TWI663239B - Temporary bonding film, laminated body, temporary bonding composition, device manufacturing method and kit - Google Patents

Abstract

The invention provides a temporary bonding film, a laminated body, a temporary bonding composition, a component manufacturing method, and a kit. The temporary bonding film can stably temporarily bond a component wafer when mechanically or chemically processing the component wafer. It can easily release the temporary bonding to the element wafer, and has excellent chemical resistance. The temporary adhesive film has a bonding region and a mold release region on the surface of the bonding region, and the mass reduction rate of the bonding region at 400 ° C when the temperature is raised at 10 ° C / min from 25 ° C is 1% by mass or less. The solubility of N-methylpyrrolidone at 25 ° C is 1 g / 100 g or less of solvent.

Description

Temporary bonding film, laminated body, temporary bonding composition, device manufacturing method and kit

The present invention relates to a temporary bonding film, a laminated body, a temporary bonding composition, a method for manufacturing a device, and a kit. More specifically, the present invention relates to a temporary bonding film, a laminated body, a temporary bonding composition, a method for manufacturing a device, and a kit which can be preferably used for manufacturing various devices such as semiconductor devices.

In the manufacturing process of a semiconductor device such as an integrated circuit (IC) or a large scale integration (LSI), a plurality of IC chips are formed on the element wafer, and the dicing ( dicing) and singulation.

With the further miniaturization and high performance needs of electronic equipment, IC chips mounted on electronic equipment are also required to be further miniaturized and highly integrated, but the product in the plane direction of the element wafer The high integration of the body circuit is approaching the limit.

As a method of electrically connecting an integrated circuit in an IC chip to an external terminal of the IC chip, a wire bonding method has been widely known, but in order to achieve miniaturization of the IC chip, the following method has been known in recent years: A through-hole is provided on the wafer, and a metal plug serving as an external terminal is connected to the integrated circuit so as to penetrate through the through-hole (so-called through silicon through-electrode (Through Silicon) Via, TSV)). However, the method of forming only the through-silicon electrodes is difficult to sufficiently meet the demand for further high integration of IC chips in recent years.

In view of the above, a technique is known in which the integrated circuit in an IC wafer is multilayered, thereby increasing the integration degree per unit area of an element wafer. However, since the multilayer of the integrated circuit increases the thickness of the IC chip, it is necessary to reduce the thickness of the components constituting the IC chip. Regarding the reduction in thickness of such members, for example, the reduction in thickness of element wafers has been studied. This method not only contributes to miniaturization of IC wafers, but also saves labor in the process of manufacturing through-holes of element wafers in the manufacture of silicon through-electrodes. , So it is considered promising. In addition, in semiconductor devices such as power devices and image sensors, attempts have been made to reduce the thickness from the viewpoint of increasing the integration degree or increasing the degree of freedom of the device structure.

As element wafers, those having a thickness of about 700 μm to 900 μm are widely known. In recent years, attempts have been made to reduce the thickness of element wafers to 200 μm or less for the purpose of miniaturization of IC wafers and the like.

However, element wafers with a thickness of 200 μm or less are very thin, and components for manufacturing semiconductor elements using the substrate as substrates are also very thin. Therefore, it is difficult to stabilize such components when further processing is performed or only such components are moved. Support members without damage.

In order to solve the problems described above, a technique is known in which a component wafer before thinning and a support substrate (carrier substrate) are temporarily fixed (temporarily adhered) by a temporary adhesive, and the rear surface of the component wafer is ground to be thin. After conversion, the support substrate is detached from the element wafer.

For example, Patent Document 1 discloses a method for manufacturing a semiconductor device, which includes a step of interposing a film for temporary fixation containing a specific polyimide resin between a support member and an element wafer, and interposing the element crystal. The circle is temporarily fixed on the supporting member; the element wafer temporarily fixed on the supporting member is subjected to predetermined processing; the organic solvent is brought into contact with the temporarily fixing film to dissolve a part or all of the temporarily fixing film, and the processed component is dissolved. The wafer is separated from the supporting member; and the processed element wafer is singulated.

On the other hand, Patent Document 2 discloses an invention related to a semiconductor element fixing adhesive (adhesive for die bonding) for bonding semiconductor elements to each other or a semiconductor element to a support substrate. As this adhesive, it has been disclosed that the following adhesive composition is formed into a sheet shape, the adhesive composition containing: (A) a thermoplastic resin containing (A1) a glass transition temperature of 60 ° C. or lower and a weight average A polyimide resin having a molecular weight of 10,000 to 100,000 and (A2) were dissolved in N-methyl-2-pyrrolidone so that the resin content became 20% by mass. The viscosity at 25 ° C was 10 poise. ) The above non-polyimide resin; and (B) a thermosetting component, containing (B1) an epoxy resin and (B2) a bismaleimide resin.

[Prior Art Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2014-29999

[Patent Document 2] Japanese Patent Laid-Open No. 2012-241134

In the case of temporarily bonding the surface of the element wafer to the support substrate, in order to stably support the element wafer, a temporary bonding film between the surface of the element wafer and the support substrate is required to have a strong bonding force, and it is required to be easy. The characteristics of the temporary bonding state of the element wafer and the support substrate are released in a grounded manner.

In Patent Document 1, the temporary support for the element wafer is released by using a film for temporary fixation that is soluble in an organic solvent and bringing the organic solvent into contact with the film for temporary fixation. However, according to research by the inventors, the chemical resistance of the film for temporary fixing disclosed in Patent Document 1 is poor.

In the manufacturing process of components, various chemicals are sometimes used. For example, when a thin film of an element wafer is formed by a wet process, an etchant is used. Therefore, in the manufacturing process of a device, it is required to improve chemical resistance to a temporary adhesive film which is sometimes exposed to various chemicals.

In addition, in the manufacturing process of the element, in recent years, the element is sometimes subjected to processing at a higher temperature. Therefore, in order to cope with various manufacturing processes, it is required to further improve the heat resistance of the temporary adhesive film.

Furthermore, the invention disclosed in Patent Document 2 is an invention related to a semiconductor element fixing adhesive for bonding semiconductor elements to each other or a semiconductor element and a support substrate, and does not temporarily suspend the element wafer and the support substrate. then. Therefore, the adhesive for fixing a semiconductor element of Patent Document 2 does not have a characteristic that the temporary bonding of the element wafer and the support substrate can be released.

The present invention has been made in view of the background, and an object thereof is to provide a temporary The film, the laminate, the temporary bonding composition, the device manufacturing method, and the kit can be used to stably temporarily bond the device wafer when the device wafer is mechanically or chemically treated, and can be easily adhered. The device temporarily releases temporary bonding to the element wafer and has excellent chemical resistance.

The present inventors conducted intensive studies in order to solve the above problems, and as a result, found that the temporary bonding film having the bonding region and the release region on the surface of the bonding region can stably temporarily bond the element wafer, and can easily bond the element wafer. The temporary bonding of the element wafer was released, and the chemical resistance was excellent. Based on these findings, the present invention has been completed, and the bonding region has a mass reduction rate of 400 ° C at a temperature of 10 ° C / min from 25 ° C to 1 Mass% or less, and solubility in N-methylpyrrolidone at 25 ° C is 1 g / 100 g or less of solvent (Solvent). The present invention provides the following.

<1> A temporary bonding film having a bonding region and a mold release region on the surface of the bonding region, and the mass reduction rate at 400 ° C when the bonding region is heated at a temperature of 10 ° C / min from 25 ° C is 1% by mass or less. The solubility in N-methylpyrrolidone at 25 ° C is 1 g / 100 g or less of solvent (Solvent).

<2> The temporary adhesive film according to <1>, wherein the adhesive region includes a resin containing a heterocyclic ring and a maleimide resin, wherein the resin containing a heterocyclic ring is selected from the group consisting of polyimide resin and polyfluorene At least one of an amine imine resin, a polybenzimidazole resin, and a polybenzoxazole resin.

<3> The temporary adhesive film according to <2>, wherein the heterocyclic-containing resin is a pair selected from γ-butyrolactone, cyclopentanone, N-methylpyrrolidone, cyclohexanone, glycol ether, Second Polyimide resin having a solubility at least at least one of a solvent of methylimide and tetramethylurea at 25 ° C. of 10 g / 100 g of a solvent (Solvent).

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

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

<7> The temporary adhesive film according to <6>, wherein the one-minute half-life temperature of the thermal polymerization initiator is 130 ° C to 300 ° C.

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

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

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

<11> A laminated body having an element wafer on a surface on the side of a release region of a temporary adhesive film according to any one of <1> to <10>.

<12> A composition for temporary adhesion, including a heterocyclic-containing resin, a cross-linking component, and a solvent, and 50% to 100% by mass of the cross-linking component is a maleimide resin, wherein the heterocyclic-containing Resin contains polyimide resin, polyimide resin At least one of an amine resin, a polybenzimidazole resin, and a polybenzoxazole resin.

<13> The composition for temporary bonding according to <12>, wherein the heterocyclic-containing resin is a compound selected from γ-butyrolactone, cyclopentanone, N-methylpyrrolidone, cyclohexanone, and diol. Polyimide resin having a solubility at 25 ° C. of at least one of ether, dimethylimide, and tetramethylurea at 10 ° C./100 g of a solvent (Solvent).

<14> The temporary bonding composition according to <12> or <13>, wherein the maleimide resin is a bismaleimide resin.

<15> The temporary bonding composition according to any one of <12> to <14>, further containing a thermal polymerization initiator.

<16> The composition for temporary bonding according to <15>, wherein the one-minute half-life temperature of the thermal polymerization initiator is 130 ° C to 300 ° C.

<17> The temporary bonding composition according to <16>, wherein the thermal polymerization initiator is an organic peroxide.

<18> The temporary bonding composition according to any one of <12> to <17>, further containing a mold release component.

<19> The composition for temporary bonding according to <18>, wherein the release component includes a compound containing at least one selected from a fluorine atom and a silicon atom.

<20> The temporary bonding composition according to <18> or <19>, wherein the mold release component is a fluorine-based silane coupling agent.

<21> A method for producing a device, comprising the step of applying the temporary bonding composition according to any one of <12> to <20>.

<22> A set for forming any one of <1> to <10> The set of temporary adhesive films includes the temporary adhesive composition according to any one of <12> to <20>, and a composition for forming a mold release region containing a mold release component and a solvent.

According to the present invention, it is possible to provide a temporary bonding film which can stably and temporarily bond the element wafer when the element wafer is mechanically or chemically treated, and can easily release the temporary bonding of the element wafer. , And excellent chemical resistance. In addition, the present invention can provide a laminated body, a temporary bonding composition, a device manufacturing method, and a kit.

11‧‧‧ followed by area

12‧‧‧ support substrate

60‧‧‧component wafer

60a‧‧‧ thin component wafer

61‧‧‧ silicon substrate

61a‧‧‧Surface of silicon substrate

61b‧‧‧ Back of silicon substrate

Back of 61c‧‧‧ thin component wafer

62‧‧‧Element wafer, structure

71‧‧‧ demolding area

80‧‧‧ temporarily adhere to the film

100‧‧‧ Adhesive support

FIG. 1 (A), FIG. 1 (B), and FIG. 1 (C) are schematic cross-sectional views explaining a temporary and subsequent explanation of a support substrate and an element wafer, respectively, and showing element crystals temporarily adhered by the support substrate. A circle schematic cross-sectional view and a schematic cross-sectional view showing a state where the element wafer temporarily attached by the support substrate is thinned.

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

In the description of the group (atomic group) in the present specification, the descriptions that are not substituted and unsubstituted include groups that do not have a substituent and also include groups that have a substituent. For example, "alkyl" includes not only an alkyl group (unsubstituted alkyl group) having no substituent, but also an alkyl group (substituted alkyl group) having a substituent.

"Actinic rays" or "radiation" in this specification means Light, ultraviolet, far ultraviolet, electron beam, X-ray, etc.

In this specification, "light" means actinic radiation or radiation.

In this specification, the term "exposure" means not only exposure using mercury lamp, ultraviolet light, far-ultraviolet light represented by excimer laser, X-ray, extreme ultraviolet (EUV) light, etc., but also It refers to drawing using particle beams such as electron beams and ion beams.

In this specification, "(meth) acrylate" means acrylate and methacrylate, "(meth) acrylate" means acrylic and methacrylate, and "(meth) acryl" refers to "propylene "Methyl" and "methacryl".

In this specification, weight average molecular weight and number average molecular weight are defined as polystyrene conversion values measured by gel permeation chromatography (GPC). In this specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) can be obtained, for example, by using HLC-8220 (manufactured by Tosoh Corporation) and using TSKgel Super AWM-H (East Manufactured by Cao Co., Ltd. (6.0 mm ID × 15.0 cm) as a column, and a 10 mmol / L lithium bromide N-methyl pyrrolidinone (NMP) solution was used as the eluent.

In this specification, "monomer" and "monomer" have the same meaning. The haploid in the present invention refers to a compound that is distinguished from oligomers and polymers and has a weight average molecular weight of 2,000 or less.

The polymer compound in the present invention refers to a compound having a weight average molecular weight exceeding 2,000.

In the embodiments described below, descriptions of components and the like already described with reference to the drawings are simplified or omitted by using the same or corresponding symbols in the drawings.

<Temporarily adhere film>

The temporary adhesive film of the present invention has a bonding region and a mold release region on the surface of the bonding region, and the mass reduction rate of the bonding region at 400 ° C at a temperature increase of 10 ° C / min from 25 ° C is 1% by mass or less, and The solubility in N-methylpyrrolidone at 25 ° C is 1 g / 100 g or less of solvent (Solvent).

The temporary bonding film of the present invention has a release region on the surface of the bonding region. Therefore, the element wafer is laminated on the surface of the release region of the temporary bonding film, and the layer of the temporary bonding film and the element wafer is laminated. A support substrate is arranged on the opposite surface, which can appropriately protect element wafers with structures such as bumps. After mechanically or chemically treating the element wafer by mechanical peeling or other methods, the element wafer can be temporarily adhered to the wafer. The component wafer is simply stripped.

In addition, since the mass reduction rate at 400 ° C at a temperature increase of 10 ° C / min from 25 ° C in the bonding region is 1% by mass or less, it has excellent heat resistance and can be stable even when subjected to a process at a high temperature. The component wafer is temporarily attached. Furthermore, the temporary bonding film is not easily thermally deteriorated, so even after a high-temperature process, the temporary bonding film can be easily peeled from the element wafer by a method such as mechanical peeling.

In addition, since the peeling of the element wafer and the support substrate in the present invention can be performed by mechanical peeling, the solubility of N-methylpyrrolidone at 25 ° C. in the bonding region can be 1 g / 100 g or less of solvent (Solvent). , Excellent chemical resistance. So, for example, in During the processing of the element wafer, even if chemicals such as an etchant adhere to the temporary adhesion film, the element wafer can be stably temporarily adhered.

As described above, even when the temporary bonding film of the present invention is subjected to various processes such as high-temperature processing and chemical processing on the element wafer, the temporary bonding film can be stably temporarily bonded, and the element wafer can be easily peeled from the processed element wafer.

In the present invention, the mass reduction rate is a value measured by a thermogravimetric analyzer (TGA) under a nitrogen flow under the temperature rising condition.

In addition, in the present invention, regarding the solubility, a certain amount is added to 100 g of the solvent while stirring the sample, and the solubility is confirmed. When the sample is completely dissolved, the sample is further added with a certain amount under stirring, and the operation is repeated to The final amount of the sample immediately before dissolution when stirred at 25 ° C for 1 hour was taken as the solubility.

The temporary adhesive film of the present invention has a bonding region and a release region on the surface of the bonding region.

In the temporary adhesive film of the present invention, the mass reduction rate at 400 ° C at a temperature increase of 10 ° C / min from 25 ° C is 1 mass% or less, preferably 0.90 mass% or less, and more preferably 0.8 mass%. Hereinafter, it is more preferably 0.7% by mass or less, particularly preferably 0.6% by mass or less, and most preferably 0.5% by mass or less. Within this range, even in the case of a high-temperature process up to 400 ° C., the element wafer can be temporarily adhered stably. In addition, the temporary bonding film is not easily thermally deteriorated, so even after a high-temperature process, the temporary bonding film can be easily peeled from the element wafer by a method such as mechanical peeling.

In the temporary bonding film of the present invention, the N-methylpyrrolidine at 25 ° C in the bonding region The solubility of the ketone is 1 g / 100 g or less of Solvent, preferably 0.8 g / 100 g or less of Solvent, more preferably 0.5 g / 100 g or less of Solvent, and even more preferably 0.1 g / 100 g of Solvent. the following. According to this aspect, even in the case where the chemical liquid used in the manufacturing process of the element comes into contact with the temporarily adhered film, the element wafer can be stably temporarily adhered.

In the temporary adhesive film of the present invention, the adhesive region and the mold release region may exist as separate adhesive layers and mold release layers, and the boundary between the adhesive region and the mold release region may not be clear. An example of an aspect in which the boundary between the subsequent region and the demolding region is unclear may include an aspect in which the demolding component is biased to exist in the surface layer to form a demolding region in the temporary adhesion layer. In addition, the bonding region may include two or more bonding layers, and the mold release region may include two or more bonding layers.

Hereinafter, the temporary adhesive film of this invention is demonstrated concretely.

<< Next area >>

The temporary bonding film of the present invention has a bonding region. The next area attaches the element wafer to the support substrate.

The following area can be used: the mass reduction rate at 400 ° C at a temperature increase of 10 ° C / min from 25 ° C is 1% by mass or less, and the solubility to 25 ° C N-methylpyrrolidone is 1g / 100g of solvent ( Solvent).

The average thickness of the next region is preferably 0.1 μm to 500 μm, more preferably 0.5 μm to 500 μm, more preferably 0.5 μm to 50 μm, and even more preferably 0.5 μm to 10 μm. In addition, when the temporary bonding 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 bonding region is larger than that of a device wafer described later. The height is thicker.

In the case where the temporary adhesive film of the present invention includes a laminated structure in which a layer forming a release region is laminated on a surface layer of a layer forming the adhesive region, the average thickness of the layer forming the adhesive region is preferably 1 μm to 50 μm, more It is preferably 2 μm to 20 μm.

In the case where the temporary adhesive film of the present invention is in a state where the release component in the temporary adhesive layer is biased to exist on the surface layer to form a release region, the average thickness of the adhesive region is preferably 1 μm to 50 μm, and more preferably 2 μm to 20 μm. .

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

As long as the mass reduction rate and solubility can be achieved in the next region, they can be preferably used, and preferably contain the resin component A and maleimide resin described later. When the resin component A and the maleimide imine resin described later are contained in the subsequent region, the resin component A can be interposed between the maleimide resins which are three-dimensionally crosslinked, and it is easy to obtain a resin having excellent heat resistance and chemical resistance. Then the area.

<<< resin composition A >>>

In the present invention, as long as the resin component A that can be contained in the bonding region satisfies the above-mentioned mass reduction rate and solubility, any resin component can be used. In addition, in the present invention, it is considered that the maleimide resin is not included in the resin component A.

Examples of the resin component A include a heterocyclic-containing resin (polyimide resin, polyimide resin, polybenzimidazole resin, polybenzoxazole resin), terpene resin, and terpene Phenol resin, modified terpene 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 resin, hydrogenated petroleum resin, modified petroleum resin, alicyclic petroleum resin, coumarone Petroleum resin, indene petroleum resin, olefin copolymer (such as methylpentene copolymer), cycloolefin copolymer (such as norbornene copolymer, dicyclopentadiene copolymer, tetracyclododecene copolymer), phenolic Varnish resin, phenol resin, epoxy resin, melamine resin, urea resin, unsaturated polyester resin, alkyd resin, polyurethane resin, polyethylene resin, polypropylene resin, ethylene propylene copolymer (EPDM rubber) , Polyvinyl chloride resin, polystyrene resin, polystyrene copolymer resin (such as acrylonitrile-butadiene-styrene copolymer (ABS resin), acrylonitrile-styrene copolymer (AS resin), methyl methacrylate Ester styrene copolymer resin (MS resin)), polyvinyl acetate resin, polytetrafluoroethylene resin (PTFE resin), copolymer of tetrafluoroethylene and perfluoroalkoxyethylene (PFA resin), tetrafluoroethylene- Hexafluoropropylene (FEP resin), ethylene-tetrafluoroethylene (TFE) copolymer resin, polyvinylidene fluoride (PVDF resin), polychlorotrifluoroethylene (PCTFE resin), ethylene-chlorotrifluoroethylene resin (CTFE resin ), TFE-perfluorodimethyl dioxole copolymer resin, polyvinyl fluoride resin (PVF resin), acrylic resin, cellulose resin, polyamide resin, polyacetal resin , Polycarbonate resin, polyphenylene ether resin, polybutylene terephthalate resin, polyethylene terephthalate resin, cyclic polyolefin resin, polyphenylene sulfide resin, polyfluorene resin, polyetherfluorene Synthetic resins such as resins, polyarylate resins, and polyetherketone resins, or natural resins such as natural rubber.

Among these, polyimide resins, polyamidoimide resins, and polybenzoimides are preferred. Azole resin, polybenzoxazole resin, polycarbonate resin, polyether resin, polyester resin, more preferably polyimide resin, polyimide resin, polybenzimidazole resin, polybenzo The oxazole resin is further preferably a polyimide resin or a polyimide resin, and particularly preferably a polyimide resin. Since these resins are excellent in heat resistance, it is easy to achieve the aforementioned mass reduction rate.

In addition, the polyfluorene imine resin is preferably selected from the group consisting of γ-butyrolactone, cyclopentanone, N-methylpyrrolidone, cyclohexanone, glycol ethers, dimethylimide, and tetramethylurea. Polyimide resin having a solubility at 25 ° C. of at least one solvent of 10 g / 100 g of a solvent (Solvent) or more. According to this aspect, a bonding region can be formed by a coating method.

<<< Polyimide resin >>>>

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

Known methods include, for example, mixing approximately equimolar tetracarboxylic dianhydride and diamine in an organic solvent, and reacting at a reaction temperature of 80 ° C or lower to obtain a polyamic acid, and dehydrating the obtained polyamino acid. Closed-loop methods, etc. Here, the term "approximately equal molarity" means that the molar ratio of tetracarboxylic dianhydride to diamine is around 1: 1. Furthermore, if necessary, the composition ratio of the tetracarboxylic dianhydride to the diamine can be adjusted so that the total of the tetracarboxylic dianhydride is 1.0 mol and the total of the diamine is 0.5 mol to 2.0 mol. By adjusting the composition ratio of tetracarboxylic dianhydride to diamine within the above range, the weight average molecular weight of the polyfluoreneimide resin can be adjusted.

Tetracarboxylic dianhydride is not particularly limited, and examples thereof include pyromellitic dianhydride, 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, 2,2', 3,3'-bi Pyromellitic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propane dianhydride, 1,1-bis (2,3-dicarboxyphenyl) ethane Dianhydride, 1,1-bis (3,4-dicarboxyphenyl) ethane dianhydride, bis (2,3-dicarboxyphenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) methane Dianhydride, bis (3,4-dicarboxyphenyl) fluorene dianhydride, 3,4,9,10-fluorenetetracarboxylic dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, benzene- 1,2,3,4-tetracarboxylic dianhydride, 3,4,3 ', 4'-benzophenone tetracarboxylic dianhydride, 2,3,2', 3'-benzophenone tetracarboxylic acid Acid dianhydride, 2,3,3 ', 4'-benzophenonetetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic acid Acid dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,2,4,5-naphthalenetetracarboxylic dianhydride, 2,6-dichloronaphthalene-1,4,5,8- Tetracarboxylic dianhydride, 2,7-dichloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 2,3,6,7-tetrachloronaphthalene-1,4,5,8-tetracarboxylic acid Acid dianhydride, phenanthrene-1,8,9,10-tetracarboxylic dianhydride, pyrazine-2,3,5,6-tetracarboxylic dianhydride, thiophene-2,3,5,6-tetracarboxylic acid Dianhydride, 2,3,3 ', 4'-biphenyltetracarboxylic dianhydride, 3,4,3', 4'-biphenyltetracarboxylic dianhydride, 2,3,2 ', 3'-bi Pyromellitic dianhydride, bis (3,4-dicarboxyphenyl) dimethylsilane dianhydride, bis (3,4-dicarboxyl ) Methylphenylsilane dianhydride, bis (3,4-dicarboxyphenyl) diphenylsilane dianhydride, 1,4-bis (3,4-dicarboxyphenyldimethylsilyl) benzene Anhydride, 1,3-bis (3,4-dicarboxyphenyl) -1,1,3,3-tetramethyldicyclohexane dianhydride, p-phenylene bis (trimellitic anhydride ester), and ethyl tetraethylene Carboxylic dianhydride, 1,2,3,4-butanetetracarboxylic dianhydride, decalin-1,4,5,8-tetracarboxylic dianhydride, 4,8-dimethyl-1,2 , 3,5,6,7-hexahydronaphthalene-1,2,5,6-tetracarboxylic dianhydride, cyclopentane-1,2,3,4-tetracarboxylic dianhydride, pyrrolidine-2, 3,4,5-tetracarboxylic dianhydride, 1,2,3,4-cyclobutane tetracarboxylic dianhydride, bis (exo-bicyclo [2,2,1] heptane-2,3-dicarboxylic acid Acid dianhydride, bicyclo- [2,2,2] -oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane Dianhydride, 2,2-bis [4- (3,4-dicarboxyphenyl) phenyl] propane dianhydride, 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride, 2 , 2-bis [4- (3,4-dicarboxyphenyl) phenyl] Hexafluoropropane dianhydride, 4,4'-bis (3,4-dicarboxyphenoxy) diphenylsulfide dianhydride, 1,4-bis (2-hydroxyhexafluoroisopropyl) benzenebis (partial Trimellitic anhydride), 1,3-bis (2-hydroxyhexafluoroisopropyl) benzenebis (trimellitic anhydride), 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3- Cyclohexene-1,2-dicarboxylic dianhydride, tetrahydrofuran-2,3,4,5-tetracarboxylic dianhydride, 4,4'-oxydiphthalic dianhydride, 1,2- ( Ethyl) bis (trimellitic anhydride ester), 1,3- (trimethylene) bis (trimellitic anhydride ester), 1,4- (tetramethylene) bis (trimellitic anhydride ester), 1,5- (pentamethylene ) Bis (trimellitic anhydride ester), 1,6- (hexamethylene) bis (trimellitic anhydride ester), 1,7- (heptamethylene) bis (trimellitic anhydride ester), 1,8- (octamethylene) bis (Trimellitic anhydride ester), 1,9- (ninemethylene) bis (trimellitic anhydride ester), 1,10- (decamethylene) bis (trimellitic anhydride ester), 1,12- (dodecylmethylene) bis ( Trimellitic anhydride ester), 1,16- (hexamethylene) bis (trimellitic anhydride ester), 1,18- (octadecyl methylene) bis (trimellitic anhydride ester), etc. These tetracarboxylic dianhydrides can be used alone One type or a combination of two or more types. Among these tetracarboxylic dianhydrides, 3,4,3 ', 4'-benzophenone tetracarboxylic dianhydride and 2,3,2', 3'-benzophenone tetracarboxylic dianhydride are preferred. Anhydride and 2,3,3 ', 4'-benzophenonetetracarboxylic dianhydride, more preferably 3,4,3', 4'-benzophenonetetracarboxylic dianhydride.

The diamine is not particularly limited, and examples thereof include o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 3,3'-diaminodiphenyl ether, and 3,4'-diaminodiphenyl Ether, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, bis (4-amino-3, 5-dimethylphenyl) methane, bis (4-amino-3,5-diisopropylphenyl) methane, 3,3'-diaminodiphenyldifluoromethane, 3,4'- Diaminodiphenyldifluoromethane, 4,4'-diaminodiphenyldifluoromethane, 3,3'-diaminodiphenylphosphonium, 3,4'-diaminodiphenylphosphonium , 4,4'-diaminodiphenylphosphonium, 3,3'-diaminodiphenylsulfide, 3,4'-diaminodiphenyl Phenyl sulfide, 4,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl ketone, 3,4'-diaminodiphenyl ketone, 4,4'- Diaminodiphenyl ketone, 3- (4-aminophenyl) -1,1,3-trimethyl-5-aminoindan, 2,2-bis (3-aminophenyl) propane , 2,2 '-(3,4'-diaminodiphenyl) propane, 2,2-bis (4-aminophenyl) propane, 2,2-bis (3-aminophenyl) hexadecane Fluoropropane, 2,2- (3,4'-diaminodiphenyl) hexafluoropropane, 2,2-bis (4-aminophenyl) hexafluoropropane, 1,3-bis (3-amine Phenylphenoxy) benzene, 1,4-bis (3-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 3,3 '-(1,4- Phenylbis (1-methylethylene)) bisaniline, 3,4 '-(1,4-phenylenebis (1-methylethylene)) bisaniline, 4,4'-(1 , 4-phenylenebis (1-methylethylene)) bisaniline, 2,2-bis (4- (3-aminophenoxy) phenyl) propane, 2,2-bis (4- (3-aminophenoxy) phenyl) hexafluoropropane, 2,2-bis (4- (4-aminophenoxy) phenyl) hexafluoropropane, bis (4- (3-aminoethyl) (Oxy) phenyl) sulfide, bis (4- (4-aminoethoxy) phenyl) sulfide, bis (4- (3-aminoethoxy) phenyl) fluorene, bis (4- (4-Aminoethoxy) phenyl) fluorene, 3,3'-dihydroxy-4,4'-diamine Aromatic diamines such as biphenyl, 3,5-diaminobenzoic acid, 1,3-bis (aminomethyl) cyclohexane, 2,2-bis (4-aminophenoxyphenyl) propane , Polyoxypropylene diamine, 4,9-dioxadecane-1,12-diamine, 4,9,14-trioxaheptadecan-1,17-diamine, 1,2- Diaminoethane, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-di Aminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, 1,12- Diaminododecane, 1,2-diaminocyclohexane, 1,3-bis (3-aminopropyl) tetramethyldisilaxane, and the like.

Among these diamines, it is preferably selected from 3- (4-aminophenyl) -1,1,3-trimethyl-5-aminoindan, 1,3-bis (3-aminopropyl) Group) tetramethyldisilaxane, polyoxypropylene diamine, 2,2-bis (4-aminophenoxyphenyl) propane, 4,9-dioxadecane-1,12- Diamine, 1,6- One or more of the group consisting of diaminohexane and 4,9,14-trioxaheptadecan-1,17-diamine, more preferably 3- (4-aminophenyl) -1 , 1,3-trimethyl-5-aminoindan.

Examples of the solvent used in the reaction of the tetracarboxylic dianhydride and diamine include N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N, N-dimethylformamide Lamine. In order to adjust the solubility of raw materials and the like, a non-polar solvent (for example, toluene or xylene) may be used in combination.

The reaction temperature of the tetracarboxylic dianhydride and diamine is preferably lower than 100 ° C, and more preferably lower than 90 ° C. In addition, the fluorene imidization of polyamic acid is typically performed by performing a heat treatment in an inert environment (typically, a vacuum or nitrogen atmosphere). The heat treatment temperature is preferably 150 ° C or higher, and more preferably 180 ° C to 450 ° C.

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

In the present invention, the polyfluorene imide resin is preferably selected from the group consisting of γ-butyrolactone, cyclopentanone, N-methylpyrrolidone, cyclohexanone, glycol ether, dimethylsulfinium, and tetramethyl. Polyimide resin having at least one solvent in urea having a solubility at 25 ° C. of 10 g / 100 g of a solvent (Solvent) or more.

Examples of the polyimide resin having such a solubility include 3,4,3 ', 4'-benzophenonetetracarboxylic dianhydride and 3- (4-aminophenyl) -1,1, Polyimide resin obtained by 3-trimethyl-5-aminoindan reaction and the like. This polyimide resin is particularly excellent in heat resistance.

A commercially available polyimide resin can also be used. Examples include: Durimide (registered trademark) 200, Durimide 208A, Durimide 284 (manufactured by Fujifilm), GPT-LT (group Sakae Chemical Co., Ltd.), SOXR-S, SOXR-M, SOXR-U, SOXR-C (all manufactured by Nippon Kogyo Paper Co., Ltd.), etc.

<<< Polyamidamine imine resin >>>>

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

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

Examples of acid components used in the production of polyamidoamine imine resins include: trimellitic acid, trimellitic anhydride, trimellitic chloride; pyromellitic acid (benzene-1,2,4,5-tetracarboxylic acid ), Tetracarboxylic acids such as biphenyltetracarboxylic acid, biphenylphosphonium tetracarboxylic acid, benzophenone tetracarboxylic acid, diphenyl ether tetracarboxylic acid, ethylene glycol ditrimellitic acid ester, propylene glycol ditrimellitic acid ester, etc. Acids and their anhydrides or chloros; oxalic acid, adipic acid, malonic acid, sebacic acid, azelaic acid, dodecanedicarboxylic acid, dicarboxylic polybutadiene, dicarboxylic poly (acrylonitrile- Butadiene), dicarboxylic poly (styrene-butadiene) and other aliphatic dicarboxylic acids; 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 4,4'- Cycloaliphatic dicarboxylic acids such as dicyclohexylmethanedicarboxylic acid and dimer acid; terephthalic acid, isophthalic acid, diphenylphosphonium dicarboxylic acid, diphenyl ether dicarboxylic acid, naphthalenedicarboxylic acid, etc. Aromatic dicarboxylic acid.

These acid components may be used alone or in combination of two or more. Among these acid components, trimellitic anhydride is preferred from the viewpoints of reactivity, heat resistance, and solubility.

Examples of diamines or diisocyanates used in the manufacture of polyamidoamine imine resins include:

Aliphatic diamines such as ethylene diamine, propylene diamine, hexamethylene diamine, and diisocyanates of these diamines; 1,4-cyclohexanediamine, 1,3-cyclohexanediamine, isophor Alicyclic diamines such as ketone diamine, 4,4'-dicyclohexylmethane diamine and diisocyanates of these diamines; m-phenylenediamine, p-phenylenediamine, 4,4'-diamine Phenylmethane, 4'-diaminodiphenyl ether, 4,4'-diaminodiphenylphosphonium, benzidine, o-toluidine, 2,4-toluenediamine, 2,6-toluenediamine Aromatic diamines such as amines, xylylene amines, and diisocyanates of these diamines.

These compounds may be used alone or in combination of two or more. Among them, in terms of heat resistance, mechanical properties, solubility, etc., 4,4'-diaminodiphenylmethane and its diisocyanate, 2,4-toluenediamine and its diisocyanate, and vicinal are preferred. Toluidine and its diisocyanate, isophorone diamine and its diisocyanate, p-phenylenediamine and its diisocyanate, particularly preferably p-phenylenediamine.

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

When the number average molecular weight (Mn) of the polyamidoamine imine resin is 5,000 or more, durability is good. When the number average molecular weight (Mn) of the polyamidofluorine imine resin is 100,000 or less, the viscosity of the solution decreases, and it is easy to apply to form a bonding region.

A commercially available polyimide / imide resin can also be used. Examples include: Durimide (registered trademark) 10, Durimide 32 (manufactured by Fujifilm), Vylomax (registered trademark) 13NX (Manufactured by Toyobo Co., Ltd.), Rikacoat (manufactured by New Japan Physicochemical Co., Ltd.), etc.

<<<< Polybenzimidazole resin >>>>

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

Examples of the aromatic tetraamine include 1,2,4,5-tetraaminobenzene, 1,2,5,6-tetraaminonaphthalate, and 2,3,6,7-tetraaminonaphthalene Diformate, 3,3 ', 4,4'-tetraaminodiphenylmethane, 3,3', 4,4'-tetraaminodiphenylethane, 3,3 ', 4,4 '-Tetraaminodiphenyl-2,2-propane, 3,3'4,4'-tetraaminodiphenyl sulfide and 3,3', 4,4'-tetraaminodiphenylsulfonium Wait. The preferred aromatic tetraamine is 3,3 ', 4,4'-tetraaminobiphenyl.

Examples of the dicarboxylic acid component include isophthalic acid, terephthalic acid, 4,4'-biphenyldicarboxylic acid, 1,4-naphthalenedicarboxylic acid, and 2,2'-biphenyldicarboxylic acid (dophenic acid), phenylindane dicarboxylic acid, 1,6-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 4,4'-diphenylsulfide dicarboxylic acid, 4,4'-diphenyl Hydrazone dicarboxylic acid, 4,4'-diphenyl sulfide dicarboxylic acid.

The dicarboxylic acid component is preferably introduced at a dicarboxylic acid component ratio of about 1 mole per mole of the aromatic tetraamine. Moreover, the optimum ratio of the polymerization-type reactant can be easily determined by those skilled in the art.

Examples of the polybenzimidazole resin include poly-2,2 '-(m-phenylene) -5,5'-dibenzimidazole (poly-2,2'-(m-phenylene) -5,5 '-bibenzimidazole), Poly-2,2'-(Extended Biphenyl-2 "2" ')-5,5'-dibenzimidazole, Poly-2,2'-(Extended Biphenyl-4 " 4 "')-5,5'-dibenzimidazole, poly-2,2'-(1", 1 ", 3" -trimethylindanyl-3 "5" -p-phenylene- 5,5'-dibenzimidazole, 2,2 '-(m-phenylene) -5,5'-dibenzimidazole / 2,2- (1 ", 1", 3 "-trimethylbenzyl (Indanyl) 5 ", 3"-(p-phenylene) -5,5'-dibenzimidazole Copolymer, 2,2 '-(m-phenylene) -5,5'-dibenzimidazole / 2,2'-biphenylphenyl-2 ","')-5,5'-dibenzo Imidazole copolymer, poly-2,2 '-(furanyl-2 ", 5")-5,5'-dibenzimidazole, poly-2,2'-(m-phenylene) -5,5 '-Dibenzimidazole, poly-2,2'-(naphthalene-1 ", 6")-5,5'-dibenzimidazole, poly-2,2 '-(naphthalene-2 ", 6") -5,5'-dibenzimidazole, poly-2,2'-pentene-5,5'-dibenzimidazole, poly-2,2'-octamethylene-5,5'-diphenyl Benzimidazole, poly-2,2 '-(m-phenylene) -diimidazobenzene, poly-2,2'-cyclohexenyl-5,5'-dibenzimidazole, poly-2,2' -(M-phenylene) -5,5'-bis (benzimidazole) ether, poly-2,2 '-(m-phenylene) -5,5'-bis (benzimidazole) sulfide, poly -2,2 '-(m-phenylene) -5,5'-bis (benzimidazole) fluorene, poly-2,2'-(m-phenylene) -5,5'-bis (benzimidazole) ) Methane, poly-2,2 '-(m-phenylene) -5,5'-bis (benzimidazole) propane and poly-methylene-1,2-2,2 "-(m-phenylene ) -5,5 "-dibenzimidazole-ethenyl-1,2, etc.

As a polybenzimidazole resin, you may use a commercial item. Examples thereof include MRS0810H (manufactured by PBI).

<<<< Polybenzoxazole resin >>>>

The polybenzoxazole resin can be used: a polybenzoxazole resin obtained by dissolving a polyhydroxyamidine synthesized from a bisaminophenol compound and a dicarboxylic acid derivative in a solvent and subjecting it to a dehydration ring-closing reaction.

Examples of the diaminophenol compound include 2,4-diaminoresorcinol, 4,6-diaminoresorcinol, 2,2-bis (3-amino-4-hydroxyphenyl) hexa Fluoropropane, 2,2-bis (4-amino-3-hydroxyphenyl) hexafluoropropane, 2,2-bis (3-amino-4-hydroxyphenyl) propane, 2,2-bis (4 -Amino-3-hydroxyphenyl) propane, 3,3'-diamino-4,4'-dihydroxydiphenylphosphonium, 4,4'-diamino-3,3'-dihydroxydi Phenylhydrazone, 3,3'-diamino-4,4'-dihydroxybiphenyl, 4,4'-diamino-3,3'-dihydroxybiphenyl, 9,9-bis (4-((4-amino-3-hydroxy) phenoxy) phenyl) fluorene, 9,9 -Bis (4-((3-amino-4-hydroxy) phenoxy) phenyl) fluorene, 9,9-bis (4- (3-amino-4-hydroxy) phenyl) fluorene, 9 ,, 9-bis (4- (4-amino-3-hydroxy) phenyl) fluorene, 1,1'-binapthyl-3,3'-diamino-2,2'-diol, bis (2- ((4-amino-3-hydroxy) phenoxy))-1,1'-binaphalene, bis (2-((3-amino-4-hydroxy) phenoxy))-1,1 ' -Binaphthalene, 3,3'-diamino-4,4'-dihydroxydiphenyl ether, 4,4'-diamino-3,3'-dihydroxydiphenyl ether, 2,2- Bis (3-amino-4-hydroxy-2-trifluoromethylphenyl) propane, 2,2-bis (4-amino-3-hydroxy-2-trifluoromethylphenyl) propane, 2, 2-bis (3-amino-4-hydroxy-5-trifluoromethylphenyl) propane, 2,2-bis (4-amino-3-hydroxy-5-trifluoromethylphenyl) propane, 2,2-bis (3-amino-4-hydroxy-6-trifluoromethylphenyl) propane, 2,2-bis (4-amino-3-hydroxy-6-trifluoromethylphenyl) Propane, 2,2-bis (3-amino-4-hydroxy-2-trifluoromethylphenyl) hexafluoropropane, 2,2-bis (4-amino-3-hydroxy-2-trifluoromethyl) Phenyl) hexafluoropropane, 2,2-bis (3-amino-4-hydroxy-5-trifluoromethylphenyl) hexafluoropropane, 2,2-bis (4-amino- 3-hydroxy-5-trifluoromethylphenyl) hexafluoropropane, 2,2-bis (3-amino-4-hydroxy-6-trifluoromethylphenyl) hexafluoropropane, 2,2-bis (4-amino-3-hydroxy-6-trifluoromethylphenyl) hexafluoropropane, 3,3'-diamino-4,4'-dihydroxy-2,2'-bis (trifluoromethyl) Group) biphenyl, 4,4'-diamino-3,3'-dihydroxy-2,2'-bis (trifluoromethyl) biphenyl, 3,3'-diamino-4,4 ' -Dihydroxy-5,5'-bis (trifluoromethyl) biphenyl, 4,4'-diamino-3,3'-dihydroxy-5,5'-bis (trifluoromethyl) biphenyl , 3,3'-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 the dicarboxylic acid derivative include isophthalic acid, terephthalic acid, 4,4'-biphenyldicarboxylic acid, 3,4'-biphenyldicarboxylic acid, and 3,3'-biphenyl. Dicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 4,4'-sulfofluorenylbisbenzoic acid, 3,4'-sulfofluorenylbisbenzoic acid Acid, 3,3'-sulfobibenzoic acid, 4,4'-oxybisbenzoic acid, 3,4'-oxybisbenzoic acid, 3,3'-oxybisbenzoic acid, 2,2 -Bis (4-carboxyphenyl) propane, 2,2-bis (3-carboxyphenyl) propane, 2,2-bis (4-carboxyphenyl) hexafluoropropane, 2,2-bis (3-carboxy Phenyl) hexafluoropropane, 4,4'-bis (4-carboxyphenoxy) biphenyl, 4,4'-bis (3-carboxyphenoxy) biphenyl, 3,4'-bis (4- Carboxyphenoxy) biphenyl, 3,4'-bis (3-carboxyphenoxy) biphenyl, 3,3'-bis (4-carboxyphenoxy) biphenyl, 3,3'-bis (3 -Carboxyphenoxy) biphenyl, 4,4'-bis (4-carboxyphenoxy) -p-terphenyl, 4,4'-bis (4-carboxyphenoxy) -m-terphenyl, 3, 4'-bis (4-carboxyphenoxy) -p-terphenyl, 3,3'-bis (4-carboxyphenoxy) -p-terphenyl, 3,4'-bis (4-carboxyphenoxy) -M-terphenyl, 3,3'-bis (4-carboxyphenoxy) -m-terphenyl, 4,4'-bis (3-carboxyphenoxy) -p-terphenyl, 4,4'- Bis (3-carboxyphenoxy) -m-terphenyl, 3,4'-bis (3-carboxyphenoxy) -p-terphenyl, 3,3'-bis (3-carboxyphenoxy) -paraphenyl Triphenyl, 3,4'-bis (3-carboxyphenoxy) -m-terphenyl, 3,3'-bis (3-carboxyphenoxy) -m-terphenyl, 2,2'-bis ( Trifluoro (Methyl) -4,4'-biphenyldicarboxylic acid, 3,3'-bis (trifluoromethyl) -4,4'-biphenyldicarboxylic acid, 2,2'-bis (trifluoromethyl) ) -3,3'-biphenyldicarboxylic acid, 2,2'-dimethyl-4,4'-biphenyldicarboxylic acid, 3,3'-dimethyl-4,4'-biphenyldicarboxylic acid Carboxylic acid, 2,2'-dimethyl-3,3'-biphenyldicarboxylic acid, 3-fluoroisophthalic acid, 2-fluoroisophthalic acid, 2-fluoroterephthalic acid, 2,4 Dicarboxylic acids in 5,5,6-tetrafluoroisophthalic acid, 2,3,5,6-tetrafluoroterephthalic acid, 5-trifluoromethylisophthalic acid, etc., and selected from 1-hydroxyl A carboxylic acid derivative obtained by reacting one or more of benzotriazole, 1-hydroxybenzothiazole, and p-nitrophenol, and the like.

As the polybenzoxazole resin, a commercially available product can also be used. Examples include CRC-8800 (manufactured by Sumitomo Bakelite).

The adjoining area is preferably relative to the total solids content of the adjoining area (except for Amount other than the solvent) and contains 1% to 99% by mass of the resin component A, more preferably 10% to 90% by mass, and even more preferably 25% to 75% by mass.

In addition, the temporary bonding film preferably contains 1% to 99% by mass of the resin component A relative to the total solid content (amount other than the solvent) of the temporary bonding film, and more preferably 10% to 90% by mass. Especially preferred is 25% to 75% by mass.

The resin component A may be only one type, or two or more types. When the resin component A is two or more types, it is preferable that the total thereof is within the above range.

<<< crosslinking component >>>

In the present invention, the bonding region preferably contains a maleimide resin as a crosslinking component. The maleimide resin can be used arbitrarily as long as the cured product satisfies the aforementioned mass reduction rate and solubility.

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

In the present invention, the maleimide imine resin is preferably a bismaleimide resin.

The bismaleimide resin is more preferably, for example, a bismaleimide resin represented by the following general formula (III), and a novolak-type maleimide resin represented by the following general formula (IV) At least one of.

[Chemical 1]

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

R is preferably a group such as a phenyl group, a tolyl group, a xylyl group, a naphthyl group, a linear or branched chain or a cyclic saturated hydrocarbon group, or a divalent group composed of a combination of these groups.

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

[Chemical 3]

In General Formula (IV), s represents an integer of 0-20.

In the present invention, the maleimide imine resin described in Japanese Patent Application Laid-Open No. 2003-321608 may be used as the maleimide resin described in paragraph number 0020 to paragraph number 023.

Examples of commercially available products of maleimide imine resin include: BMI-1000, BMI-2000, BMI-3000, BMI-4000, BMI-5000, BMI-5100, and BMI-7000 (manufactured by Yamato Chemical Industries, double-Malaysian Imine resin), BANI-X (manufactured by Shin Nakamura Chemical, bismaleimide imine resin), BANI-M (manufactured by Shin Nakamura Chemical, bismaleimide imine resin), etc.

The next region preferably contains 1% to 99% by mass of maleimide resin relative to the total solid content (amount other than solvent) of the next region, more preferably 10% to 90% by mass, especially It is preferably 25% to 75% by mass. When the content of the maleimide resin is within the above range, the heat resistance of the bonding region can be further improved.

In addition, the temporary bonding film preferably contains 1 to 99% by mass of the maleimide tree based on the total solid content (amount other than the solvent) of the temporary bonding film. Fat, more preferably 10% to 90% by mass, and even more preferably 25% to 75% by mass.

The maleimide resin preferably contains 10% to 100% by mass, more preferably 20% to 100% by mass, and even more preferably 50% to 100% by mass of the total mass of the crosslinking component contained in the bonding region. Mass%, particularly preferably from 80% to 100% by mass. Most preferably, the crosslinking component consists essentially of a maleimide resin. The term “substantially only composed of maleimide resin” means that the content of cross-linking components other than maleimide resin in the total amount of crosslinking components is preferably, for example, 1% by mass or less, and more preferably It is 0.5% by mass or less, and particularly preferably 0.1% by mass or less. According to this aspect, the heat resistance of the bonding region can be further improved.

The adhesive region of the present invention may contain a crosslinking component (other crosslinking component) other than the maleimide resin. As the other crosslinking component, a known compound having two or more polymerizable groups and polymerizable by the action of actinic rays, radiation, light, heat, radicals, or acids can be used. Examples of the polymerizable group include a group having an ethylenically unsaturated bond, an epoxy group, and the like. The ethylenically unsaturated bond group is preferably a vinyl group, an acrylic group, a methacrylic group, or an allyl group.

Examples of the compound containing 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, and 6 to 35 carbon atoms. Aromatic vinyl compounds, vinyl ether compounds having 3 to 20 carbon atoms, and the like.

Examples of the compound having an epoxy group include glycidyl ether of bisphenol A type (or AD type, S type, and F type), glycidyl ether of hydrogenated bisphenol A type, and ethylene oxide adduct bisphenol A. Type glycidyl ether, propylene oxide adduct bisphenol A type Glycidyl ether, glycidyl ether of phenol novolac resin, glycidyl ether of cresol novolac resin, glycidyl ether of bisphenol A novolac resin, glycidyl ether of naphthalene resin, trifunctional (or tetrafunctional) Glycidyl ether, glycidyl ether of dicyclopentadiene phenol resin, diallyl bisphenol A diglycidyl ether, polycondensation product of allyl bisphenol A and epichlorohydrin, glycidol of dimer acid Ester, trifunctional (or tetrafunctional) glycidylamine, glycidylamine of naphthalene resin, and the like.

In the present invention, a compound having an epoxy group may be contained as a cross-linking component, and the content of the compound having an epoxy group in 100 parts by mass of the cross-linking component may be set to 10 for reasons of further improving heat resistance. It may be set to 5% by mass or less, more preferably not more than 5% by mass, and may not substantially contain a compound having an epoxy group. The term “substantially free” means, for example, that the content of the compound having an epoxy group is preferably 1% by mass or less, more preferably 0.5% by mass or less, even more preferably 0.1% by mass or less, and particularly preferably not contained.

<<< Thermal polymerization initiator >>>

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

As the preferred thermal polymerization initiator, a compound having a one-minute half-life temperature of 130 ° C. to 300 ° C., preferably 150 ° C. to 260 ° C. can be preferably used. According to this aspect, the heat resistance of the bonding 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 residual amount (mass) becomes 1/2 in one minute. The one-minute half-life temperature of the thermal polymerization initiator can be measured, for example, by preparing a thermal polymerization initiator at 0.1 mol / l in benzene, heating at multiple points of temperature Ti (absolute temperature), and measuring each The half-life t _{1/2, T1 at the} temperature Ti is plotted against 1 / Ti with 1nt _{1/2, T1} , and the temperature at which the half-life is 1 minute is obtained from the obtained straight line.

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

Examples of the thermal radical generator include aromatic ketones, onium salt compounds, organic peroxides, sulfur compounds, hexaarylbiimidazole compounds, ketoxime ester compounds, borate compounds, azineium compounds, metallocene compounds, Active ester compounds, compounds having a carbon halogen bond, azo compounds, and the like. Among these, an organic peroxide or an azo compound is more preferable, and an organic peroxide is more preferable.

Specific examples of the thermal radical generator include compounds described in paragraphs 0074 to 0118 of Japanese Patent Laid-Open No. 2008-63554.

In addition, among the commercially available products, examples of organic peroxides include: Percumyl D, Percumyl H, Percumyl ND, and Percumyl Road ( Percumyl P, Perloyl IB, Perloyl IP, Perloyl L, Perloyl NPP, Perloyl SA, Par Perloyl SBP, Perloyl TCP, Perloyl OPP, Perloyl 355, Perbutyl D, Perbutyl ) ND, Perbutyl NHP, Perbutyl PV, Perbutyl P, Perbutyl Z, Perbutyl Z, Perbutyl O, Pahai Perhexyl ND, Perhexyl O, Perhexyl PV, Parhexyl Perocta ND, Perocta O, Nyper BMT, Nyper BW, Nyper PMB, PerhexaHC, Perhaita Perhexa MC, PerhexTMH, PerhexV, Perhex 25B, Perhex 25O, Perhexyne 25B , Permethane H and others. Examples of the azo compound include V-601 manufactured by Wako.

The next region preferably contains 0.5 to 20% by mass of the thermal polymerization initiator with respect to the total solid content (amount other than the solvent) of the next region, more preferably 1 to 10% by mass, and even more preferably It is 2% to 8% by mass. When the content of the thermal polymerization initiator is within the above range, the heat resistance of the bonding region can be further improved.

In addition, the temporary bonding film preferably contains a thermal polymerization initiator in an amount of 0.5% to 20% by mass, and more preferably 1% to 10% by mass relative to the total solid content (amount other than the solvent) of the temporary bonding film. %, Particularly preferably 2% to 8% by mass.

<<< Interactive Agent >>>

The bonding region of the temporary bonding film of the present invention may contain a surfactant. As the surfactant, various surfactants such as a fluorine-based surfactant, a non-ionic surfactant, a cationic surfactant, an anionic surfactant, and a silicone surfactant can be used, and a fluorine-based surfactant is preferred. .

When a bonding region is formed by a coating method, the solution characteristics (especially fluidity) when preparing a coating solution are improved, and the uniformity of coating thickness or the liquid saving property can be further improved.

The fluorine content of the fluorine-based surfactant is preferably 3% by mass to 40% by mass. %, More preferably 5 mass% to 30 mass%, and even more preferably 7 mass% to 25 mass%. A fluorine-based surfactant having a fluorine content in this range is effective in terms of the uniformity of the thickness of the coating film or the liquid-saving property.

Examples of the fluorine-based surfactant include: Megafac F171, Megafac F172, Megafac F173, Megafac F176, Megafac F177, Megafac F141 , Megafac F142, Megafac F143, Megafac F144, Megafac R30, Megafac F437, Megafac F475, Megafac F479, Megafac F482, Megafac F554, Megafac F780, Megafac F781 (the above are manufactured by DIC), Fluorad FC430, Ferox Fluorad FC431, Fluorad FC171 (the above are made by Sumitomo 3M), Surflon S-382, Surflon SC-101, Surflon ) SC-103 、 Surflon SC-104 、 Surflon SC-105 、 Surflon SC1068 、 Surflon SC-381 、 Surflon SC -383, Surflon S393, Surflon KH-40 (the above are manufactured by Asahi Glass), PF636, PF656, PF6320, PF6520, PF7002 (manufactured by OMNOVA), etc. .

Non-ionic surfactants include glycerol, trimethylolpropane, trimethylolethane, and ethoxylates and propoxylates of these compounds (e.g., propoxylated glycerol, ethoxylated glycerol Etc.), polyoxyethylene lauryl ether, polyoxyethylene Stearyl ether, polyoxyethyl oleyl ether, polyoxyethyl octylphenyl ether, polyoxyethyl nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol Distearate, sorbitan fatty acid ester (Pluronic L10, BASF), Pluronic L31, Pluronic L61, Pluronic L62, Pronick (Pluronic) 10R5, Pluronic 17R2, Pluronic 25R2, Tetronic 304, Tetronic 701, Tetronic 704, Tetronic 901 , Tetronic 904, Tetronic 150R1, Solsperse 20000 (manufactured by Lubrizol Japan).

Examples of the cationic surfactant include a phthalocyanine derivative (trade name: EFKA-745, manufactured by Morishita Industries, Ltd.), an organosiloxane polymer KP341 (made by Shin-Etsu Chemical Industry Co., Ltd.), and (meth) acrylic acid Department of (co) polymer Polyflow No. 75, Polyflow No. 90, Polyflow No. 95 (manufactured by Kyoeisha Chemical Co., Ltd.), W001 (Manufactured by Yushang)

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

Examples of the silicone-based surfactant include: "Toray Silicone DC3PA", "Toray Silicone SH7PA", "Toray Silicone" manufactured by Toray-Dow corning Co., Ltd. Toray Silicone DC11PA "," Toray Silicone SH21PA "," Toray Silicone Silicone SH28PA "," Toray Silicone SH29PA "," Toray Silicone SH30PA "," Toray Silicone SH8400 ", Momentive Performance Materials "TSF-4440", "TSF-4300", "TSF-4445", "TSF-4460", "TSF-4452" manufactured by the company, "KP341", "KF6001", " "KF6002", "BYK307", "BYK323", "BYK330", etc. manufactured by BYK Chemie Japan.

When a surfactant is contained in the adjoining region, the content of the surfactant is preferably 0.001% by mass to 1% by mass, more preferably 0.01% by mass to 0.5% by mass, and even more preferably, relative to the total solid content of the adjoining region. 0.05% by mass to 0.1% by mass.

In addition, the temporary bonding film preferably contains 0.001% by mass to 1% by mass of the surfactant, more preferably 0.01% by mass to 0.5% by mass, relative to the total solid content (amount other than the solvent) of the temporary bonding film. It is particularly preferably from 0.05% by mass to 0.1% by mass.

The surfactant may be only one kind, or two or more kinds. When there are two or more kinds of surfactants, it is preferable that the total thereof is within the above range.

<<< Antioxidant >>>

The bonding region of the temporary bonding film of the present invention may contain an antioxidant from the viewpoint of preventing the low-molecularization or gelation of the bonding region caused by oxidation during heating. Examples of the antioxidant include phenol-based antioxidants, sulfur-based antioxidants, quinone-based antioxidants, and nitrogen-based antioxidants.

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

Examples of the sulfur-based antioxidant include 3,3'-thiodipropionate distearate, "Sumilizer TPM" manufactured by Sumitomo Chemical Co., Ltd., and "Sumilizer" TPS "," Sumilizer TP-D ", etc.

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

Examples of the amine-based antioxidant include dimethylaniline and phenothiazine.

The antioxidant is preferably Irganox 1010, Irganox 1330, 3,3'-thiodipropionate distearate, and more preferably Irganox 1010 1, Irganox (1330), especially preferably Irganox (1010).

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 even more preferably 750 or more.

In the case where the next region contains an antioxidant, the content of the antioxidant is preferably 0.001% to 10% by mass, more preferably 0.01% to 5% by mass, and even more preferably 0.1% relative to the total solid content of the next region. % ~ 1% by mass.

In addition, the temporary bonding film preferably contains 0.001% by mass to 10% by mass of the antioxidant relative to the total solid content (amount other than the solvent) of the temporary bonding film, more preferably 0.01% by mass to 5% by mass, particularly It is preferably 0.1% by mass to 1% by mass.

The antioxidant may be only one kind, or two or more kinds. When there are two or more antioxidants, it is preferable that the total thereof is within the above range.

<< Release area >>

The temporary bonding film of the present invention has a release region on the surface of the bonding region. The demolding region is used for the purpose of adjusting the bonding force between the element wafer and the bonding region to easily peel the temporary bonding film from the element wafer.

The average thickness of the demolding region is preferably 0.001 μm to 1 μm, and more preferably 0.01 μm to 0.5 μm. Within this range, the temporary adhesive film has a moderate adhesive force and good adhesion to the element wafer, and the temporary adhesive film can be easily peeled from the element wafer.

In the case where the temporary adhesive film of the present invention includes a laminated structure in which a layer forming a release region is laminated on a surface layer of a layer forming the adhesive region, the average thickness of the layer forming the release region is preferably 0.001 μm to 1 μm. , More preferably 0.01 μm to 0.5 μm.

In the case where the temporary adhesive film of the present invention is in a state where the release component in the temporary adhesive layer is biased to exist on the surface layer to form a release region, the average thickness of the release region is preferably 0.001 μm to 1 μm, and more preferably 0.01. μm ~ 0.5μm. In this case, the ratio of the average thickness of the bonding region to the average thickness of the demolding region is preferably the average thickness of the bonding region / average thickness of the demolding region = 10 to 1000, and more preferably 50 to 500.

In addition, in this invention, the average thickness of a mold release area is defined as the average value of the five points measured by the ellipsometry.

The release region of the temporary adhesive film of the present invention preferably contains a compound containing at least one selected from the group consisting of a fluorine atom and a silicon atom, and more preferably a fluorine-based silane coupler. mixture.

The fluorine content in the demolding region is preferably 30% by mass to 80% by mass, more preferably 40% by mass to 76% by mass, and even more preferably 60% by mass to 75% by mass. The fluorine content rate is defined by "{(the number of fluorine atoms in one molecule × the mass of fluorine atoms) / the mass of all atoms in one molecule} × 100".

In addition, the demolding region is preferably a compound containing at least one kind selected from a fluorine atom and a silicon atom with respect to the total solid content of the demolding region, and more preferably 50 mass% to 100 quality%.

In addition, in the temporarily-adhered film, the compound containing at least one selected from a fluorine atom and a silicon atom with respect to the total solid content of the temporarily-adhered film is preferably 10% to 100% by mass, and more preferably 50% to 100% quality%.

In the present invention, from the viewpoint of heat resistance, the release region preferably includes a three-dimensional crosslinked product containing a fluorine atom. Among them, a fluorine-containing polyfunctional monomer is preferred. The three-dimensional crosslinked product of the oligomer or the three-dimensional crosslinked product of the fluorine-containing silane coupling agent is particularly preferably the three-dimensional crosslinked product of the fluorine-containing silane coupling agent. The fluorine-containing silane coupling agent is preferably a non-halogen-based silane coupling agent having low danger to the human body and low corrosiveness to the metal, and particularly preferably a fluorine-containing alkoxysilane. Commercially available products include Optool DAC-HP and Optool DSX manufactured by Daikin Industrial Co., Ltd. Examples of the halogen-based silane coupling agent include fluorochlorosilane compounds.

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

The so-called non-three-dimensional cross-linked structure means that the compound does not contain a cross-linked structure or a shape. The ratio of the cross-linked structure forming a three-dimensional cross-linked structure to all the cross-linked structures in the compound is 5% or less, preferably 1% or less. It is preferable to contain a non-three-dimensional crosslinked structure substantially.

As the polymer compound having a fluorine atom-containing non-three-dimensional cross-linked structure, a polymer containing one or two or more fluorine-containing monofunctional monomers can be preferably used. More specific examples include at least one fluorine-containing resin selected from the group consisting of tetrafluoroethylene, hexafluoropropylene, tetrafluoroethylene oxide, hexafluoropropylene oxide, perfluoroalkyl vinyl ether, chlorotrifluoroethylene, Homopolymer or copolymer of one or more fluorine-containing monofunctional monomers of vinylidene fluoride, perfluoroalkyl group-containing (meth) acrylate, or one or two or more of them A copolymer of a fluorine-containing monofunctional monomer and ethylene, and a copolymer of one or two or more fluorine-containing monofunctional monomers and chlorotrifluoroethylene.

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

Specifically, the (meth) acrylate containing a perfluoroalkyl group is preferably a compound represented by the following formula (101).

In the general formula (101), R ¹⁰¹ , R ¹⁰² , and R ¹⁰³ each independently represent a hydrogen atom, an alkyl group, or a halogen atom. Y ¹⁰¹ represents a single bond or a divalent linking group selected from the group consisting of -CO-, -O-, -NH-, a divalent aliphatic group, a divalent aromatic group, and a combination of these groups. Rf is a fluorine atom or a monovalent organic group having at least one 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 methyl, ethyl, propyl, octyl, Isopropyl, third butyl, isopentyl, 2-ethylhexyl, 2-methylhexyl, cyclopentyl and the like. Examples of the aryl group are 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. Among them, R ¹⁰¹ to R ^{103 are} preferably a hydrogen atom or a methyl group.

Y ¹⁰¹ represents a single bond or a divalent linking group selected from the group consisting of -CO-, -O-, -NH-, a divalent aliphatic group, a divalent aromatic group, and a combination of these groups, For a divalent aliphatic group, a chain structure is better than a cyclic structure, and a linear structure is better 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, even more preferably from 1 to 12, even more preferably from 1 to 10, even more preferably from 1 to 8, and even more preferably 1 ~ 4.

Examples of the divalent aromatic group include phenylene, substituted phenylene, naphthyl, and substituted naphthyl, and phenylene is preferred.

Y ^{101 is} preferably an aliphatic group having a divalent linear structure.

The monovalent organic group having a fluorine atom represented by Rf is not particularly limited, but is preferably a fluorine-containing alkyl group having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and even more preferably 1 to 15 carbon atoms. Fluoroalkyl. The fluorine-containing alkyl group may be 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. } And may have a branch structure {for example, -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.}, may also have an alicyclic structure (preferably a 5-membered ring or a 6-membered ring, such as perfluorocyclohexyl, perfluorocyclopentyl, or alkyl substituted with these groups, etc.), also May contain ether bonds (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.). Alternatively, it may be a perfluoroalkyl group.

The (fluoro) acrylic resin containing a perfluoroalkyl group specifically contains a repeating unit represented by the following formula (102).

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

The (meth) acrylic resin containing a perfluoroalkyl group can select a copolymerization component other than the (meth) acrylate containing a perfluoroalkyl group from the viewpoint of releasability. Examples of the radical polymerizable compound capable of forming a copolymerization component are selected from the group consisting of acrylates, methacrylates, N, N-disubstituted acrylamides, and N, N- Radical polymerizable compounds among disubstituted methacrylamide, styrene, acrylonitrile, and methacrylonitrile.

More specifically, for example, acrylates (e.g., methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, acrylic acid) such as alkyl acrylate (the number of carbon atoms of the alkyl group is preferably 1 to 20) can be cited. Amyl ester, ethylhexyl acrylate, octyl acrylate, tertiary octyl acrylate, chloroethyl acrylate, -2,2-dimethylhydroxypropyl acrylate, 5-hydroxypentyl acrylate, trimethylol Propane monoacrylate, pentaerythritol monoacrylate, glycidyl acrylate, benzyl acrylate, methoxybenzyl acrylate, furfuryl acrylate, tetrahydrofurfuryl acrylate, etc.), aryl acrylate (eg, phenyl acrylate, etc.), Methacrylic acid alkyl esters (the number of carbon atoms of the alkyl group is preferably 1 to 20) and other methacrylic acid esters (e.g. methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate) Ester, amyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, chlorobenzyl methacrylate, octyl methacrylate, 4-hydroxybutyl methacrylate, 5-hydroxypentyl methacrylate, methyl Enoic acid-2,2-dimethyl-3-hydroxypropyl ester, trimethylolpropane monomethacrylate, pentaerythritol monomethacrylate, glycidyl methacrylate, furfuryl methacrylate, methyl Tetrahydrofurfuryl acrylate, etc.), aryl methacrylates (such as phenyl methacrylate, toluene methacrylate, naphthyl methacrylate, etc.), styrenes such as styrene, alkylstyrene (such as methylbenzene Ethylene, dimethylstyrene, trimethylstyrene, ethylstyrene, diethylstyrene, isopropylstyrene, butylstyrene, hexylstyrene, cyclohexylstyrene, decylstyrene, Benzylstyrene, chloromethylstyrene, trifluoromethylstyrene, ethoxymethylstyrene, acetamidine Oxymethylstyrene, etc.), alkoxystyrene (such as methoxystyrene, 4-methoxy-3-methylstyrene, dimethoxystyrene, etc.), halogen styrene (such as chlorine Styrene, dichlorostyrene, trichlorostyrene, tetrachlorostyrene, pentachlorostyrene, bromostyrene, dibromostyrene, iodostyrene, fluorostyrene, trifluorostyrene, 2-bromo-4 -Trifluoromethylstyrene, 4-fluoro-3-trifluoromethylstyrene, etc.), acrylonitrile, methacrylonitrile, acrylic acid, radical polymerizable compounds containing carboxylic acid (acrylic acid, methacrylic acid, clothing Conic acid, butenoic acid, methacrylic acid, maleic acid, p-carboxystyrene, and metal salts of these acid groups, ammonium salt compounds, etc.), from the standpoint of releasability, it is particularly preferred to have a carbon number of 1 to Examples of the (meth) acrylic acid ester of the hydrocarbon group of 24 include methyl (meth) acrylic acid, butyl ester, 2-ethylhexyl ester, lauryl ester, stearyl ester, and glycidyl ester. The (meth) acrylate of a higher alcohol such as ethylhexyl, lauryl, and stearyl is particularly preferably an acrylate.

As the polymer compound having a non-three-dimensional crosslinked structure having a fluorine atom as described above, a commercially available product can also be used. Examples include: Teflon (registered trademark) (Dupont), Tefzel (Dupont), Fluon (Asahi Glass), Halar ) (Solvay Solexis), Hylar (Solvay Solexis), Lumiflon (Asahi Glass), Afras (Aflas) (Asahi Glass Company), Cytop (Asahi Glass Company), Cefral Soft (Central Glass Company), Cefral Coat (Central Glass), Daionin (3M) and other fluororesins, Vuitton (Dupont) Company), Kalrez (Dupont), SIFEL (Shin-Etsu Chemical Industry Co., Ltd.), and other fluororubbers with Krytox (Dupont) Companies), Fomblin (Daitokutech), Demnum (Daikin Industrial Company) and other perfluoropolyether oils as representative Fluorine-containing release agents such as Daifree FB series (Daikin Industries), Megafac series (DIC) and other brand names.

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

The content of the polymer compound having a non-three-dimensional crosslinked structure having a fluorine atom in the release region is preferably 1% to 99% by mass with respect to the total solid content in the release region from the viewpoint of good peelability. %, More preferably 3% to 95% by mass, and even more preferably 5% to 90% by mass.

The ratio (mass ratio) of the fluorine atom-containing three-dimensional crosslinked product to the non-three-dimensional crosslinked polymer compound having a fluorine atom in the demolding region is preferably 5:95 to 50:50, and more preferably 10:90 to 40:60, further preferably 15: 85 ~ 30: 70.

The polymer compound having a non-three-dimensional crosslinked structure of a fluorine atom may be only one kind, or two or more kinds. When there are two or more cases, it is preferable that the total thereof is within the above range.

<Composition for temporary use>

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

The composition for temporary bonding of the present invention includes a heterocyclic-containing resin, a cross-linking component containing 50% by mass to 100% by mass of a maleimide resin, and a solvent, wherein the heterocyclic-containing resin includes a member selected from polyfluorene At least one of an imine resin, a polyfluorene imine resin, a polybenzimidazole resin, and a polybenzoxazole resin.

By using the temporary bonding composition of the present invention, the bonding region of the temporary bonding film of the present invention described above can be formed.

<< Heterocyclic resin >>

As the heterocyclic-containing resin, one or more members selected from the group consisting of a polyimide resin, a polyimide resin, a polybenzimidazole resin, and a polybenzoxazole resin can be used. As specific examples of these resins, the resins described in the section of the next region can be preferably used. Among these, polyimide resin is preferable. In addition, the polyfluorene imine resin is preferably selected from the group consisting of γ-butyrolactone, cyclopentanone, N-methylpyrrolidone, cyclohexanone, glycol ethers, dimethylimide, and tetramethylurea. Polyimide resin having a solubility at 25 ° C. of one or more solvents of 10 g / 100 g of a solvent (Solvent) or more.

The content of the heterocyclic-containing resin is preferably 1% to 99% by mass, and more preferably 10% to 90% by mass, relative to the total solid content (amount other than the solvent) of the composition to be temporarily used. It is preferably 25% to 75% by mass.

<< Crosslinking Ingredients >>

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

Here, the maleimide imide resin is preferably a bismaleimide resin. As a specific example of the maleimide resin, the maleimide described in the item of the next region can be preferably used. Resin.

The content of the maleimide resin in the crosslinking component is preferably 80% to 100% by mass of all the crosslinking components. Most preferably, the crosslinking component consists essentially of a maleimide resin. The term “substantially only composed of maleimide resin” means that the content of cross-linking components other than maleimide resin is, for example, preferably 1% by mass or less, more preferably 0.5% by mass or less, especially It is preferably 0.1% by mass or less. As the cross-linking component other than the maleimide resin, the components described in the item of other cross-linking components in the bonding region can be preferably used.

The content of the maleimide imide resin is preferably 1% to 99% by mass, and more preferably 10% to 90% by mass relative to the total solid content (amount other than the solvent) of the composition to be temporarily used. Especially preferred is 25% to 75% by mass.

<< Solvent >>

As the solvent, a known solvent can be used without limitation. For example, ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyrate Esters, methyl lactate, ethyl lactate, alkyl oxyacetate (e.g. methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate (e.g. methyl methoxyacetate, ethyl methoxyacetate) , Butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.)), alkyl 3-oxypropionates (e.g. methyl 3-oxypropionate, 3-oxypropionate, etc.) Ethyl propionate (e.g. methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.), Alkyl 2-oxypropionates (e.g. methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, etc.) (e.g. methyl 2-methoxypropionate , Ethyl 2-methoxypropionate, Propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), methyl 2-oxy-2-methylpropionate and 2-oxyl Ethyl-2-methylpropanoate (e.g. methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, pyruvate Ethyl acetate, propyl pyruvate, methyl ethyl acetate, ethyl acetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, propylene glycol monomethyl ether acetate acetate, PGMEA) (1-methoxy-2-propyl acetate); diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellulose Agent acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, Ethers such as propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate; methylpentyl ketone, methyl ethyl ketone, 2-butanone, cyclohexanone, 2-heptanone, 3-heptanone, N -Ketones such as methyl-2-pyrrolidone; aromatic hydrocarbons such as toluene, xylene, anisole, mesitylene, limonene, etc. Class; N, N-dimethylacetamide and the like.

Among them, anisole, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, 2-butanone, methylpentyl ketone, limonene, mesitylene, methyl Ethyl ketone, PGMEA (1-methoxy-2-propyl acetate), etc., more preferably N-methyl-2-pyrrolidone, N, N-dimethylacetamide, methylpentyl Ketone, limonene.

From the viewpoint of improving the coating surface, these solvents are also preferably in the form of a mixture of two or more.

As for the content of the solvent, it is preferable to concentrate the solid content of the composition temporarily It is used so that the degree becomes 5 to 60% by mass.

The solvent may be only one kind, or two or more kinds. When there are two or more solvents, it is preferable that the total thereof is within the above range.

<< Thermal polymerization initiator >>

The composition for temporary subsequent use preferably further contains a thermal polymerization initiator. By including a thermal polymerization initiator, a temporary adhesive film having more excellent heat resistance and chemical resistance can be formed. As the thermal polymerization initiator, the thermal polymerization initiator described in the item of the next region is preferably used, and the preferable range is also the same.

The content of the thermal polymerization initiator is preferably 0.001% by mass to 1% by mass, and more preferably 0.01% by mass to 0.5% by mass, relative to the total solid content (amount other than the solvent) of the composition to be temporarily used. It is preferably from 0.05% by mass to 0.1% by mass.

<< Release component >>

It is preferable that the composition for temporary adhesion further contains a mold release component. By containing the mold release component, when the composition for temporary bonding is applied in a film form, the mold release component is biased to exist on the surface layer, and a temporary bonding film in which the mold release region is biased to exist on the surface layer of the bonding area can be formed.

The mold release component is preferably a material containing at least one selected from a fluorine atom and a silicon atom. Examples of the material containing at least one selected from a fluorine atom and a silicon atom include a polymerizable monomer containing a fluorine atom or a silicon atom. More preferred is a fluorine-based silane coupling agent.

<<< Polymerizable monomer containing fluorine atom or silicon atom >>>

The polymerizable monomer containing a fluorine atom or a silicon atom is preferably a radical polymerizable monomer or oligomer containing one or more fluorine atoms or silicon atoms in one molecule, particularly preferably A polymerizable monomer having two or more fluorine atoms in one molecule and having a group generally called a perfluoro group.

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

It is preferred that the radical polymerizable monomer or oligomer containing a fluorine atom or a silicon atom has two or more radical polymerizable functional groups, thereby further improving the process under high temperature in the manufacturing process of the device. After the release from the component wafer.

<<<< Polymer monomer containing fluorine atom >>>>

The polymerizable monomer containing a fluorine atom can be selected from known monomers, and is preferably a monomer having a polymerizable group, and more preferably a fluorine-based silane coupling agent. Examples of the polymerizable group include a silyl group having a hydroxyl group or a hydrolyzable group (for example, an alkoxysilyl group, an alkoxysilyl group, etc.), and a group having a reactive unsaturated double bond ((meth) propylene). Fluorenyl, allyl, vinyloxy, etc.), ring-opening polymerization reactive groups (epoxy, oxetanyl, oxazolyl, etc.), groups with active hydrogen atoms (e.g. hydroxyl, carboxyl, amine, etc.) Groups, carbamoyl groups, mercapto groups, β-ketoester groups, hydrosilyl groups, silanol groups, etc.), acid anhydrides, groups (active halogen atoms, sulfonate esters, etc.) that can be substituted with nucleophiles.

The fluorine atom-containing radical polymerizable monomer is preferably a compound represented by the following general formula (1).

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

(In the formula, Rf represents a chain or cyclic n-valent group containing at least a carbon atom and a fluorine atom, and may contain any of an oxygen atom and a hydrogen atom, and n represents an integer of 2 or more. L represents a single bond or Divalent linking group. Y represents a polymerizable group)

In the general formula (I), Y is a polymerizable group, and for example, a silyl group having a hydroxyl group or a hydrolyzable group (for example, an alkoxysilyl group, a methoxysilyl group, etc.) is preferred, and Groups with saturated double bonds ((meth) acrylfluorenyl, allyl, vinyloxy, etc.), ring-opening polymerization reactive groups (epoxy, oxetanyl, oxazolyl, etc.), active Groups of hydrogen atoms (e.g. hydroxyl, carboxyl, amine, carbamoyl, mercapto, β-ketoester, hydrosilyl, silanol, etc.), acid anhydrides, groups that can be substituted by nucleophiles (active halogens Atom, sulfonate, etc.).

More preferably, Y represents a radical polymerizable group, and even more preferably a group having a reactive unsaturated double bond. Specifically, Y is preferably a radical polymerizable functional group represented by the following general 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. A dotted line indicates a bond with a group connected to L)

Examples of the alkyl group 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, an isopropyl group, a third butyl group, an isopentyl group, a 2-ethylhexyl group, 2-methylhexyl, cyclopentyl and the like. Examples of the aryl group are 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. Among them, R ⁹⁰¹ to R ^{903 are} preferably a hydrogen atom or a methyl group.

L represents a single bond or a divalent linking group. The divalent linking group represents a divalent aliphatic group, a divalent aromatic group, -O-, -S-, -CO-, -N (R)-, and a divalent obtained by combining two or more of these groups. Linker. Here, R represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.

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

Rf represents a chain or cyclic n-valent group containing at least a carbon atom and a fluorine atom, and may also contain any of an oxygen atom and a hydrogen atom. Rf may be a linear or branched polymer structure containing a repeating unit having a fluorine atom.

As such a fluorine atom-containing monomer, the compounds described in paragraph number 0019 to paragraph number 0033 of Japanese Patent Laid-Open No. 2011-48358 can be preferably used, and these contents are incorporated into the specification of the present application.

In addition, the radical polymerizable monomer having a fluorine atom is also preferably selected from the group consisting of the following structural formula (1), structural formula (2), structural formula (3), structural formula (4), and structural formula (5) At least one of the compounds represented.

CH ₂ = CR ¹ COOR ² R ^f … Structural formula (1)

(In the structural formula (1), R ¹ represents a hydrogen atom or a methyl group. R ² represents -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-. R ^f represents -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 -N (C _p H _{2p +1} ) SO ₂ C _n F _{2n + 1.} Among them, p represents an integer from 1 to 10, n represents an integer from 1 to 16, m represents an integer from 0 to 10, and i represents an integer from 0 to 16)

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 … Structural formula (4)

(In the structural formula (4), R ³ and R ⁴ represent a hydrogen atom or a methyl group. R ⁵ and R ⁶ represent -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 from 1 to 10, and t is an integer from 1 to 16)

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

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

Examples of the singular body 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 ) 2CF (CF2) ₆ (CH2) 3OCOCH = CH2, (CF ₃ ) 2CF (CF2) 10 (CH2) 3OCOC (CH3) = CH2, CF ₃ (CF2) 4CH (CH3) OCOC (CH3) = CH2, CF ₃ CH ₂ OCH ₂ CH ₂ OCOCH = CH ₂ , C ₂ F ₅ (CH2CH2O) 2CH2OCOCH = CH2, (CF ₃ ) ₂ CFO (CH2) 5OCOCH = CH2, 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 and so on. These single bodies can be used singly or in combination of two or more kinds.

Examples of the fluoroalkylated olefin represented by the structural formula (2) or the structural formula (3) include 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 , C ₈ F ₁₇ OCF = CF ₂ and so on.

Examples of the singular body represented by the structural formula (4) or the structural formula (5) include: 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.

Further, as the radical polymerizable monomer or oligomer containing a fluorine atom, an oligomer containing a repeating unit having a fluorine atom and a repeating unit having a radical polymerizable functional group can be preferably used.

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

In formula (6), R ¹ , R ² , R ^3, and R ⁴ each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, or a monovalent organic group, and at least one of R ¹ , R ² , R ^3, and R ⁴ is A fluorine atom or a monovalent organic group having 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, and Y1 represents a single bond or is selected from the group consisting of -CO-, -O-, -NH-, A divalent linking group in a group consisting of a divalent aliphatic group, a divalent aromatic group, and a combination of these groups. Rf represents a fluorine atom or a monovalent organic group having a fluorine atom.

In formula (10), R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , and R ¹³ each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, or a monovalent organic group, and Y ² and Y ³ represent a single bond or an optional group. A divalent linking group in a group consisting of -CO-, -O-, -NH-, a divalent aliphatic group, a divalent aromatic group, and a combination of these groups. Rf represents a divalent organic group having a fluorine atom.

The monovalent organic group having a fluorine atom in the formulae (6) and (7) is not particularly limited, but is preferably a fluorine-containing alkyl group having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and particularly preferably A fluoroalkyl group having 1 to 15 carbon atoms. The fluorine-containing alkyl group may be 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. ), May also have a branch structure (for example -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 also have an alicyclic structure (preferably a 5-membered ring or a 6-membered ring, such as perfluorocyclohexyl, perfluorocyclopentyl, or alkyl substituted with these groups, etc.), also May contain ether bonds (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.). Alternatively, it may be a perfluoroalkyl group.

The divalent organic group having a fluorine atom in the formula (10) is not particularly limited, but is preferably a fluorine-containing alkylene group having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and particularly preferably 1 to 2 carbon atoms. 15 fluorine-containing alkylene. The fluorine-containing alkylene may be linear (e.g. -CF ₂ CF _2- , -CH ₂ (CF ₂ ) _4- , -CH ₂ (CF ₂ ) ₈ CF _2- , -CH ₂ CH ₂ (CF ₂ ) ₄ -etc.), may also have a branched structure (e.g. -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 -etc.), or may have an alicyclic structure (preferably a 5-membered ring or a 6-membered ring, such as perfluorocyclohexyl, perfluorocyclopentyl, or via these groups) (Such as a substituted alkyl group) may contain an ether bond (for example, -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.). Alternatively, it may be perfluoroalkylene.

The monovalent organic group in the formula (6), the formula (7), and the formula (10) is preferably an organic group composed of a trivalent to 10-valent nonmetal atom, and examples thereof include: one selected from one to 60 An organic group composed of at least one element among carbon atoms, 0 to 10 nitrogen atoms, 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 alone or in combination.

The monovalent organic group may further have a substituent. Examples of the substituent that can be introduced include a halogen atom, a hydroxyl group, a carboxyl group, a sulfonato group, a nitro group, a cyano group, a fluorenylamino group, an amine group, an alkyl group, Alkenyl, alkynyl, aryl, substituted oxy, substituted sulfonyl, substituted carbonyl, substituted sulfinyl, sulfo, phosphono, phosphonato ), Silyl, heterocyclic and the like. The organic group may contain an ether bond, an ester bond, or a urea 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 methyl, ethyl, propyl, octyl, isopropyl, third butyl, isopentyl, 2-ethylhexyl, 2- Methylhexyl, cyclopentyl and the like. The alkenyl group is preferably an alkenyl group having 2 to 20 carbon atoms, and examples thereof include a vinyl group, an allyl group, a prenyl group, a geranyl group, and an oleyl group. The alkynyl group is preferably an alkynyl 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. Furthermore, the heterocyclic group is preferably a heterocyclic group having 2 to 10 carbon atoms, and examples thereof include furyl and thienyl. (thiophenyl), pyridyl and the like.

R ¹ , R ² , R ³ and R ⁴ in formula (6), R ⁵ , R ⁶ , R ⁷ in formula (7), R ⁸ , R ⁹ , R ¹⁰ , R ^{11 in} formula (10) The monovalent organic group represented by R ¹² , R ¹² and R ¹³ is preferably an alkyl group or an aryl group.

Examples of the alkyl group are preferably an alkyl group having 1 to 8 carbon atoms, and examples thereof include methyl, ethyl, propyl, octyl, isopropyl, third butyl, isopentyl, and 2-ethylhexyl , 2-methylhexyl, cyclopentyl and the like. Examples of the aryl group are 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. Among them, R ¹ to R ^{13 are} preferably a hydrogen atom or a methyl group.

In the following, Y ¹ in Formula (7) and Y ² and Y ³ in Formula (10) are selected from the group consisting of -CO-, -O-, -NH-, a divalent aliphatic group, and a divalent aromatic group. And specific examples of divalent linking groups in a group composed of a combination of these groups. In the following examples, the left side is bonded to the main chain and the right side is bonded to Rf.

L1: -CO-NH-divalent aliphatic group-O-CO-NH-divalent aliphatic group-O-CO-

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

L3: -CO-divalent aliphatic group -O-CO-

L4: -CO-O-divalent aliphatic group -O-CO-

L5: -divalent aliphatic group -O-CO-

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

L7: -CO-divalent aromatic group -O-CO-

L8: -divalent aromatic group -O-CO-

L9: -CO-O-divalent aliphatic group-CO-O-divalent aliphatic group-O-CO-

L10: -CO-O-divalent aliphatic group-O-CO-divalent aliphatic group-O-CO-

L11: -CO-O-divalent aromatic group-CO-O-divalent aliphatic group-O-CO-

L12: -CO-O-divalent aromatic group-O-CO-divalent aliphatic group-O-CO-

L13: -CO-O-divalent aliphatic group-CO-O-divalent aromatic group-O-CO-

L14: -CO-O-divalent aliphatic group-O-CO-divalent aromatic group-O-CO-

L15: -CO-O-divalent aromatic group-CO-O-divalent aromatic group-O-CO-

L16: -CO-O-divalent aromatic group-O-CO-divalent aromatic group-O-CO-

L17: -CO-O-divalent aromatic group-O-CO-NH-divalent aliphatic group-O-CO-

L18: -CO-O-divalent aliphatic group-O-CO-NH-divalent aliphatic group-O-CO-

L19:-divalent aromatic group-divalent aliphatic group

L20: -divalent aromatic group-divalent aliphatic group-O-divalent aliphatic group-

L21: -divalent aromatic group-divalent aliphatic group-O-divalent aliphatic group-O-

L22: -CO-O-divalent aliphatic group-

L23: -CO-O-divalent aliphatic group -O-

The divalent aliphatic group herein refers to an alkylene group, a substituted alkylene group, an alkylene group, a substituted alkylene group, an alkylene group, a substituted alkylene group, or a polyalkyleneoxy group. Among them, alkylene, substituted alkylene, alkylene and substituted alkylene are preferred, and alkylene and substituted alkylene are more preferred.

For a divalent aliphatic group, a chain structure is better than a cyclic structure, and a linear structure is better 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, even more preferably from 1 to 12, even more preferably from 1 to 10, Furthermore, it is more preferably 1 to 8, and even more preferably 1 to 4.

Examples of the substituent of the divalent aliphatic group include a halogen atom (F, Cl, Br, I), a hydroxyl group, a carboxyl group, an amine group, a cyano group, an aryl group, an alkoxy group, an aryloxy group, a fluorenyl group, and an alkane group. Oxycarbonyl, aryloxycarbonyl, fluorenyloxy, monoalkylamino, dialkylamino, arylamino, and diarylamino groups.

Examples of the divalent aromatic group include phenylene, substituted phenylene, naphthyl, and substituted naphthyl, and phenylene is preferred. 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 with respect to all repeating units of the radically polymerizable oligomer having a fluorine atom is preferably 2 mol% to 98 mol%, and more preferably 10 mol% to 90 mol. %.

The repeating unit having a radical polymerizable functional group is preferably a repeating unit represented by the following 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. Y ⁸ represents a single bond or is selected from the group consisting of -CO-, -O-, -NH-, and a divalent aliphatic group. Group, a divalent aromatic group, and a divalent linking group in a group consisting of a combination of these groups. T represents a structure having a radical 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).

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

Examples of the alkyl group are preferably an alkyl group having 1 to 8 carbon atoms, and examples thereof include methyl, ethyl, propyl, octyl, isopropyl, third butyl, isopentyl, 2-ethylhexyl, 2-methylhexyl, cyclopentyl and the like. Examples of the aryl group are 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. Among them, R ⁹⁰¹ to R ^{903 are} preferably a hydrogen atom or a methyl group.

Y ⁸ represents a single bond or a divalent linking group selected from the group consisting of -CO-, -O-, -NH-, a divalent aliphatic group, a divalent aromatic group, and a combination of these groups. Specific examples of Y ⁸ including combinations are listed below. In the following examples, the left side is bonded to the main chain, and the right side is bonded to Formula (9).

L1: -CO-NH-divalent aliphatic group-O-CO-NH-divalent aliphatic group-O-CO-

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

L3: -CO-divalent aliphatic group -O-CO-

L4: -CO-O-divalent aliphatic group -O-CO-

L5: -divalent aliphatic group -O-CO-

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

L7: -CO-divalent aromatic group -O-CO-

L8: -divalent aromatic group -O-CO-

L9: -CO-O-divalent aliphatic group-CO-O-divalent aliphatic group-O-CO-

L10: -CO-O-divalent aliphatic group-O-CO-divalent aliphatic group-O-CO-

L11: -CO-O-divalent aromatic group-CO-O-divalent aliphatic group-O-CO-

L12: -CO-O-divalent aromatic group-O-CO-divalent aliphatic group-O-CO-

L13: -CO-O-divalent aliphatic group-CO-O-divalent aromatic group-O-CO-

L14: -CO-O-divalent aliphatic group-O-CO-divalent aromatic group-O-CO-

L15: -CO-O-divalent aromatic group-CO-O-divalent aromatic group-O-CO-

L16: -CO-O-divalent aromatic group-O-CO-divalent aromatic group-O-CO-

L17: -CO-O-divalent aromatic group-O-CO-NH-divalent aliphatic group-O-CO-

L18: -CO-O-divalent aliphatic group-O-CO-NH-divalent aliphatic group-O-CO-

The divalent aliphatic group herein refers to an alkylene group, a substituted alkylene group, an alkylene group, a substituted alkylene group, an alkylene group, a substituted alkylene group, or a polyalkyleneoxy group. Among them, alkylene, substituted alkylene, alkylene and substituted alkylene are preferred, and alkylene and substituted alkylene are more preferred.

For a divalent aliphatic group, a chain structure is better than a cyclic structure, and a linear structure is better than a branched chain structure. The number of carbon atoms of the divalent aliphatic group is better It is 1 to 20, more preferably 1 to 15, still more preferably 1 to 12, even more preferably 1 to 10, still more preferably 1 to 8, and even more preferably 1 to 4.

Examples of the substituent of the divalent aliphatic group include a halogen atom (F, Cl, Br, I), a hydroxyl group, a carboxyl group, an amine group, a cyano group, an aryl group, an alkoxy group, an aryloxy group, a fluorenyl group, and an alkane group. Oxycarbonyl, aryloxycarbonyl, fluorenyloxy, monoalkylamino, dialkylamino, arylamino, and diarylamino groups.

Examples of the divalent aromatic group include phenylene, substituted phenylene, naphthyl, and substituted naphthyl, and phenylene is preferred. 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 2 mol% to 98 mol%, and more preferably 10 mol% with respect to all repeating units of the radically polymerizable oligomer having a fluorine atom. ~ 90 Mol%.

The weight-average molecular weight of polystyrene-equivalent polystyrene conversion obtained by the gel permeation chromatography (GPC) method of the radically polymerizable oligomer having a fluorine atom is preferably 2,000 to 20,000, more preferably 2,000 to 15,000, and most preferably 2,000. ~ 10000.

The weight-average molecular weight of a polystyrene-equivalent polystyrene-converted radical polymerizable oligomer having a fluorine atom obtained by a gel permeation chromatography (GPC) method is preferably 2000 to 10,000, more preferably 8000 to 2000, and most preferably 6000. ~ 2000.

When the composition for forming a release 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 is relative to The total solid content of the composition for forming a release region is preferably 0.01% by mass to 15% by mass. If it is 0.01% by mass or more, Then, sufficient peelability can be obtained. When it is 15% by mass or less, a sufficient adhesive force can be obtained.

There may be only one type of a radically polymerizable monomer or oligomer having a fluorine atom, or two or more types. When there are two or more kinds of polymerizable monomers, it is preferable that the total thereof is within the above range.

<<< Radical polymerizable monomer or oligomer having a silicon atom >>>

The radically polymerizable monomer or oligomer having a silicon atom is preferably a silicone monomer or a silicone oligomer, and examples thereof include at least one end of a polydimethylsiloxane bond as (meth) propylene. The compound having an ethylenically unsaturated group such as a fluorenyl group and a styryl group is preferably a compound having a (meth) acrylic fluorenyl group.

The polystyrene-equivalent number average molecular weight of the radically polymerizable oligomer having a silicon atom by gel permeation chromatography is preferably 1,000 to 10,000. When the polystyrene-equivalent number-average molecular weight of the radically polymerizable oligomer having a silicon atom by gel permeation chromatography is less than 1,000 or 10,000 or more, it is difficult to exhibit peelability by a silicon atom. And other properties.

The radical polymerizable monomer having a silicon atom is preferably a compound represented by the general formula (11) or the general formula (12).

[Chemical 10]

(In the general formula (11) and the general formula (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. Z ¹¹ , Z ^12, and Z ¹³ are each (L ¹¹ , L ^12, and L ¹³ each independently represent a single bond or a divalent linking group. N and m each independently represent an integer of 0 or more)

In the general formula (11) and the general formula (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 or branched, and is preferably an alkyl group having 1 to 5 carbon atoms. Specific examples include methyl, ethyl, n-propyl, and isopropyl. The alkoxy group means -OR ²⁰ , and R ²⁰ represents an alkyl group (preferably an alkyl group having 1 to 5 carbon atoms). Specific examples include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, and a butoxy group. Base etc. 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). Specific examples include a methoxycarbonyl group, an ethoxycarbonyl group, and a propyl group. Oxycarbonyl and the like. Examples of the aryl group include phenyl, tolyl, and naphthyl. These groups may also have a substituent. Examples include phenylmethyl (benzyl), phenylethyl, phenylpropyl, phenylbutyl, Naphthylmethyl and the like.

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 divalent aliphatic group, a divalent aromatic group, and a combination of these groups.

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

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

(In the general formula (i), R ¹⁰¹ to R ¹⁰³ each independently represent 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. (Organic)

In the general formula (i), R ¹⁰¹ to R ¹⁰³ each independently represent a hydrogen atom or a monovalent organic group. Preferred examples of R ¹⁰¹ include a hydrogen atom and an alkyl group which may have a substituent. Among these, a hydrogen atom and a methyl group are preferred because of their high reactivity. In addition, R ¹⁰² and R ¹⁰³ each independently preferably represent a hydrogen atom, a halogen atom, an amine group, a carboxyl group, an alkoxycarbonyl group, a sulfo group, a nitro group, a cyano group, an alkyl group which may have a substituent, or a substituent which may have a substituent. Aryl group, alkoxy group which may have a substituent, aryloxy group which may have a substituent, alkylamine group which may have a substituent, arylamine group which may have a substituent, alkyl group which may have a substituent Sulfonyl or arylsulfonyl which may have a substituent, among which a hydrogen atom, a carboxyl group, an alkoxycarbonyl group, an alkyl which may have a substituent, and an aromatic gene which may have a substituent are highly reactive and preferable .

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. Examples of the monovalent organic group include an alkyl group which may have a substituent. When R ¹⁰⁴ is a hydrogen atom, a methyl group, an ethyl group, or an isopropyl group, it is preferable because the radical reactivity is high.

Examples of the substituent that can be introduced include an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an alkoxy group, an aryloxy group, a halogen atom, an amine group, an alkylamino group, an arylamino group, a carboxyl group, and an alkoxycarbonyl group. , Sulfo, nitro, cyano, amidino, alkylsulfonyl, arylsulfonyl and the like.

(In the general formula (ii), R ²⁰¹ to R ²⁰⁵ each independently represent 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. (Organic)

In the general formula (ii), R ²⁰¹ to R ²⁰⁵ each independently represent a hydrogen atom or a monovalent organic group. R ²⁰¹ to R ²⁰⁵ are each independently preferably a hydrogen atom, a halogen atom, an amine group, a carboxyl group, an alkoxycarbonyl group, a sulfo group, a nitro group, a cyano group, an alkyl group which may have a substituent, and an aromatic group which may have a substituent. Group, alkoxy group which may have a substituent, aryloxy group which may have a substituent, alkylamino group which may have a substituent, arylamino group which may have a substituent, alkylsulfonyl group which may have a substituent Or an arylsulfonyl group which may have a substituent, more preferably 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.

Examples of the substituent that can be introduced include the same groups as those described in the general formula (i).

Y ²⁰¹ represents an oxygen atom, a sulfur atom, or -N (R ²⁰⁶ )-. R ²⁰⁶ has the same meaning as R ¹⁰⁴ of the general formula (i), and preferred examples are also the same.

(In the general formula (iii), R ³⁰¹ to R ³⁰³ each independently represent a hydrogen atom or a monovalent organic group. Z ³⁰¹ represents an oxygen atom, a sulfur atom, -N (R ³⁰⁴ )-or a phenylene group which may have a substituent. (R ³⁰⁴ has the same meaning as R ¹⁰⁴ of general formula (i))

In the general 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. Among these, a hydrogen atom or a methyl group is more preferable because of its high radical reactivity. R ³⁰² and R ³⁰³ are each independently preferably a hydrogen atom, a halogen atom, an amine group, a carboxyl group, an alkoxycarbonyl group, a sulfo group, a nitro group, a cyano group, an alkyl group which may have a substituent, and an aromatic group which may have a substituent. Group, alkoxy group which may have a substituent, aryloxy group which may have a substituent, alkylamino group which may have a substituent, arylamino group which may have a substituent, alkylsulfonyl group which may have a substituent Or an arylsulfonyl group which may have a substituent, a hydrogen atom, a carboxyl group, an alkoxycarbonyl group, an alkyl group which may have a substituent, or an aromatic gene which may have a substituent is highly reactive and free.

Examples of the substituent that can be introduced include the same groups 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 has the same meaning as R ¹⁰⁴ of the general formula (i). Examples of the monovalent organic group include an alkyl group which may have a substituent. Among these, methyl, ethyl, and isopropyl gene radicals have high reactivity and are preferred.

When the composition for mold release region formation contains a radical polymerizable monomer or oligomer having a silicon atom, the radical polymerizable monomer having a silicon atom is contained in the total solid content of the composition for mold release region formation. The content of the polymer or oligomer is preferably 0.01% by mass to 15% by mass. When it is 0.01% by mass or more, sufficient peelability can be obtained. When it is 15% by mass or less, a sufficient adhesive force can be obtained.

There may be only one type of radical polymerizable monomer or oligomer having a silicon atom, or two or more types. When there are two or more kinds of radically polymerizable monomers or oligomers having a silicon atom, it is preferable that the total thereof is within the above range.

Examples of the radically polymerizable monomer having a fluorine atom or a silicon atom include, for example, RS-75, RS-72-K, RS-76-E, and RS-72-K manufactured by DIC Corporation. Optool DAC-HP (Fluorine Silane Coupling Agent) manufactured by Daikin Industry Co., Ltd., X-22-164, X-22-164AS, X- 22-164A, X-22-164B, X-22-164C, X-22-164E, EBECRYL 350, EBECRYL 1360 manufactured by Daicel Cytec Co., Ltd., Germany TEGORad 2700, UV-3500B (Bi (BYK) company) and so on.

In addition to the above, examples of the material having a fluorine atom or a silicon atom include: (heptadecafluoro-1,1,2,2-tetrahydrodecyl) trichlorosilane, (fluoro) alkyl phosphate, and fluorinated polypara Copolymers of parylene fluoride, silicon acrylate copolymer, tetrafluoroethylene and 2,2-bis-trifluoromethyl-4,5-difluoro-1,3-dioxolene, Polymers with pendant perfluoroalkoxy groups, fluoroethylene-propylene copolymers, etc.

The content of the mold release component is preferably 0.01% by mass to 10% by mass, more preferably 0.05% by mass to 5% by mass, and even more preferably 0.1 mass% to 1 mass%.

<< Interactive Agent >>

The composition for temporary subsequent use preferably contains a surfactant. As the surfactant, the surfactant described in the item of the next region is preferably used, and the preferable range is also the same.

The content of the surfactant is preferably 0.001% by mass to 1% by mass, more preferably 0.01% by mass to 0.5% by mass, and even more preferably, relative to the total solid content (amount other than the solvent) of the composition for temporary bonding. 0.05% by mass to 0.1% by mass.

The surfactant may be only one kind, or two or more kinds. When there are two or more kinds of surfactants, it is preferable that the total thereof is within the above range.

<< Antioxidant >>

The composition for temporary follow-up preferably contains an antioxidant. As the antioxidant, the antioxidant described in the item of the next region can be preferably used, and the preferable range is the same.

The content of the antioxidant is preferably 0.001% by mass to 10% by mass, and more preferably 0.01 relative to the total solid content (amount other than the solvent) of the composition for temporary bonding. Mass% to 5 mass%, particularly preferably 0.1 mass% to 1 mass%.

The antioxidant may be only one kind, or two or more kinds. When there are two or more antioxidants, it is preferable that the total thereof is within the above range.

<< Plasticizer >>

The temporary bonding composition preferably contains a plasticizer in order to improve the flatness of bonding at a high temperature.

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

Examples of phthalic acid esters are: DMP, DEP, DBP, # 10, BBP, DOP, DINP, DIDP (the above are manufactured by Big Eight Chemicals), PL-200, DOIP (the above are manufactured by CG Ester) ), Sansocizer DUP (manufactured by New Japan Physicochemical), etc.

Examples of fatty acid esters include: butyl stearate, Unistar M-9676, Unistar M-2222SL, Unistar H-476, Unistar H -476D, Panasate 800B, Panasate 875, Panasate 810 (above are manufactured by Nippon Oil), DBA, DIBA, DBS, DOA, DINA, DIDA, DOS , BXA, DOZ, DESU (the above are manufactured by Da Ya Chemical) and so on.

Examples of aromatic polycarboxylic acid esters are: TOTM (manufactured by Daiha Chemical), Monocizer W-705 (manufactured by Daiha Chemical), UL-80, UL-100 (manufactured by ADEKA) Wait.

Polyester can be listed: Polycizer TD-1720, Polysizer (Polycizer) S-2002, Polycizer S-2010 (above, manufactured by DIC), BAA-15 (made by Da Ya Chemicals), etc.

Among the plasticizers, preferred are DIDP, DIDA, TOTM, Unistar M-2222SL, Polycizer TD-1720, more preferably DIDA, TOTM, and most preferably TOTM.

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

Regarding the molecular weight of the plasticizer, from the viewpoint of preventing sublimation during heating, the temperature at which the weight is reduced by 1% by mass when measured under a nitrogen flow at a constant temperature increase rate of 20 ° C / min is preferably 250 ° C or more, and more The temperature is preferably 270 ° C or higher, and particularly preferably 300 ° C or higher. The upper limit is not particularly limited, and may be set to 500 ° C or lower, for example.

The content of the plasticizer is preferably 1% by mass to 50.0% by mass, and more preferably 5% by mass to 20.0% by mass relative to the total mass of the composition to be temporarily adhered.

There may be only one plasticizer or two or more plasticizers. When there are two or more plasticizers, it is preferable that the total thereof is within the above range.

<< Other additives >>

The composition for temporary bonding of the present invention may be formulated with various additives such as a hardener, a curing catalyst, a filler, an ultraviolet absorber, an anti-agglomerating agent, and the like, as long as the effect of the present invention is not impaired. When these additives are blended, the total blended amount is preferably set to 3% by mass or less of the solid content of the composition for temporary bonding.

The bonding region of the temporary bonding film of the present invention can be formed by using a conventionally known spin coating method, spray method, roll coating method, flow coating method, and doctor blade coating. In the cloth method, the dipping method, and the like, the composition described above is temporarily applied to the support substrate and then dried. Among them, a spin coating method, a spray method, and a screen printing method are preferred, a spin coating method, a spray method is more preferred, and a spin coating method is particularly preferred.

<Composition for forming mold release area>

Next, the composition for mold release area formation is demonstrated.

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

<< Release component >>

The mold release component is preferably a material containing at least one selected from a fluorine atom and a silicon atom. Examples of the material containing at least one selected from a fluorine atom and a silicon atom include a polymerizable monomer containing a fluorine atom or a silicon atom. More preferred is a fluorine-based silane coupling agent. With the fluorine-based silane coupling agent, a layer in the release region can be firmly formed on the surface of the bonding region. Therefore, the solvent does not easily penetrate into the interface between the layer in the bonding region and the layer in the release region, and a temporary bonding film having excellent chemical resistance can be formed. The details of the mold release component are the same as those described in the section of the mold release component of the composition for the time being, and the preferred ranges are also the same.

From the viewpoint of good peelability, the content of the mold release component is preferably 5% to 100% by mass, and more preferably 50% to 100% by mass, relative to the total solid content of the composition for forming the mold release region. , And further preferably 90% by mass to 100% by mass.

<< Solvent >>

As long as the solvent can form a mold release region, a known solvent can be used without limitation, and the same solvent as the solvent in the temporary bonding composition described above can be used. In addition, perfluoroalkanes can be used. Among them, N-methyl-2-pyrrolidone, 2-butanone, Methylpentyl ketone, limonene, 1-methoxy-2-propyl acetate, perfluoroalkane, methyl ethyl ketone, more preferably N-methyl-2-pyrrolidone, 2-butanone , Methylpentyl ketone, limonene, 1-methoxy-2-propyl acetate.

From the viewpoint of improving the coating surface, these solvents are also preferably in the form of a mixture of two or more.

<< Other ingredients >>

In addition to the above-mentioned components, the composition for forming a mold release region may further contain various compounds depending on the purpose, as long 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. As these components, the components described in the temporary application composition described above can be used.

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

The demolding region can be formed by using a conventionally known spin coating method, spray method, roll coating method, flow coating method, doctor blade coating method, dipping method, and the like, and forming the aforementioned demolding region forming composition. The object is coated on a support substrate and then dried. Among them, a spin coating method, a spray method, and a screen printing method are preferred, a spin coating method, a spray method is more preferred, and a spin coating method is particularly preferred.

<Set>

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

The kit of the present invention includes the composition for temporary bonding described above and the composition for forming a mold release region containing a mold release component and a solvent.

The temporary adhesive film of the present invention can be produced by sequentially coating the temporary adhesive composition and the release region forming composition on the support substrate.

In addition, the temporary adhesive film of the present invention can also be produced by sequentially applying a composition for forming a release region and a composition for temporary adhesion on an element wafer.

Each composition, preferable range, and the like of the composition for temporary use and the composition for forming a release region are the same as those described above.

<Layered body>

Next, the laminated body of this invention is demonstrated.

The laminated body of the present invention is obtained by laminating element wafers on the surface of the release region of the temporary bonding film of the present invention described above.

As the element wafer, a known element wafer can be used without limitation, and examples thereof include a silicon substrate and a compound semiconductor substrate. Specific examples of the compound semiconductor substrate include a SiC substrate, a SiGe substrate, a ZnS substrate, a ZnSe substrate, a GaAs substrate, an InP substrate, and a GaN substrate.

Mechanical structures or circuits can also be formed on the surface of the element wafer. For example, a device wafer formed with a mechanical structure or a circuit may include a micro electro mechanical system (MEMS), a power device, an image sensor, a microsensor, and a light emitting diode , LED), optical components, interposers, embedded components, micro-components, etc.

The element wafer preferably has a structure such as a metal bank. The temporary bonding film of the present invention can also stably perform temporary bonding on a device wafer having a structure on the surface, and can easily release the temporary bonding on the device wafer. The height of the structure is not particularly limited It is preferably, for example, 5 μm to 100 μm.

The film thickness of the element wafer before the mechanical or chemical treatment is preferably 500 μm or more, more preferably 600 μm or more, and even more preferably 700 μm or more.

The film thickness of the element wafer after being thinned by mechanical or chemical treatment is, for example, preferably less than 500 μm, more preferably 400 μm or less, and even more preferably 300 μm or less.

In the multilayer body of the present invention, it is preferable that a support substrate is disposed on a surface of the element wafer that is temporarily adhered to the film and that is on the opposite side to the element 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 preferred in terms of not easily contaminating a silicon substrate that is typically used as a substrate of a semiconductor element, or an aspect that can use an electrostatic chuck that is widely used in manufacturing steps of a semiconductor element.

The thickness of the support substrate is not particularly limited, but is preferably 300 μm to 5 mm, for example.

<Element Manufacturing Method>

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

The device manufacturing method of the present invention includes the step of applying the temporary bonding composition of the present invention described above. Hereinafter, the element manufacturing method of the present invention will be described in more detail.

<< Manufacture of Supporting Substrate-Temporary Adhesive Film-Element Wafer Laminate >>

The support substrate-temporary bonding film-element wafer laminated body (hereinafter also referred to as a laminated body) can be manufactured by any one of the following methods (1) to (4).

(1) The temporary bonding composition of the present invention is coated on a support substrate, and Heat (bake) to form a layer that adheres to the area. Examples of the coating method for temporarily applying the composition include conventionally known methods such as a spin coating method, a spray method, a roll coating method, a flow coating method, a doctor blade coating method, and a dipping method.

Then, the above-mentioned composition for forming a mold release region is applied to the layer of the adhesive region, and the layer of the mold release region is formed by heating (baking) to form the temporary adhesive film of the present invention. Examples of a method for applying the composition for forming a mold release region include a conventionally known method such as a spin coating method, a spray method, a roll coating method, a flow coating method, a doctor blade coating method, and a dipping method.

Then, the element wafer is press-bonded onto a surface on the side opposite to the surface on which the supporting substrate is temporarily disposed of the film (that is, the surface on the side of the release region of the film) to produce a laminated body. The pressure bonding conditions are preferably, for example, a temperature of 100 ° C. to 200 ° C., a pressure of 0.01 MPa to 1 MPa, and a time of 1 minute to 15 minutes.

(2) The above-mentioned composition for forming a mold release region is applied to the element wafer, and the layer is formed by heating (baking) the mold release region.

Then, the composition for temporary adhesion of this invention is apply | coated on the layer of a mold release area | region, and it heats (bakes), and forms the layer of an adhesion area | region, and forms the temporary adhesion film of this invention.

Then, the substrate is pressed and supported on the surface on the side opposite to the surface on which the element wafer is temporarily disposed of the film (that is, the surface on the side of the region where the film is temporarily adhered) to produce a laminated body. The pressure bonding conditions are preferably the conditions described above.

(3) The composition for temporary bonding of the present invention containing a mold release component is coated on any surface of the support substrate and the element wafer, and heating (baking) is performed to form a mold release region that is biased to a surface layer existing in the adhesion region The film is temporarily adhered.

Then, the substrate or the element wafer is pressed and supported on the surface of the temporarily adhered film to manufacture a laminated body. The pressure bonding conditions are preferably the conditions described above.

(4) The above-mentioned composition for forming a release region is coated on the element wafer, and the layer is formed on the element wafer by heating (baking).

Then, the temporary bonding composition of the present invention described above is applied to the support substrate, and the substrate is heated (baked) to form a layer of a bonding region on the support substrate.

Then, the release region on the element wafer and the bonding region on the support substrate are press-bonded to form a temporary bonding film, and a laminated body is manufactured. The pressure bonding conditions are preferably the conditions described above.

Hereinafter, a method for manufacturing an element wafer after the step of manufacturing a laminated body by the method shown in (4) above will be described with reference to FIG. 1.

FIG. 1 (A), FIG. 1 (B), and FIG. 1 (C) are schematic cross-sectional views explaining a temporary and subsequent explanation of a support substrate and an element wafer, respectively, and showing element crystals temporarily adhered by the support substrate. A circle schematic cross-sectional view and a schematic cross-sectional view showing a state where the element wafer temporarily attached by the support substrate is thinned.

As shown in FIG. 1A, the element wafer 60 is formed by providing a plurality of element wafers 62 on the surface 61 a of the silicon substrate 61. Further, a release region 71 is provided on a surface on the structure 62 side of the element wafer 60.

The element wafer 60 preferably has an average film thickness of 500 μm or more. The structure 62 is called an element wafer or a bump, and the average height is preferably in a range of 5 μm to 100 μm.

As shown in FIG. 1 (A), it is prepared to provide a bonding area on the support substrate 12. 11 is an adhesive support 100. The adhesive support 100 can be formed by coating the temporarily adherent composition of the present invention with a conventionally known spin coating method, spray method, roll coating method, flow coating method, doctor blade coating method, dipping method, or the like. It is spread on the support substrate 12 and then dried.

Next, the temporary support of the adhesive support 100 and the element wafer 60 obtained as described above, the thickness reduction of the element wafer 60, and the peeling of the adhesive support 100 from the element wafer will be described.

The surface of the mold release region 71 provided on the element wafer is pressed against the bonding region 11 of the bonding support 100. Thereby, as shown in FIG.1 (B), the mold release area 71 and the bonding area 11 are continued, and the temporary bonding film 80 which has the mold release area 71 and the bonding area 11 is formed.

Next, the back surface 61b of the silicon substrate 61 is subjected to a mechanical treatment or a chemical treatment (there is no particular limitation, such as grinding or chemical-mechanical polishing (CMP)), and a thin film treatment such as chemical vapor deposition (Chemical High temperature such as Vapor Deposition (CVD) or Physical Vapor Deposition (PVD). Treatment under vacuum, treatment with chemicals such as organic solvents, acidic treatment solutions or alkaline treatment solutions, plating treatment, actinic rays Irradiation, heating, cooling treatment, etc.), as shown in FIG. 1 (C), the thickness of the silicon substrate 61 is reduced (for example, the average thickness is preferably less than 500 μm, more preferably 1 μm to 200 μm) to obtain a thin element crystal Circle 60a.

In addition, the following process may be performed as a mechanical process or a chemical process. After the thin film process, a silicon substrate is formed from the back surface 61c of the thin element wafer 60a to penetrate the silicon substrate. A through hole (not shown) is formed with a silicon through electrode (not shown) in the through hole. Specifically, the maximum temperature reached during the heat treatment is preferably 130 ° C to 400 ° C, and more preferably 180 ° C to 350 ° C. The maximum temperature reached during the heat treatment is set to a temperature lower than the softening point of the subsequent region. The heat treatment is preferably heating for 30 seconds to 30 minutes at the highest reaching temperature, and more preferably heating for 1 minute to 10 minutes at the highest reaching temperature.

Then, the film 80 is temporarily peeled from the surface 61a of the thin element wafer 60a.

The peeling of the film 80 temporarily is preferably performed by a physical action such as tearing. In addition, it is preferable that the thin element wafer 60 a is slid with respect to the adhesive support 100, or the thin element wafer 60 a is peeled from the adhesive support 100. By this method, the temporary adhesive film 80 can be peeled from the surface 61a of the thin element wafer 60a.

After the film 80 is temporarily detached from the thin element wafer 60a, the surface 61a of the thin element wafer 60a may be treated with a stripping solution or the like as necessary. As the peeling liquid, for example, the peeling liquid described in paragraph number 0203 to paragraph number 0212 of Japanese Patent Laid-Open No. 2014-80570 can be used. In addition, the temporary bonding film 80 of the present invention does not necessarily need to be treated with a peeling liquid or the like. The temporary adhesive film 80 may be removed from the surface 61a of the thin element wafer 60a only by mechanical peeling without causing peeling residues or the like.

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

In addition, in the embodiment described above, the release layer has a single-layer structure, but the release layer The mold layer may have a multilayer structure.

In addition, in the embodiment described above, the substrate to be processed may be a silicon substrate, but it is not limited thereto, and may be any substrate to be processed that can be mechanically processed or chemically processed in the element manufacturing method. For example, a compound semiconductor substrate may be mentioned. Specific examples of the compound semiconductor substrate include a SiC substrate, a SiGe substrate, a ZnS substrate, a ZnSe substrate, a GaAs substrate, an InP substrate, and a GaN substrate.

In addition, in the embodiment described above, the mechanical treatment or chemical treatment of the silicon substrate supported by the support substrate may include a thin film processing of the silicon substrate and a process of forming a silicon through electrode, but the invention is not limited to this. These processes may also be arbitrarily required in the element manufacturing method.

In addition, the shape, size, number, arrangement position, and the like of the element wafer among the element wafers exemplified in the embodiment described above are arbitrary and are not limited.

[Example]

Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples as long as the present invention does not exceed the gist thereof. In addition, unless otherwise specified, "part" and "%" are quality standards.

(Example 1)

<Formation of Adjoining Area>

A spin coater (Opticoat MS-A100 manufactured by Mikasa, 1200 rpm, 30 seconds) was used to apply the composition 1 for forming a bonding region having the composition shown in Table 1 to a 4-inch Si crystal. After being rounded, the wafer 1 was baked at 120 ° C. for 3 minutes and 250 ° C. for 3 minutes to form a wafer 1 having a bonding region having a thickness of 5 μm.

<Formation of demolding area>

For the bonding area of the wafer 1, a mold release having the composition shown in Table 2 was applied by a spin coater (Opticoat MS-A100, 1200, rpm, 30 seconds manufactured by Mikasa). After the composition 1 for area formation, it was baked on a hot plate at 120 ° C for 30 seconds, and then baked at 190 ° C for 3 minutes. A release area having a thickness of 0.1 μm was formed on the adhesion area, and a temporary adhesion film was formed. Of the wafer 1.

<Production of test strip>

Wafer 1 was bonded to a 4-inch Si wafer (wafer 2) without any coating on the surface to prepare a test piece.

[Crimp]

The surface of the wafer 1 having the temporary adhesive film was overlapped with the surface of the wafer 2 without any coating, and then pressed at 190 ° C and 0.20 MPa for 3 minutes.

[bake]

After pressing, heating was performed at 280 ° C for 30 minutes.

(Example 2 to Example 32, Example 35)

In Example 1, the bonding region formation composition and the mold release region formation composition were each combined with the composition shown in Table 3 to form the bonding region and the mold release region, and a temporary bonding film was prepared in accordance with Example 1. Audition.

(Example 33)

A composition prepared by mixing 99% by mass of the composition 19 for forming an adhesive region and 1% by mass of the composition 1 for forming a mold release region, the composition was prepared by a spin coater (Optika made by Mikasa) ) MS-A100, 1200rpm, 30 Seconds) after coating on a 4-inch Si wafer, baking at 120 ° C for 3 minutes, and baking at 250 ° C for 3 minutes to form a wafer 1 with a bonding region having a thickness of 5 μm. A test piece provided with a temporary adhesive film was produced.

(Example 34)

A composition prepared by mixing 99% by mass of the composition 19 for forming an adhesive region and 1% by mass of the composition 2 for forming a release region by a spin coater (Optika made by Mikasa) ) MS-A100, 1200 rpm, 30 seconds) After coating on a 4-inch Si wafer, bake at 120 ° C for 3 minutes and 250 ° C for 3 minutes to form a crystal with a 5 μm thickness bonding area Circle 1, a test piece provided with a temporary adhesive film was produced in accordance with Example 1.

(Comparative example 1)

In Example 1, a test piece provided with a temporary adhesive film was produced in accordance with Example 1 except that the composition 1 for forming a release region was not used.

(Comparative example 2)

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

(Comparative Example 3 to Comparative Example 7)

In Example 1, except that the comparative composition 1 to the comparative composition 7 were used in place of the bonding region forming composition 1, the test piece provided with the temporary bonding film was prepared in accordance with Example 1.

<Adherence>

Using a tensile tester (manufactured by Imada) at 50 mm / min. The condition is that the tensile measurement is performed along the direction of the surface where the film is temporarily adhered, and the shear adhesion of the produced test piece is evaluated in accordance with the following criteria. In the following evaluation criteria, 2 to 5 are practical, and 3 to 5 are preferred.

5: 80N or more

4: Adhesion force above 60N and less than 80N

Adhesive force above 3: 40N and less than 60N

2: Adhesion force above 20N and less than 40N

1: Adhesive force less than 20N

<Peelability>

The produced test piece was subjected to tensile measurement at a condition of 50 mm / min in a direction perpendicular to the surface where the film was temporarily adhered, and evaluated based on the following criteria. In the following evaluation criteria, 2 to 5 are practical, and 3 to 5 are preferred.

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

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

1: The wafer is broken during the peeling process

<Chemical resistance>

The prepared test piece was placed in a glass container filled with N-methyl-2-pyrrolidone at 25 ° C, and after applying ultrasonic waves for 15 minutes using an ultrasonic cleaner, 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 preferred.

5: There is no peeling of the wafer, and the surface of the film temporarily adhered after peeling is not eroded by the solvent.

4: There is no peeling of the wafer, but the range where the distance from the side where the film is in contact with the solvent temporarily after the peeling is less than 1 mm is eroded by the solvent.

3: There is no peeling of the wafer, but the distance from the side where the film is temporarily adhered to the solvent after peeling is in the range of 1 mm or more and less than 5 mm due to the solvent.

2: There is no peeling of the wafer, but the range of 5 mm or more from the side surface in contact with the solvent after the peeling of the temporarily adhered film is eroded by the solvent.

1: Wafer peeling.

<Void (void)>

When forming the wafer 1, a 4-inch glass wafer was used instead of a 4-inch Si wafer, and no change was made except for the temporary bonding layers of Examples 1 to 35 and Comparative Examples 1 to 9, and Inch Si wafer. The obtained sample was heated at 400 ° C for 3 hours in an oven under a nitrogen atmosphere. Thereafter, the temporarily adhered layer was visually observed from the glass wafer side of the sample, and evaluated according to the following criteria. In the following evaluation criteria, 2 to 5 are practical, and 3 to 5 are preferred.

In addition, the pore means a void generated at the interface between the adhesion layer and the glass wafer temporarily.

5: No pores were seen at all.

4: Less than 5 pores are visible.

3: 5 or more and less than 10 pores are visible.

2: 10 or more and less than 15 pores are visible.

1: 15 or more pores are visible.

The compounds described in Table 1 are as follows.

[Resin composition]

B-1: Durimide (registered trademark) 284

(Soluble polyimide resin made by Fujifilm)

B-2: Durimide (registered trademark) 10

(Polyfluoride and imide resin soluble in solvents made by Fujifilm)

B-3: GPT-LT (solvent-soluble polyimide resin manufactured by Qunrong Chemical)

B-4: Rikacoat (manufactured by New Japan Physicochemical Co., Ltd.)

B-5: Vylomax (registered trademark) 13NX

(Manufactured by Toyobo Co., Ltd.)

B-6: MRS0810H

(Manufactured by PBI, polybenzimidazole resin)

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

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

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

[Crosslinking component]

C-1: BMI-1000 (manufactured by Daiwa Chemical Industry, bismaleimide resin)

C-2: BMI-2000 (manufactured by Yamato Chemical Industry, bismaleimide resin)

C-3: BMI-3000 (manufactured by Daiwa Chemical Industries, bismaleimide resin)

C-4: BMI-4000 (manufactured by Daiwa Chemical Industry, bismaleimide resin)

C-5: BMI-5000 (manufactured by Daiwa Chemical Industry, bismaleimide resin)

C-6: BMI-7000 (manufactured by Yamato Chemical Industry, bismaleimide resin)

C-7: BANI-X (manufactured by Shin Nakamura Chemical, bismaleimide resin)

C-8: BANI-M (manufactured by Shin Nakamura Chemical, bismaleimide resin)

C-9: A-9300 (manufactured by Shin Nakamura Chemical, acrylic resin)

[Thermal polymerization initiator]

D-1: Percumyl H (manufactured by Nippon Oil, organic peroxide, one-minute half-life temperature of 254 ° C)

D-2: Percumyl P (manufactured by Nippon Oil, organic peroxide, one-minute half-life temperature of 232.5 ° C)

D-3: Perbutyl Z (manufactured by Nippon Oil, organic peroxide, one-minute half-life temperature of 166.8 ° C)

D-4: NyperBW (manufactured by Nippon Oil, organic peroxide, one-minute half-life temperature of 130.0 ° C)

D-5: V-601 (manufactured by Wako, azo initiator, one-minute half-life temperature 120 ° C)

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

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

Comparative composition 2: The composition of Example 2 of Japanese Patent Laid-Open No. 2014-29999 was prepared.

Comparative composition 3: A composition of Example 3 of Japanese Patent Laid-Open No. 2014-29999 was prepared.

Comparative composition 4: The composition of Example 4 of Japanese Patent Laid-Open No. 2014-29999 was prepared.

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

Comparative composition 6: A composition of Example 6 of Japanese Patent Laid-Open No. 2014-29999 was prepared.

Composition 7 for comparison: The cross-linking component C-1 was not included in the composition 1 for temporary adhesion.

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

<400 ° C mass reduction rate>

Using a thermogravimetric analyzer Q500 (manufactured by TA Corporation), a 2 mg to 3 mg sample was placed on an aluminum pan (Aluminum Pan) under a nitrogen flow of 60 mL / min under a constant temperature rising condition of 10 ° C./min from an initial temperature of 25 ° C. The temperature was raised to 400 ° C, and the residual mass at 400 ° C was measured.

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

<Solubility>

While stirring the sample, 100 g of N-methyl-2-pyrrolidone was added to a certain amount, and the solubility was confirmed. When it is completely dissolved, further add a certain amount of sample under stirring, repeat the operation, and finally stir the sample at 25 ° C for 1 hour. The amount immediately before dissolution was taken as the solubility.

The compounds described in Table 2 are as follows.

[Release component]

A-1: Optool DSX (manufactured by Daikin Industries, fluorine-based silane coupling agent)

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

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

A-4: UV-3500B (manufactured by BYK, silicon-based compound)

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

A-6: CHEMINOX FHP-2-OH (manufactured by Unimatec, fluorine compound)

A-7: Teflon (registered trademark) AF (manufactured by Mitsui Dupont Fluoro chemical company, fluorine-based compounds)

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

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

A-10: In the Daionin THV (manufactured by 3M, a fluorine-based compound), the release components constituting the three-dimensional crosslinked body of the release layer are A-1 to A-4.

[Solvent]

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

S-2: 1-methoxy-2-propyl acetate

S-3: CT-Solv180 (manufactured by AGC)

S-4: methyl ethyl ketone

Based on the results, all of the temporary adhesive films of Examples 1 to 35 had good adhesion, peelability, and chemical resistance. In addition, there are few pores.

On the other hand, Comparative Examples 1 to 9 are below practical levels in at least one or more items of adhesion, peelability, and chemical resistance.

Claims (21)

A temporary bonding film having a bonding region and a release region on a surface of the bonding region, wherein the bonding region includes a heterocyclic-containing resin and a cross-linking component, and the heterocyclic-containing resin includes a resin selected from polyfluorene At least one of imine resin, polyfluorene imine resin, polybenzimidazole resin, and polybenzoxazole resin, and the crosslinking component includes maleimide resin and the content is 0% by mass to 0.5 A compound having an epoxy group in mass%, and the mass reduction rate at 400 ° C when the bonding region is heated at 10 ° C / min from 25 ° C to 1% by mass or less, and to 25 ° C N-methylpyrrolidine The solubility of the ketone is 1 g / 100 g or less of the solvent. The temporary adhesive film according to item 1 of the scope of patent application, wherein the heterocyclic-containing resin is a pair selected from γ-butyrolactone, cyclopentanone, N-methylpyrrolidone, cyclohexanone, and diol. Polyimide resin having a solubility at 25 ° C. of at least one of ether, dimethylimide, and tetramethylurea at 10 ° C./100 g of a solvent. The temporary adhesive film according to item 1 or item 2 of the patent application scope, wherein the maleimide resin is a bismaleimide resin. The temporary adhesive film according to item 1 or item 2 of the patent application scope, wherein 50% to 100% by mass of the crosslinking component contained in the adhesive region is the maleimide resin. The temporary adhesive film according to any one of claims 1 to 2, wherein the adhesive region further contains a thermal polymerization initiator. The temporary adhesive film according to item 5 of the patent application scope, wherein the one-minute half-life temperature of the thermal polymerization initiator is 130 ° C to 300 ° C. The temporary adhesive film according to item 5 of the patent application scope, wherein the thermal polymerization initiator is an organic peroxide. The temporary adhesive film according to any one of claims 1 to 2, wherein the release region includes a compound containing at least one selected from a fluorine atom and a silicon atom. The temporary adhesive film according to any one of claims 1 to 2, wherein the demolding region contains a fluorine-based silane coupling agent. A laminated body having an element wafer on a surface on the side of a release region of a temporarily-adhesive film according to any one of claims 1 to 9 of the scope of patent application. A composition for temporary adhesion, comprising: a heterocyclic-containing resin including at least one selected from the group consisting of polyimide resin, polyimide resin, polybenzimidazole resin, and polybenzoxazole resin; A crosslinking component; and a solvent, and 50% to 100% by mass of the crosslinking component is a maleimide resin, and 0% to 0.5% by mass is a compound having an epoxy group. The composition for temporary bonding according to item 11 of the scope of the patent application, wherein the heterocyclic-containing resin is a compound selected from the group consisting of γ-butyrolactone, cyclopentanone, N-methylpyrrolidone, cyclohexanone, Polyimide resin having a solubility at 25 ° C. of at least one solvent of glycol ether, dimethylimide, and tetramethylurea of 10 g / 100 g or more of a solvent. The composition for temporary bonding according to item 11 or item 12 of the scope of patent application, wherein the maleimide resin is a bismaleimide resin. The composition for temporary bonding as described in item 11 or 12 of the scope of patent application, further contains a thermal polymerization initiator. The composition for temporary bonding according to item 14 of the scope of the patent application, wherein the one-minute half-life temperature of the thermal polymerization initiator is 130 ° C to 300 ° C. The composition for temporary bonding according to item 15 of the scope of application for patent, wherein the thermal polymerization initiator is an organic peroxide. The temporary bonding composition as described in claim 11 or 12, further contains a release component. The composition for temporary bonding according to item 17 of the scope of the patent application, wherein the mold release component includes a compound containing at least one selected from a fluorine atom and a silicon atom. The temporary bonding composition according to item 17 of the scope of application for a patent, wherein the mold release component is a fluorine-based silane coupling agent. A method for manufacturing an element, comprising the step of applying a composition for temporary bonding as described in any one of claims 11 to 19 of the scope of patent application. A kit for forming a temporary bonding film having a bonding region and a mold release region on a surface of the bonding region, and the bonding region is 10 ° C from 25 ° C. The mass reduction rate at 400 ° C at a temperature rise per minute is 1% by mass or less, and the solubility to 25 ° C N-methylpyrrolidone is 1g / 100g or less of a solvent, and the kit includes: The composition for temporary adhesion according to any one of items 11 to 19, and the composition for forming a mold release region containing a mold release component and a solvent.