone, cyclohexanone, glycol ether, dimethylsulfoxide and tetramethylurea Is a polyimide resin having a solubility of 10 g / 100 g Solvent or more at 25 占 폚. The method according to claim 12 or 13,
Wherein the maleimide resin is a bismaleimide resin. The method according to claim 12 or 13,
And further contains a thermal polymerization initiator. 16. The method of claim 15,
Wherein the thermal polymerization initiator has a half-life temperature for one minute of 130 to 300 占 폚. 18. The method of claim 16,
Wherein the thermal polymerization initiator is an organic peroxide. The method according to claim 12 or 13,
And further comprising a releasing component. 19. The method of claim 18,
Wherein the releasing component comprises a compound containing at least one selected from a fluorine atom and a silicon atom. 19. The method of claim 18,
Wherein the releasing component is a fluorine-based silane coupling agent. A method for manufacturing a device, comprising the step of applying the adhesive composition according to claim 12 or 13. Wherein the adhesive region has a mass reduction rate of 1% by mass or less at 400 占 폚 when the temperature is raised at 25 占 폚 at 10 占 폚 / -Methylpyrrolidone having a solubility of 1 g / 100 g Solvent or less,
The adhesive bonding composition according to claim 12 or 13,
A composition for forming a mold release region comprising a mold release component and a solvent
&Lt; / RTI &gt; The method of claim 12,
Wherein the maleimide resin is represented by the following general formula (III).

[In the formula (III), R represents an aromatic ring or a divalent organic group containing a straight-chain, branched-chain or cyclic aliphatic hydrocarbon group.] The method of claim 12,
And a half-life temperature for one minute of 150 ° C to 260 ° C.

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