WO2015182469A1 - Temporary bonding film, laminate, composition for temporary bonding, and method and kit for manufacturing device - Google Patents
Temporary bonding film, laminate, composition for temporary bonding, and method and kit for manufacturing device Download PDFInfo
- Publication number
- WO2015182469A1 WO2015182469A1 PCT/JP2015/064571 JP2015064571W WO2015182469A1 WO 2015182469 A1 WO2015182469 A1 WO 2015182469A1 JP 2015064571 W JP2015064571 W JP 2015064571W WO 2015182469 A1 WO2015182469 A1 WO 2015182469A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- group
- resin
- temporary
- region
- adhesive film
- Prior art date
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/10—Adhesives in the form of films or foils without carriers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/14—Peroxides
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/20—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for coatings strippable as coherent films, e.g. temporary coatings strippable as coherent films
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J179/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09J161/00 - C09J177/00
- C09J179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J179/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09J161/00 - C09J177/00
- C09J179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C09J179/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J179/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09J161/00 - C09J177/00
- C09J179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C09J179/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C09J179/085—Unsaturated polyimide precursors
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J201/00—Adhesives based on unspecified macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/40—Adhesives in the form of films or foils characterised by release liners
- C09J7/401—Adhesives in the form of films or foils characterised by release liners characterised by the release coating composition
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
- C09J2203/326—Applications of adhesives in processes or use of adhesives in the form of films or foils for bonding electronic components such as wafers, chips or semiconductors
Definitions
- the present invention relates to a temporary adhesive film, a laminate, a temporary adhesive composition, a device manufacturing method, and a kit. More specifically, the present invention relates to a temporary adhesive film, a laminate, a temporary adhesive composition, a device manufacturing method, and a kit that can be preferably used for manufacturing various devices such as semiconductor devices.
- a wire bonding method As an electrical connection method from an integrated circuit in an IC chip to an external terminal of the IC chip, a wire bonding method has been widely known.
- a device wafer In order to reduce the size of an IC chip, a device wafer is used.
- a method is known in which a through-hole is provided in the semiconductor device and a metal plug as an external terminal is connected to an integrated circuit so as to pass through the through-hole (so-called silicon through electrode (TSV) forming method).
- TSV silicon through electrode
- a technique for improving the degree of integration per unit area of a device wafer by multilayering an integrated circuit in an IC chip is known.
- the multilayered integrated circuit increases the thickness of the IC chip, it is necessary to reduce the thickness of the members constituting the IC chip.
- the thinning of the device wafer is being considered as a thinning of such a member, which not only leads to the miniaturization of the IC chip, but also saves the process of manufacturing the through hole of the device wafer in the production of the silicon through electrode. Because it is possible, it is considered promising.
- thinning of semiconductor devices such as power devices and image sensors has been attempted from the viewpoint of improving the degree of integration and improving the degree of freedom of the device structure.
- a device wafer having a thickness of about 700 to 900 ⁇ m is widely known, but in recent years, for the purpose of reducing the size of an IC chip or the like, the thickness of the device wafer can be reduced to 200 ⁇ m or less. Has been tried. However, since a device wafer having a thickness of 200 ⁇ m or less is very thin and a semiconductor device manufacturing member based on the device wafer is very thin, such a member may be further processed, or When the member is simply moved, it is difficult to support the member stably and without damage.
- the device wafer before thinning and the support substrate (carrier substrate) are temporarily fixed (temporary bonding) with a temporary adhesive, and the back surface of the device wafer is ground and thinned.
- a technique for removing the support substrate from the device wafer later is known.
- a temporary fixing film including a specific polyimide resin is interposed between a support member and a device wafer, and a device wafer is temporarily fixed to the support member, and temporarily fixed to the support member.
- a step of subjecting the device wafer to predetermined processing a step of bringing the organic solvent into contact with the temporary fixing film, dissolving a part or all of the temporary fixing film, and separating the processed device wafer from the support member; And a method of manufacturing a semiconductor device, including a step of dividing a processed device wafer into individual pieces.
- Patent Document 2 discloses an invention related to an adhesive for fixing a semiconductor element (adhesive for die bonding) that adheres between semiconductor elements or between a semiconductor element and a support substrate.
- an adhesive As such an adhesive, (A1) a polyimide resin having a glass transition temperature of 60 ° C. or less and a weight average molecular weight of 10,000 to 100,000, and (A2) N-methyl-2-pyrrolidone so that the resin content is 20% by mass.
- molding the adhesive composition containing a sex component in a sheet form is disclosed.
- the temporary adhesive film between the surface of the device wafer and the support substrate When temporarily bonding the surface of the device wafer to the support substrate, the temporary adhesive film between the surface of the device wafer and the support substrate must have a certain level of adhesive strength in order to stably support the device wafer. In addition, there is a demand for characteristics that can easily release the temporarily bonded state between the device wafer and the support substrate.
- a film that is soluble in an organic solvent is used as a temporary fixing film, and the temporary support for the device wafer is released by bringing the organic solvent into contact with the temporary fixing film.
- the temporary fixing film disclosed in Patent Document 1 has poor chemical resistance.
- Various chemicals may be used in the device manufacturing process. For example, when a device wafer is thinned by a wet process, an etching solution is used. For this reason, the temporary adhesive film that may be exposed to various chemicals in the device manufacturing process is required to have improved chemical resistance.
- Patent Document 2 is an invention related to an adhesive for fixing a semiconductor element used for bonding semiconductor elements to each other or a semiconductor element and a support substrate. It does not adhere. For this reason, the adhesive for fixing a semiconductor element disclosed in Patent Document 2 does not have a property capable of releasing the temporary adhesion between the device wafer and the support substrate.
- the present invention has been made in view of the above background, and its object is to stably attach a device wafer temporarily and perform temporary adhesion to the device wafer when the device wafer is subjected to mechanical or chemical treatment. It is an object of the present invention to provide a temporary adhesive film, a laminate, a temporary adhesive composition, a device manufacturing method, and a kit that can be easily released.
- the present inventors have found that the mass decrease rate at 400 ° C. when heated from 25 ° C. at 10 ° C./min is 1% by mass or less, and N-methyl at 25 ° C.
- a temporary adhesive film having an adhesion region having a solubility in pyrrolidone of 1 g / 100 g Solvent or less and a release region on the surface of the adhesion region can stably and temporarily bond a device wafer, and easily allows temporary adhesion to a device wafer. Based on these findings, the present invention has been completed.
- the present invention provides the following.
- the adhesive region contains a heterocyclic-containing resin containing at least one selected from a polyimide resin, a polyamideimide resin, a polybenzimidazole resin, and a polybenzoxazole resin, and a maleimide resin, according to ⁇ 1>.
- the solubility at 25 ° C. in a heterocyclic ring-containing resin in at least one solvent selected from ⁇ -butyrolactone, cyclopentanone, N-methylpyrrolidone, cyclohexanone, glycol ether, dimethyl sulfoxide and tetramethylurea is 10 g /
- ⁇ 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 adhesion region is a maleimide resin.
- ⁇ 6> The temporary adhesive film according to any one of ⁇ 1> to ⁇ 5>, wherein the adhesion region further contains a thermal polymerization initiator.
- ⁇ 7> The temporary adhesive film according to ⁇ 6>, wherein the thermal polymerization initiator has a one-minute half-life temperature of 130 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.
- the release region includes a compound containing at least one selected from a fluorine atom and a silicon atom.
- the release region contains a fluorine-based silane coupling agent.
- the heterocyclic ring-containing resin has a solubility at 25 ° C. of 10 g / in at least one solvent selected from ⁇ -butyrolactone, cyclopentanone, N-methylpyrrolidone, cyclohexanone, glycol ether, dimethyl sulfoxide and tetramethylurea.
- the composition for temporary adhesion according to ⁇ 12> which is a polyimide resin of 100 g Solvent or more.
- the thermal polymerization initiator is an organic peroxide.
- the ⁇ 19> mold release component is a composition for temporary adhesion as described in ⁇ 18> containing the compound containing at least 1 type chosen from a fluorine atom and a silicon atom.
- a device manufacturing method comprising a step of applying the temporary bonding composition according to any one of ⁇ 12> to ⁇ 20>.
- ⁇ 22> A kit for forming the temporary adhesive film according to any one of ⁇ 1> to ⁇ 10>, and the temporary adhesive composition according to any one of ⁇ 12> to ⁇ 20> A release region forming composition containing a mold component and a solvent.
- the device wafer when a mechanical or chemical treatment is performed on a device wafer, the device wafer can be stably temporarily bonded, temporary bonding to the device wafer can be easily released, and excellent in chemical resistance.
- a temporary adhesive film can be provided.
- FIG. 1A, FIG. 1B, and FIG. 1C are respectively a schematic cross-sectional view illustrating temporary bonding between a support substrate and a device wafer, a schematic view illustrating a device wafer temporarily bonded by a support substrate, and temporary bonding by a support substrate. It is a schematic sectional drawing which shows the state by which the made device wafer was thinned.
- substitution and non-substitution includes what does not have a substituent and what has a substituent.
- the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
- Actinic light” or “radiation” in the present specification means, for example, those including visible light, ultraviolet rays, far ultraviolet rays, electron beams, X-rays and the like. In this specification, “light” means actinic rays or radiation.
- exposure is not limited to exposure with far-ultraviolet rays such as mercury lamps, ultraviolet rays, and excimer lasers, X-rays, EUV light, etc., but also particle beams such as electron beams and ion beams. It also means drawing with.
- (meth) acrylate represents acrylate and methacrylate
- (meth) acryl represents acrylic and methacryl
- (meth) acryloyl” represents “acryloyl” and “methacryloyl”. Represents.
- a weight average molecular weight and a number average molecular weight are defined as a polystyrene conversion value by gel permeation chromatography (GPC) measurement.
- the weight average molecular weight (Mw) and the number average molecular weight (Mn) are, for example, HLC-8220 (manufactured by Tosoh Corporation), and TSKgel Super AWM-H (manufactured by Tosoh Corporation, 6) as a column.
- 0.0 mm ID ⁇ 15.0 cm can be determined by using a 10 mmol / L lithium bromide NMP (N-methylpyrrolidinone) solution as the eluent.
- monomer and “monomer” are synonymous.
- the monomer in the present invention is distinguished from an oligomer and a polymer and refers to a compound having a weight average molecular weight of 2,000 or less.
- the polymer compound in the present invention refers to a compound having a weight average molecular weight exceeding 2000.
- the members and the like described in the drawings already referred to are denoted by the same or corresponding reference numerals in the drawings, and the description is simplified or omitted.
- the temporary adhesive film of the present invention has an adhesive region and a release region on the surface of the adhesive region, and the adhesive region has a mass reduction rate at 400 ° C. when the temperature is increased from 25 ° C. at 10 ° C./min.
- the solubility in N-methylpyrrolidone at 25 ° C. is 1 g / 100 g Solvent or less.
- the temporary adhesive film of the present invention has a release region on the surface of the adhesive region, the device wafer is laminated on the surface of the release region in the temporary adhesive film, and the laminated surface of the device wafer in the temporary adhesive film
- a support substrate on the opposite surface, the device wafer having a structure such as a bump is appropriately protected, and a temporary adhesive film is applied from the device wafer after mechanical or chemical treatment is applied to the device wafer. It can be easily peeled off by mechanical peeling.
- the adhesion region is excellent in heat resistance, and even when subjected to a process at high temperature, The wafer can be temporarily bonded stably. Further, since the temporary adhesive film is not easily deteriorated by heat, the temporary adhesive film can be easily peeled from the device wafer by a method such as mechanical peeling even after a high temperature process.
- the device wafer and the support substrate in the present invention can be peeled off by mechanical peeling, so that the solubility in N-methylpyrrolidone at 25 ° C. in the adhesion region can be 1 g / 100 g Solvent or less, and the chemical resistance is excellent. .
- the device wafer can be stably temporarily bonded.
- the temporary adhesive film of the present invention can be stably temporarily bonded to a device wafer even when various processes such as high temperature processing and chemical processing are performed, and from the device after processing. It can be easily peeled off.
- the mass reduction rate is a value measured by the calorimeter measuring device (TGA) under the above temperature rising condition under a nitrogen stream.
- TGA calorimeter measuring device
- the solubility is added to a solvent in 100 g of a sample while stirring the sample, and the solubility is confirmed. If the sample is completely dissolved, the sample is further added to the solution with stirring. The amount immediately before the sample was not dissolved when finally stirred at 25 ° C. for 1 hour was defined as the solubility.
- the temporary adhesive film of the present invention has an adhesive region and a release region on the surface of the adhesive region.
- the mass reduction rate at 400 ° C. when the temperature is increased from 25 ° C. to 10 ° C./min in the adhesion region is 1% by mass or less, preferably 0.90% by mass or less. 8 mass% or less is more preferable, 0.7 mass% or less is more preferable, 0.6 mass% or less is especially preferable, and 0.5 mass% or less is the most preferable. Within this range, the device wafer can be stably and temporarily bonded even when a high temperature process up to 400 ° C. is performed.
- the temporary adhesive film since the temporary adhesive film is unlikely to be thermally deteriorated, the temporary adhesive film can be easily peeled from the device wafer by a method such as mechanical peeling even after a high temperature process.
- the solubility of the adhesive region in N-methylpyrrolidone at 25 ° C. is 1 g / 100 g Solvent or less, preferably 0.8 g / 100 g Solvent or less, more preferably 0.5 g / 100 g Solvent or less, 0 .1 g / 100 g Solvent or less is more preferable.
- the device wafer can be stably temporarily bonded even when the chemical used during the device manufacturing process comes into contact with the temporary adhesive film.
- the adhesive region and the release region may exist as independent adhesive layers and release layers, respectively, or the boundary between the adhesive region and the release region may not be clear.
- the boundary between the adhesive region and the release region is not clear, an aspect in which the release component is unevenly distributed in the surface layer in the temporary adhesive layer to form the release region.
- the adhesive region may be composed of two or more types of adhesive layers, and the release region may be composed of two or more release layers.
- the temporary adhesive film of the present invention has an adhesive region.
- the adhesion region is for bonding the device wafer and the support substrate.
- the bonding area has a mass reduction rate at 400 ° C. of 1% by mass or less when the temperature is raised from 25 ° C. at 10 ° C./min, and the solubility in N-methylpyrrolidone at 25 ° C. is 1 g / 100 g Solvent or less. Is used.
- the average thickness of the adhesion region is preferably 0.1 to 500 ⁇ m, preferably 0.5 to 500 ⁇ m, more preferably 0.5 to 50 ⁇ m, and particularly preferably 0.5 to 10 ⁇ m.
- the average thickness of the adhesion region is preferably thicker than the height of the structure of the device wafer described later.
- the average thickness of the layer forming the bonding region is 1 to 50 ⁇ m. 2 to 20 ⁇ m is more preferable.
- the average thickness of the adhesive region is preferably 1 to 50 ⁇ m, and preferably 2 to 20 ⁇ m.
- the average thickness of the adhesion region is defined as the average value of five points measured by ellipsometry.
- Any adhesive region can be used as long as it can achieve the above-described mass reduction rate and solubility, but it preferably contains a resin component A and a maleimide resin described later.
- the adhesion region includes a resin component A and a maleimide resin, which will be described later, the resin component A can be interposed between the three-dimensionally cross-linked maleimide resins, and an adhesion region excellent in heat resistance and chemical resistance can be easily obtained.
- any resin component A that can be contained in the adhesive region can be used as long as it satisfies the mass reduction rate and solubility.
- the resin component A does not include a maleimide resin.
- the resin component A examples include a heterocyclic ring-containing resin (preferably, a polyimide resin, a polyamideimide resin, a polybenzimidazole resin, a polybenzoxazole resin), a terpene resin, a terpene phenol resin, a modified terpene resin, a hydrogenated terpene resin, Hydrogenated terpene phenol resin, rosin, rosin ester, hydrogenated rosin, hydrogenated rosin ester, polymerized rosin, polymerized rosin ester, modified rosin, rosin modified phenolic resin, alkylphenol resin, aliphatic petroleum resin, aromatic petroleum resin, hydrogenated Petroleum resin, modified petroleum resin, alicyclic petroleum resin, coumarone petroleum resin, indene petroleum resin, olefin copolymer (for example, methylpentene copolymer), cycloolefin copolymer (for example, norbornene copolymer, dicyclopenta
- polyimide resin polyimide resin, polyamideimide resin, polybenzimidazole resin, polybenzoxazole resin, polycarbonate resin, polyethersulfone resin, and polyester resin are preferable, and polyimide resin, polyamideimide resin, polybenzimidazole resin, and polybenzoxazole resin are more preferable.
- a polyimide resin or a polyamideimide resin is more preferable, and a polyimide resin is particularly preferable. Since these resins are excellent in heat resistance, it is easy to achieve the mass reduction rate.
- the polyimide resin has a solubility at 25 ° C.
- the adhesion region can be formed by a coating method.
- polyimide resin a resin obtained by subjecting tetracarboxylic dianhydride and diamine to a condensation reaction by a known method can be used.
- Known methods include, for example, a method of dehydrating and ring-closing the polyamic acid obtained by mixing approximately equimolar amounts of tetracarboxylic dianhydride and diamine in an organic solvent and reacting at a reaction temperature of 80 ° C. or lower. It is done.
- substantially equimolar means that the molar ratio of tetracarboxylic dianhydride and diamine is close to 1: 1.
- the composition ratio of tetracarboxylic dianhydride and diamine is 0.5 to 2.0 mol of diamine with respect to 1.0 mol of tetracarboxylic dianhydride in total. You may adjust as follows. By adjusting the composition ratio of tetracarboxylic dianhydride and diamine within the above range, the weight average molecular weight of the polyimide resin can be adjusted.
- the tetracarboxylic dianhydride is not particularly limited, and examples thereof include pyromellitic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,2 ′, 3,3′-biphenyltetracarboxylic 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) sulfone dianhydride, 3,4,9,10-perylenetetracar
- More than one species can be used in combination.
- 3,4,3 ′, 4′-benzophenone tetracarboxylic dianhydride, 2,3,2 ′, 3′-benzophenone tetracarboxylic dianhydride, 2,3,3 ′, 4′- Benzophenone tetracarboxylic dianhydride is preferred, and 3,4,3 ′, 4′-benzophenone tetracarboxylic dianhydride is more preferred.
- the diamine is not particularly limited and includes, for example, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 3,3′-diaminodiphenyl ether, 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'-diaminodiphenylsulfone, 3,4
- One or more selected from the group is preferred, and 3- (4-aminophenyl) -1,1,3-trimethyl-5-aminoindane is more preferred.
- Examples of the solvent used for the reaction of the tetracarboxylic dianhydride and diamine include N, N-dimethylacetamide, N-methyl-2-pyrrolidone and N, N-dimethylformamide.
- a nonpolar solvent for example, toluene or xylene
- the reaction temperature of the tetracarboxylic dianhydride and the diamine is preferably less than 100 ° C, more preferably less than 90 ° C.
- imidation of polyamic acid is typically performed by heat treatment under an inert atmosphere (typically a vacuum or nitrogen atmosphere).
- the heat treatment temperature is preferably 150 ° C. or higher, more preferably 180 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.
- the polyimide resin has a solubility at 25 ° C. of 10 g / 100 g Solvent in at least one solvent selected from ⁇ -butyrolactone, cyclopentanone, N-methylpyrrolidone, cyclohexanone, glycol ether, dimethyl sulfoxide and tetramethylurea.
- solvent selected from ⁇ -butyrolactone, cyclopentanone, N-methylpyrrolidone, cyclohexanone, glycol ether, dimethyl sulfoxide and tetramethylurea.
- the above polyimide resins are preferred.
- Polyimide resins having such solubility include, for example, 3,4,3 ′, 4′-benzophenonetetracarboxylic dianhydride and 3- (4-aminophenyl) -1,1,3-trimethyl-5- Examples thereof include a polyimide resin obtained by reacting with aminoindane. This polyimide resin is particularly excellent in heat resistance.
- a commercially available product may be used as the polyimide resin.
- Durimide registered trademark
- FUJIFILM Corporation manufactured by FUJIFILM Corporation
- GPT-LT manufactured by Gunei Chemical Co., Ltd.
- SOXR-S SOXR-M
- SOXR-U SOXR-C
- SOXR-C all of which are Nippon Advanced Paper Industries Co., Ltd.
- polyamideimide resin for example, a resin obtained by reacting an acid component such as polycarboxylic acid or a derivative thereof with diamine or diisocyanate in a polar solvent can be used.
- the polar solvent include N-methyl-2-pyrrolidone (NMP) and N, N′-dimethylacetamide. The above reaction can be performed by stirring while heating to a predetermined temperature (usually about 60 to 200 ° C.).
- Acid components used in the production of polyamideimide resin include trimellitic acid, trimellitic anhydride, trimellitic acid chloride; pyromellitic acid (benzene-1,2,4,5-tetracarboxylic acid), biphenyltetra Tetracarboxylic acids such as carboxylic acid, biphenylsulfone tetracarboxylic acid, benzophenone tetracarboxylic acid, biphenyl ether tetracarboxylic acid, ethylene glycol bis trimellitate, propylene glycol bis trimellitate and their acid anhydrides or acid chlorides; oxalic acid, Aliphatic dicarboxylic acids such as adipic acid, malonic acid, sebacic acid, azelaic acid, dodecanedicarboxylic acid, dicarboxypolybutadiene, dicarboxypoly (acrylonitrile-butadiene), dicarboxypoly (styrene-butadiene) Alicycl
- Aliphatic diamines such as ethylenediamine, propylenediamine, hexamethylenediamine and their diisocyanates; alicyclic diamines such as 1,4-cyclohexanediamine, 1,3-cyclohexanediamine, isophoronediamine, 4,4′-dicyclohexylmethanediamine, and These diisocyanates: m-phenylenediamine, p-phenylenediamine, 4,4'-diaminodiphenylmethane, 4'-diaminodiphenyl ether, 4,4'-diaminodiphenylsulfone, benzidine, o-tolidine, 2,4-tolylenediamine , Aromatic diamines such as 2,6-tolylenediamine and xylylenediamine and diisocyanates thereof.
- the number average molecular weight (Mn) of the polyamideimide resin is preferably 5,000 to 100,000. More preferably, it is 10,000 to 50,000. If the number average molecular weight (Mn) of the polyamideimide resin is 5,000 or more, the durability is good. When the number average molecular weight (Mn) of the polyamide-imide resin is 100,000 or less, the solution viscosity is low and the adhesive region is easily formed by coating.
- a commercially available product may be used as the polyamideimide resin.
- Durimide registered trademark
- Viromax registered trademark
- 13NX manufactured by Toyobo Co., Ltd.
- Rika Coat manufactured by Nippon Nippon Chemical Co., Ltd.
- polybenzimidazole resin for example, a resin obtained by reacting an aromatic tetraamine and a dicarboxylic acid component can be used.
- Aromatic tetraamines include, for example, 1,2,4,5-tetraaminobenzene, 1,2,5,6-tetraamononaphthalate, 2,3,6,7-tetraaminonaphthalate, 3,3 ′, 4,4′-tetraaminodiphenylmethane, 3,3 ′, 4,4′-tetraaminodiphenylethane, 3,3 ′, 4,4′-tetraaminodiphenyl-2,2-propane, 3,3′4 Examples include 4'-tetraaminodiphenyl thioether and 3,3 ', 4,4'-tetraaminodiphenyl sulfone.
- a preferred aromatic tetraamine is 3,3 ′, 4,4′-tetraaminobiphenyl.
- the dicarboxylic acid component include isophthalic acid, terephthalic acid, 4,4′-biphenyldicarboxylic acid, 1,4-naphthalenedicarboxylic acid, diphenic acid (2,2′-biphenyldicarboxylic acid), phenylindanedicarboxylic acid, 1, Examples thereof include 6-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 4,4′-diphenylthioether dicarboxylic acid, 4,4′-diphenylsulfone dicarboxylic acid, and 4,4′-diphenylthioether dicarboxylic acid.
- the dicarboxylic acid component is preferably introduced at a ratio of about 1 mole of dicarboxylic acid component per mole of aromatic tetraamine. Note that the optimum ratio of the reactants in the polymerization system can be easily determined by those skilled in the art.
- polybenzimidazole resins include poly-2,2 ′-(m-phenylene) -5,5′-bibenzimidazole, poly-2,2 ′-(biphenylene-2 "2" ')-5, 5'-bibenzimidazole, poly-2,2 '-(biphenylene-4 "4"')-5,5'-bibenzimidazole, poly-2,2 '-(1 ", 1", 3 "trimethyl Indanylene-3 "5" -p-phenylene-5,5'-bibenzidiimidazole, 2,2 '-(m-phenylene) -5,5'-bibenzidiimidazole / 2,2- (1 ", 1 ", 3" -trimethylindanilene) 5 ", 3"-(p-phenylene) -5,5'-bibenzimidazole copolymer, 2,2 '-(m-phenylene) -5,5'-bi Benzimidazole / 2,2'-
- a commercially available product may be used as the polybenzimidazole resin.
- MRS0810H manufactured by PBI
- PBI PBI
- Polybenzoxazole resin a resin obtained by dissolving polyhydroxyamide synthesized from a bisaminophenol compound and a dicarboxylic acid derivative in a solvent and undergoing a dehydration ring closure reaction is used.
- bisaminophenol compounds examples include 2,4-diaminoresorcinol, 4,6-diaminoresorcinol, 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, and 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'-dihydroxydiphenylsulfone, 4,4'-diamino-3,3'-dihydroxydiphenylsulfone, 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- (4-
- Dicarboxylic acid derivatives include isophthalic acid, terephthalic acid, 4,4′-biphenyldicarboxylic acid, 3,4′-biphenyldicarboxylic acid, 3,3′-biphenyldicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 1,4 -Naphthalenedicarboxylic acid, 4,4'-sulfonylbisbenzoic acid, 3,4'-sulfonylbisbenzoic acid, 3,3'-sulfonylbisbenzoic acid, 4,4'-oxybisbenzoic acid, 3,4'-oxybisbenzoic acid, 3,4'-oxybis Benzoic acid, 3,3′-oxybisbenzoic acid, 2,2-bis (4-carboxyphenyl) propane, 2,2-bis (3-carboxyphenyl) propane, 2,2-bis (4-carboxyphenyl) hexa Fluoropropane, 2,2-bis (3-carboxyphenyl
- a commercially available product may be used as the polybenzoxazole resin.
- examples thereof include CRC-8800 (manufactured by Sumitomo Bakelite Co., Ltd.).
- the adhesion region preferably contains 1 to 99% by mass, more preferably 10 to 90% by mass, and 25 to 75% by mass of the resin component A with respect to the total solid content of the adhesion region (excluding the solvent). Is particularly preferred.
- the temporary adhesive film preferably contains 1 to 99% by mass of resin component A with respect to the total solid content (excluding the solvent) of the temporary adhesive film, more preferably 10 to 90% by mass, and 25 Particularly preferred is ⁇ 75% by weight. Only one type of resin component A may be used, or two or more types may be used. When there are two or more types of resin components A, the total is preferably in the above range.
- the adhesion region preferably contains a maleimide resin as a crosslinking component.
- Any maleimide resin can be used as long as the cured product satisfies the mass reduction rate and solubility.
- a compound having a maleimide group and a crosslinked product obtained by crosslinking such a compound are collectively referred to as maleimide resin.
- the cross-linked product is preferably a three-dimensional cross-linked product using a compound having a maleimide group.
- the compound having a maleimide group may be a monomer or a polymer.
- bismaleimide resin is preferable as the maleimide resin.
- the bismaleimide resin is more preferably at least one selected from, for example, a bismaleimide resin represented by the following general formula (III) and a novolac maleimide resin represented by the following general formula (IV).
- R represents an aromatic ring or a divalent organic group containing a linear, branched or cyclic aliphatic hydrocarbon group.
- R is preferably a divalent group composed of a benzene group, a toluene group, a xylene group, a naphthalene group, a linear, branched or cyclic saturated hydrocarbon group, or a combination thereof.
- R is preferably a divalent group represented by the following formula (v), (vi) or (vii).
- s represents an integer of 0 to 20.
- maleimide resin those described in paragraph Nos. 0020 to 0023 of JP-A No. 2003-321608 may be used.
- Commercially available maleimide resins include BMI-1000, 2000, 3000, 4000, 5000, 5100, 7000 (manufactured by Daiwa Kasei Kogyo, bismaleimide resin), BANI-X (manufactured by Shin-Nakamura Chemical, bismaleimide resin), BANI- M (manufactured by Shin-Nakamura Chemical Co., Ltd., bismaleimide resin).
- the adhesion region preferably contains maleimide resin in an amount of 1 to 99% by mass, more preferably 10 to 90% by mass, and more preferably 25 to 75% by mass with respect to the total solid content of the adhesion region (excluding the solvent). Particularly preferred. If content of maleimide resin is the said range, the heat resistance of an adhesion
- the temporary adhesive film preferably contains maleimide resin in an amount of 1 to 99% by weight, more preferably 10 to 90% by weight, more preferably 25 to 25% by weight based on the total solid content (excluding the solvent) of the temporary adhesive film. 75% by mass is particularly preferred.
- the maleimide resin is preferably contained in an amount of 10 to 100% by mass, more preferably 20 to 100% by mass, further preferably 50 to 100% by mass, based on the total mass of the crosslinking component contained in the adhesion region, and 80 to 100% by mass. Is particularly preferred.
- the crosslinking component is substantially composed only of maleimide resin.
- the fact that it is substantially composed only of a maleimide resin means that the content of the crosslinking component other than the maleimide resin in the total amount of the crosslinking component is preferably, for example, 1% by mass or less, more preferably 0.5% by mass or less, 0.1 mass% or less is especially preferable. According to this aspect, the heat resistance of the adhesion region can be further improved.
- region of this invention may contain crosslinking components (other crosslinking components) other than maleimide resin.
- the other crosslinking component a compound having two or more polymerizable groups, which can be polymerized by the action of actinic rays, radiation, light, heat, radicals or acids, can be used.
- the polymerizable group include a group having an ethylenically unsaturated bond, an epoxy group, and the like.
- the ethylenically unsaturated bond group a vinyl group, an acrylic group, a methacryl group, and an allyl group are preferable.
- Examples of the compound having a group having an ethylenically unsaturated bond include a (meth) acrylamide compound having 3 to 35 carbon atoms, a (meth) acrylate compound having 4 to 35 carbon atoms, and an aromatic vinyl compound having 6 to 35 carbon atoms. And vinyl ether compounds having 3 to 20 carbon atoms.
- Examples of the compound having an epoxy group include bisphenol A type (or AD type, S type, F type) glycidyl ether, water-added bisphenol A type glycidyl ether, ethylene oxide adduct bisphenol A type glycidyl ether, and propylene oxide addition.
- a compound having an epoxy group may be contained as a cross-linking component.
- the content of the compound having an epoxy group in 100 parts by mass of the cross-linking component is 10% by mass. % Or less, more preferably 5% by mass or less, and in particular, it may not be substantially contained.
- substantially not containing, for example, the content of the compound having an epoxy group is preferably 1% by mass or less, more preferably 0.5% by mass or less, particularly preferably 0.1% by mass or less, and not contained. It is particularly preferred.
- the adhesive region of the present invention preferably further contains a thermal polymerization generator.
- a well-known thing can be used as a thermal-polymerization initiator.
- a 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.
- the heat resistance of the adhesion region can be further improved.
- the 1-minute half-life temperature of the thermal polymerization initiator is a temperature at which the thermal polymerization initiator decomposes and its residual amount (mass) becomes 1 ⁇ 2 in 1 minute.
- the one-minute half-life temperature of the thermal polymerization initiator is, for example, prepared by adding 0.1 mol / l of the thermal polymerization initiator in benzene, and heating it at several temperatures Ti (absolute temperature). The period t 1/2, T1 is measured, lnt 1/2, T1 is plotted against 1 / Ti, 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 heat energy and initiates or accelerates the reaction of a crosslinking component such as maleimide resin.
- Thermal radical generators include aromatic ketones, onium salt compounds, organic peroxides, thio compounds, hexaarylbiimidazole compounds, ketoxime ester compounds, borate compounds, azinium compounds, metallocene compounds, active ester compounds, carbon halogens. Examples thereof include a compound having a bond and an azo compound. Among these, an organic peroxide or an azo compound is more preferable, and an organic peroxide is particularly preferable. Specific examples of the thermal radical generator include compounds described in paragraphs 0074 to 0118 of JP-A-2008-63554.
- the adhesion region preferably contains the thermal polymerization initiator in an amount of 0.5 to 20% by mass, more preferably 1 to 10% by mass, based on the total solid content of the adhesion region (excluding the solvent). 8% by mass is particularly preferred. If content of a thermal-polymerization initiator is the said range, the heat resistance of an adhesion
- the adhesive region in the temporary adhesive film of the present invention may contain a surfactant.
- a surfactant various surfactants such as a fluorosurfactant, nonionic surfactant, cationic surfactant, anionic surfactant, and silicone surfactant can be used. Is preferred.
- the adhesion region is formed by a coating method, the liquid properties (particularly fluidity) when prepared as a coating liquid are improved, and the uniformity of coating thickness and the liquid-saving property can be further improved.
- the fluorine-containing surfactant preferably has a fluorine content of 3 to 40% by mass, more preferably 5 to 30% by mass, and still more preferably 7 to 25% by mass.
- a fluorine-based surfactant having a fluorine content within this range is effective in terms of uniformity of coating film thickness and liquid-saving properties.
- fluorosurfactant examples include Megafac F171, F172, F173, F176, F176, F177, F141, F142, F143, F144, R30, F437, F475, F479, F482, F554, F780, F780, F781 (above DIC Corporation), Florard FC430, FC431, FC171 (above, Sumitomo 3M Limited), Surflon S-382, SC-101, Same SC-103, Same SC-104, Same SC-105, Same SC1068, Same SC-381, Same SC-383, Same S393, Same KH-40 (manufactured by Asahi Glass Co., Ltd.), PF636, PF656, PF6320 PF6520, PF7002 (manufactured by OMNOVA), and the like.
- Nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane and their ethoxylates and propoxylates (eg, glycerol propoxylate, glycerol ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, Polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester (Pluronic L10, L31, L61, L62, 10R5, 17R2 manufactured by BASF) 25R2, Tetronic 304, 701, 704, 901, 904, 150R1, Sol Spa Scan 20000 (manufactured by Nippon Lubrizol Corporation), and the like.
- cationic surfactants examples include phthalocyanine derivatives (trade name: EFKA-745, manufactured by Morishita Sangyo Co., Ltd.), organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth) acrylic acid (co) heavy. Combined polyflow no. 75, no. 90, no. 95 (manufactured by Kyoeisha Chemical Co., Ltd.) and W001 (manufactured by Yusho Co., Ltd.).
- anionic surfactants examples include W004, W005, W017 (manufactured by Yusho Co., Ltd.), and the like.
- silicone surfactant examples include “Toray Silicone DC3PA”, “Toray Silicone SH7PA”, “Tore Silicone DC11PA”, “Tore Silicone SH21PA”, “Tore Silicone SH28PA”, “Toray Silicone” manufactured by Toray Dow Corning Co., Ltd.
- the adhesion region has a surfactant
- the content of the surfactant is preferably 0.001 to 1% by mass, more preferably 0.01 to 0.5% by mass, based on the total solid content of the adhesion region. 0.05 to 0.1% by mass is particularly preferable.
- the temporary adhesive film preferably contains the surfactant in an amount of 0.001 to 1% by mass, based on the total solid content of the temporary adhesive film (excluding the solvent), and 0.01 to 0.5% by mass. % Is more preferable, and 0.05 to 0.1% by mass is particularly preferable. Only one type of surfactant may be used, or two or more types may be used. When two or more surfactants are used, the total is preferably in the above range.
- the adhesion region in the temporary adhesion film of the present invention may contain an antioxidant from the viewpoint of preventing the adhesion region from being lowered in molecular weight or gelled by oxidation during heating.
- an antioxidant a phenol-based antioxidant, a sulfur-based antioxidant, a quinone-based antioxidant, a nitrogen-based antioxidant, and the like can be used.
- phenolic antioxidant examples include p-methoxyphenol, 2,6-di-tert-butyl-4-methylphenol, “Irganox 1010”, “Irganox 1330”, “Irganox 3114”, “Irganox 1035” manufactured by BASF Corporation, Examples thereof include “Sumilizer MDP-S” and “Sumilizer GA-80” manufactured by Sumitomo Chemical Co., Ltd.
- sulfur-based antioxidant include 3,3′-thiodipropionate distearyl, “Sumilizer TPM”, “Sumilizer TPS”, “Sumilizer TP-D” manufactured by Sumitomo Chemical Co., Ltd., and the like.
- Examples of the quinone antioxidant include p-benzoquinone and 2-tert-butyl-1,4-benzoquinone.
- Examples of amine-based antioxidants include dimethylaniline and phenothiazine.
- Irganox 1010, Irganox 1330, and 3,3′-thiodipropionate distearyl are preferable, Irganox 1010 and Irganox 1330 are more preferable, and Irganox 1010 is particularly preferable.
- the molecular weight of the antioxidant is preferably 400 or more, more preferably 600 or more, and particularly preferably 750 or more, from the viewpoint of preventing sublimation during heating.
- the content of the antioxidant is preferably 0.001 to 10% by mass, more preferably 0.01 to 5% by mass, based on the total solid content of the adhesion region. 1 to 1% by mass is particularly preferable.
- the temporary adhesive film preferably contains the antioxidant in an amount of 0.001 to 10% by mass, and 0.01 to 5% by mass relative to the total solid content (excluding the solvent) of the temporary adhesive film. More preferred is 0.1 to 1% by mass.
- One type of antioxidant may be sufficient and two or more types may be sufficient. When there are two or more kinds of antioxidants, the total is preferably within the above range.
- the temporary adhesive film of the present invention has a release region on the surface of the adhesive region.
- the release region is used for the purpose of adjusting the adhesive force between the device wafer and the bonding region, and facilitating peeling of the temporary adhesive film from the device wafer.
- the average thickness of the release region is preferably 0.001 to 1 ⁇ m, and more preferably 0.01 to 0.5 ⁇ m. If it is the said range, while a temporary adhesive film has moderate adhesive force and adhesiveness with a device wafer is favorable, a temporary adhesive film can be easily peeled from a device wafer.
- the average thickness of the layer forming the release region is 0.001. ⁇ 1 ⁇ m is preferable, and 0.01 to 0.5 ⁇ m is more preferable.
- the average thickness of the release region is preferably 0.001 to 1 ⁇ m, More preferably, it is 0.01 to 0.5 ⁇ m.
- the average thickness of the release region is defined as the average value of points measured by ellipsometry at five points.
- the release region in the temporary adhesive film of the present invention preferably contains a compound containing at least one selected from fluorine atoms and silicon atoms, and more preferably contains a fluorine-based silane coupling agent.
- the fluorine content in the release region is preferably 30 to 80% by mass, more preferably 40 to 76% by mass, and particularly preferably 60 to 75% by mass.
- the fluorine content is defined by “ ⁇ (number of fluorine atoms in one molecule ⁇ mass of fluorine atoms) / mass of all atoms in one molecule ⁇ ⁇ 100”.
- the release region preferably contains 10 to 100% by mass, preferably 50 to 100% by mass, of a compound containing at least one selected from fluorine atoms and silicon atoms, based on the total solid content of the release region. Is more preferable.
- the temporary adhesive film is preferably 10 to 100% by mass, more preferably 50 to 100% by mass, based on the total solid content of the temporary adhesive film, of a compound containing at least one selected from fluorine atoms and silicon atoms. .
- region contains the three-dimensional crosslinked material containing a fluorine atom from a heat resistant viewpoint.
- a three-dimensional crosslinked product of a fluorine-containing polyfunctional monomer / oligomer or a three-dimensional crosslinked product of a fluorine-containing silane coupling agent is preferable, and a three-dimensional crosslinked product of a fluorine-containing silane coupling agent is particularly preferable.
- a fluorine-containing silane coupling agent a non-halogen silane coupling agent having a low risk to human body and low metal corrosivity is preferable, and fluorine-containing alkoxysilane is particularly preferable.
- Commercially available products include OPTOOL DAC-HP and OPTOOL DSX manufactured by Daikin Industries, Ltd.
- the halogen-based silane coupling agent include a fluorinated chlorosilane compound.
- the release region can contain a polymer compound having a non-three-dimensional crosslinked structure having a fluorine atom.
- the non-three-dimensional crosslinked structure means that the compound does not contain a crosslinked structure or the ratio of the crosslinked structure forming the three-dimensional crosslinked structure to the total crosslinked structure in the compound is 5% or less. % Or less is preferable. It is preferable that it is contained substantially.
- the polymer compound having a non-three-dimensional crosslinked structure having a fluorine atom a polymer composed of one or more fluorine-containing monofunctional monomers can be preferably used.
- tetrafluoroethylene hexafluoropropene, tetrafluoroethylene oxide, hexafluoropropene oxide, perfluoroalkyl vinyl ether, chlorotrifluoroethylene, vinylidene fluoride, and perfluoroalkyl group-containing (meth) acrylic acid ester.
- Homopolymers of one or more fluorine-containing monofunctional monomers or copolymers of these monomers copolymers of one or more fluorine-containing monofunctional monomers with ethylene, fluorine-containing monofunctional monomers And at least one fluorine-containing resin selected from a copolymer of one or more of these and chlorotrifluoroethylene.
- the polymer compound having a fluorine atom having a non-three-dimensional crosslinked structure is preferably a perfluoroalkyl group-containing (meth) acrylic resin that can be synthesized from a perfluoroalkyl group-containing (meth) acrylic ester.
- the perfluoroalkyl group-containing (meth) acrylic acid ester is preferably a compound represented by the following formula (101).
- R 101 , R 102 , and R 103 each independently represent a hydrogen atom, an alkyl group, or a halogen atom.
- Y 101 represents a single bond or a divalent linking group selected from the group consisting of —CO—, —O—, —NH—, a divalent aliphatic group, a divalent aromatic group, and combinations thereof.
- 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 , R 103 are preferably alkyl groups having 1 to 8 carbon atoms, such as a methyl group, an ethyl group, a propyl group, Examples include octyl group, isopropyl group, tert-butyl group, isopentyl group, 2-ethylhexyl group, 2-methylhexyl group, cyclopentyl group and the like.
- Examples of the aryl group are preferably aryl groups having 6 to 12 carbon atoms, and examples thereof include a phenyl group, a 1-naphthyl group, and a 2-naphthyl group.
- R 101 to R 103 are preferably a hydrogen atom or a methyl group.
- Y 101 represents a single bond or a divalent linking group selected from the group consisting of —CO—, —O—, —NH—, a divalent aliphatic group, a divalent aromatic group, and combinations thereof.
- the divalent aliphatic group is preferably a chain structure rather than a cyclic structure, and more preferably a straight chain structure than a branched chain structure.
- the number of carbon atoms in the divalent aliphatic group is preferably 1-20, more preferably 1-15, still more preferably 1-12, and even more preferably 1-10. It is preferably 1 to 8, more preferably 1 to 4, and particularly preferably 1 to 4.
- Examples of the divalent aromatic group include a phenylene group, a substituted phenylene group, a naphthalene group, and a substituted naphthalene group, and a phenylene group is preferable.
- Y 101 is preferably an aliphatic group having a divalent linear structure.
- the monovalent organic group having a fluorine atom represented by Rf is not particularly limited, but is preferably a fluorinated alkyl group having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and more preferably 1 to Fifteen fluorine-containing alkyl groups are particularly preferred.
- This fluorine-containing alkyl group is a straight chain ⁇ for example, —CF 2 CF 3 , —CH 2 (CF 2 ) 4 H, —CH 2 (CF 2 ) 8 CF 3 , —CH 2 CH 2 (CF 2 ) 4 H, etc.
- a branched structure ⁇ eg, —CH (CF 3 ) 2 , —CH 2 CF (CF 3 ) 2 , —CH (CH 3 ) CF 2 CF 3 , —CH (CH 3 ) (CF 2 ) 5 CF 2 H and the like ⁇ and an alicyclic structure (preferably a 5- or 6-membered ring such as a perfluorocyclohexyl group, a perfluorocyclopentyl group, or an alkyl group substituted with these).
- An ether bond (for example, —CH 2 OCH 2 CF 2 CF 3 , —CH 2 CH 2 OCH 2 C 4 F 8 H, —CH 2 CH 2 OCH 2 CH 2 C 8 F 17 , —CH 2 CF 2 OCF 2 CF 2 OCF 2 CF 2 H, etc.). Further, it may be a perfluoroalkyl group.
- the perfluoroalkyl group-containing (meth) acrylic resin has a repeating unit represented by the following formula (102).
- R 101 , R 102 , R 103 , Y 101 , and Rf are each synonymous with General Formula (101), and preferred embodiments are also synonymous.
- a copolymer component can be selected in addition to the perfluoroalkyl group-containing (meth) acrylic acid ester from the viewpoint of peelability.
- the radical polymerizable compound capable of forming a copolymer component include acrylic acid esters, methacrylic acid esters, N, N-2 substituted acrylamides, N, N-2 substituted methacrylamides, styrenes, and acrylonitriles. And radical polymerizable compounds selected from methacrylonitriles and the like.
- acrylate esters such as alkyl acrylate (alkyl group preferably has 1 to 20 carbon atoms), such as methyl acrylate, ethyl acrylate, propyl acrylate, acrylic acid Butyl, amyl acrylate, ethyl hexyl acrylate, octyl acrylate, tert-octyl acrylate, chloroethyl acrylate, 2,2-dimethylhydroxypropyl acrylate, 5-hydroxypentyl acrylate, trimethylolpropane monoacrylate, pentaerythritol Monoacrylate, glycidyl acrylate, benzyl acrylate, methoxybenzyl acrylate, furfuryl acrylate, tetrahydrofurfuryl acrylate, etc.), aryl acrylate (eg phenyl Methacrylic acid esters (eg, methyl methacrylate, ethyl)
- (meth) acrylic acid esters having a hydrocarbon group having 1 to 24 carbon atoms are particularly preferred, for example, methyl (meth) acrylate, butyl , 2-ethylhexyl, lauryl, steer Le, include such glycidyl ester, 2-ethylhexyl, lauryl, higher alcohol (meth) acrylate stearyl, especially acrylate.
- a commercially available product may be used.
- Teflon registered trademark
- DuPont Teflon
- Tefzel DuPont
- Fullon Asahi Glass
- Halar SolvaySolexis
- Heiler SolvaySolexis
- Lumiflon Alignment
- Afras Alignment
- Cytop Alignment
- Cefral Soft Central Glass Co., Ltd.
- Cefral Coat Central Glass Co., Ltd.
- Dionine Dionine
- fluoro oils including perfluoropolyether oils such as fluoro rubber, Krytox (DuPont), Fomblin (Daitotech), Demnam (D
- the weight average molecular weight in terms of polystyrene determined by gel permeation chromatography (GPC) of the non-three-dimensional crosslinked polymer compound having a fluorine atom is preferably 100000 to 2000, more preferably 50000 to 2000, and 10,000 to Most preferred is 2000.
- the content of the non-three-dimensional crosslinked polymer compound having fluorine atoms in the release region is preferably 1 to 99% by mass with respect to the total solid content of the release region, from the viewpoint of good releasability. More preferably, it is preferably -95% by mass, more preferably 5-90% by mass.
- the ratio (mass ratio) of the three-dimensional crosslinked product containing fluorine atoms to the polymer compound having a non-three-dimensional crosslinked structure having fluorine atoms is preferably 5:95 to 50:50, and 10:90 to 40:60 is more preferable, and 15:85 to 30:70 is still more preferable.
- the polymer compound having a non-three-dimensional crosslinked structure having a fluorine atom may be only one kind or two or more kinds. In the case of two or more types, the total is preferably in the above range.
- the temporary bonding composition of the present invention includes a heterocyclic ring-containing resin containing at least one selected from a polyimide resin, a polyamideimide resin, a polybenzimidazole resin, and a polybenzoxazole resin, and a crosslink containing 50 to 100% by mass of a maleimide resin. Contains ingredients and solvent.
- heterocyclic ring-containing resin one or more selected from polyimide resins, polyamideimide resins, polybenzimidazole resins, and polybenzoxazole resins are used. As these specific examples, those described in the section of the adhesion region are preferably used. Of these, polyimide resin is preferable.
- the polyimide resin is a polyimide having a solubility at 25 ° C.
- the content of the heterocyclic ring-containing resin is preferably 1 to 99% by mass, more preferably 10 to 90% by mass, and more preferably 25 to 75% by mass with respect to the total solid content (excluding the solvent) of the temporary bonding composition. Is particularly preferred.
- Crosslinking component one containing 50 to 100% by mass of maleimide resin is used.
- the maleimide resin is preferably a bismaleimide resin.
- specific examples of the maleimide resin those described in the section of the adhesion region are preferably used.
- the crosslinking component preferably has a maleimide resin content of 80 to 100% by mass of the total crosslinking component.
- the crosslinking component is substantially composed only of maleimide resin.
- it is substantially comprised only with maleimide resin that content of crosslinking components other than maleimide resin is, for example, preferably 1% by mass or less, more preferably 0.5% by mass or less, and 0.1% by mass or less. Is particularly preferred.
- the crosslinking component other than the maleimide resin those described in the section of other crosslinking components in the adhesion region are preferably used.
- the content of the maleimide resin is preferably 1 to 99% by mass, more preferably 10 to 90% by mass, and particularly preferably 25 to 75% by mass with respect to the total solid content (excluding the solvent) of the temporary bonding composition. preferable.
- a known solvent can be used without limitation.
- anisole N-methyl-2-pyrrolidone, N, N-dimethylacetamide, 2-butanone, methyl amyl ketone, limonene, mesitylene, methyl ethyl ketone, PGMEA (1-methoxy-2-propyl acetate) and the like are preferable.
- Methyl-2-pyrrolidone, N, N-dimethylacetamide, methyl amyl ketone and limonene are preferred.
- These solvents are also preferably in a form of mixing two or more kinds from the viewpoint of improving the coated surface.
- the solvent content is preferably used such that the solid content concentration of the temporary bonding composition is 5 to 60% by mass.
- One type of solvent may be sufficient and two or more types may be sufficient. When there are two or more solvents, the total is preferably in the above range.
- the temporary bonding composition further contains a thermal polymerization initiator.
- a thermal polymerization initiator By containing a thermal polymerization initiator, a temporary adhesive film having more excellent heat resistance and chemical resistance can be formed.
- the thermal polymerization initiator those described in the section of the adhesion region are preferably used, and the preferred range is also the same.
- the content of the thermal polymerization initiator is preferably 0.001 to 1% by weight, more preferably 0.01 to 0.5% by weight, based on the total solid content (excluding the solvent) of the temporary bonding composition. 0.05 to 0.1% by mass is particularly preferable.
- the temporary bonding composition further contains a release component.
- a release component By including a release component, when the temporary bonding composition is applied in the form of a film, the release component is unevenly distributed on the surface layer, and the release region is unevenly distributed on the surface layer of the bonded region Can be formed.
- the release component is preferably a material containing at least one selected from fluorine atoms and silicon atoms. Examples of the material containing at least one selected from a fluorine atom and a silicon atom include polymerizable monomers having a fluorine atom or a silicon atom. A fluorine-based silane coupling agent is more preferable.
- the polymerizable monomer having a fluorine atom or a silicon atom is preferably a radical polymerizable monomer or oligomer in which one or more fluorine atoms or silicon atoms are contained in one molecule, and two or more fluorine atoms are contained in one molecule.
- Particularly preferred is a polymerizable monomer having a group generally called a perfluoro group.
- the radically polymerizable monomer or oligomer having a fluorine atom or a silicon atom has a radically polymerizable functional group, and the radically polymerizable functional group is not particularly limited, but is an unsaturated group (such as an ethylenically unsaturated bond group). ) Is preferred.
- the radically polymerizable monomer or oligomer having a fluorine atom or a silicon atom preferably has two or more radically polymerizable functional groups, whereby the device wafer after undergoing a process at a high temperature in the device manufacturing process.
- the peelability from can be further improved.
- the polymerizable monomer having a fluorine atom can be selected from known monomers, 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, alkoxysilyl group, acyloxysilyl group, etc.), a group having a reactive unsaturated double bond ((meth) acryloyl group, allyl group, Vinyloxy groups, etc.), ring-opening polymerization reactive groups (epoxy groups, oxetanyl groups, oxazolyl groups, etc.), groups having active hydrogen atoms (for example, hydroxyl groups, carboxyl groups, amino groups, carbamoyl groups, mercapto groups, ⁇ -ketoester groups, Hydrosilyl groups, silanol groups, etc.), acid anhydrides, groups that can be substituted by nucleophiles (active halogen atoms, sulfonate esters, etc.) and the like.
- a silyl group having a hydroxyl group or a hydrolyzable group for example
- the radically polymerizable monomer having a fluorine atom is preferably a compound represented by the following general formula (1).
- 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 either an oxygen atom or a hydrogen atom, and n represents an integer of 2 or more.
- L represents a single bond or a divalent linking group, and Y represents a polymerizable group.)
- Y is a polymerizable group, for example, a silyl group having a hydroxyl group or a hydrolyzable group (for example, alkoxysilyl group, acyloxysilyl group, etc.), a reactive unsaturated double bond.
- Y represents a radical polymerizable group, and more preferably a group having a reactive unsaturated double bond.
- T is preferably a radical polymerizable functional group represented by the following general formula (9).
- R 901 to R 903 each independently represents a hydrogen atom, an alkyl group or an aryl group.
- the dotted line represents a bond to a group linked to L.
- alkyl group examples are preferably alkyl groups having 1 to 8 carbon atoms.
- the aryl group are preferably aryl groups having 6 to 12 carbon atoms, and examples thereof include a phenyl group, a 1-naphthyl group, and a 2-naphthyl group.
- R 901 to R 903 are particularly preferably a hydrogen atom or a methyl group.
- L represents a single bond or a divalent linking group.
- the divalent linking group a divalent aliphatic group, a divalent aromatic group, —O—, —S—, —CO—, —N (R) —, or a combination of two or more thereof can be obtained.
- R represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.
- Rf represents a chain or cyclic n-valent group that contains at least a carbon atom and a fluorine atom, and may contain either an oxygen atom or a hydrogen atom.
- Rf may be a linear or branched polymer structure having a repeating unit having a fluorine atom.
- the radically polymerizable monomer having a fluorine atom may be at least one selected from compounds represented by the following structural formulas (1), (2), (3), (4) and (5). preferable.
- 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—, where R f is —C n F 2n + 1 , — (CF 2 ) n H, —C n F 2n + 1 —CF 3, - (CF 2) p OC n H 2n C i F 2i + 1, - (CF 2) p OC m H 2m C i F 2i H, -N (C p H 2p + 1) COC n F 2n + 1, or, -N (C p H 2p + 1) represents the SO 2 C n F 2n + 1 .
- p is an integer of 1 ⁇ 10
- n is an integer of 1 ⁇ 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.)
- 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 of 1 to 10, and t is 1 to 16 Is an integer.
- radical polymerizable monomer or oligomer having a fluorine atom an oligomer having a repeating unit having a fluorine atom and a repeating unit having a radical polymerizable functional group can also be preferably used.
- the repeating unit having a fluorine atom is preferably selected from at least one repeating unit represented by the following formulas (6), (7) and (10).
- 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 R 1 , R 2 , R 3 , At least one of R 4 is a fluorine atom or a monovalent organic group having a fluorine atom.
- R 5 , R 6 and R 7 each independently represents a hydrogen atom, a halogen atom, a hydroxyl group or a monovalent organic group
- Y 1 represents a single bond, —CO—, — It represents a divalent linking group selected from the group consisting of O—, —NH—, a divalent aliphatic group, a divalent aromatic group, and combinations thereof.
- Rf represents a fluorine atom or a monovalent organic group having a fluorine atom.
- 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
- Y 2 and Y 3 represents a single bond or a divalent linking group selected from the group consisting of —CO—, —O—, —NH—, a divalent aliphatic group, a divalent aromatic group, and combinations thereof.
- Rf represents a divalent organic group having a fluorine atom.
- the monovalent organic group having a fluorine atom in formula (6) and formula (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.
- a fluorine-containing alkyl group having 1 to 15 carbon atoms is particularly preferred.
- This fluorine-containing alkyl group is a straight chain (for example, —CF 2 CF 3 , —CH 2 (CF 2 ) 4 H, —CH 2 (CF 2 ) 8 CF 3 , —CH 2 CH 2 (CF 2 ) 4 H, etc.
- branched structures 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 and the like, and an alicyclic structure (preferably a 5- or 6-membered ring such as a perfluorocyclohexyl group, a perfluorocyclopentyl group, or an alkyl group substituted with these).
- An ether bond (for example, —CH 2 OCH 2 CF 2 CF 3 , —CH 2 CH 2 OCH 2 C 4 F 8 H, —CH 2 CH 2 OCH 2 CH 2 C 8 F 17 , — CH 2 CF 2 OCF 2 CF 2 OCF 2 CF 2 H, etc.). Further, 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 1 to 1 carbon atoms. Fifteen fluorine-containing alkylene groups are particularly preferred.
- This fluorine-containing alkylene group is a straight chain (for example, —CF 2 CF 2 —, —CH 2 (CF 2 ) 4 —, —CH 2 (CF 2 ) 8 CF 2 —, —CH 2 CH 2 (CF 2 ) 4 -, Etc.), branched structures (eg, —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- and the like) and alicyclic structures (preferably 5-membered or 6-membered rings such as perfluorocyclohexyl, perfluorocyclopentyl, or substituted therewith A linking group having an alkyl group, etc.) or an ether bond (for example, —CH 2 OCH 2 CF 2 CF 2 —, —CH 2 CH 2 OCH 2 C 4 F 8 —,
- the monovalent organic group in the formulas (6), (7), and (10) is preferably an organic group composed of 3 to 10 non-metallic atoms, for example, 1 to 60 carbon atoms. At least one or more selected from atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to 100 hydrogen atoms, and 0 to 20 sulfur atoms Examples include organic groups composed of elements. More specific examples include organic groups composed of the following structures singly or in combination. The monovalent organic group may further have a substituent.
- substituents that can be introduced include a halogen atom, a hydroxy group, a carboxy group, a sulfonate group, a nitro group, a cyano group, an amide group, and an amino group.
- the organic group may contain an ether bond, an ester bond, or a ureido bond.
- the monovalent organic group is preferably an alkyl group, an alkenyl group, an alkynyl group, or an aryl group.
- the alkyl group is preferably an alkyl group having 1 to 8 carbon atoms.
- a methyl group, an ethyl group, a propyl group, an octyl group, an isopropyl group, a t-butyl group, an isopentyl group, a 2-ethylhexyl group, a 2-ethylhexyl group, A methylhexyl group, a cyclopentyl group, etc. are mentioned.
- alkenyl group and an alkenyl group having 2 to 20 carbon atoms are preferable, 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.
- the heterocyclic group is preferably a heterocyclic group having 2 to 10 carbon atoms, and examples thereof include a furanyl group, a thiophenyl group, and a pyridinyl group.
- an alkyl group or an aryl group is preferable.
- the alkyl group are preferably alkyl groups having 1 to 8 carbon atoms.
- the aryl group are preferably aryl groups having 6 to 12 carbon atoms, and examples thereof include a phenyl group, a 1-naphthyl group, and a 2-naphthyl group.
- R 901 to R 903 are particularly preferably a hydrogen atom or a methyl group.
- the divalent aliphatic group means an alkylene group, a substituted alkylene group, an alkenylene group, a substituted alkenylene group, an alkynylene group, a substituted alkynylene group or a polyalkyleneoxy group.
- an alkylene group, a substituted alkylene group, an alkenylene group, and a substituted alkenylene group are preferable, and an alkylene group and a substituted alkylene group are more preferable.
- the divalent aliphatic group preferably has a chain structure rather than a cyclic structure, and more preferably has a straight chain structure than a branched chain structure.
- the number of carbon atoms in the divalent aliphatic group is preferably 1-20, more preferably 1-15, still more preferably 1-12, and even more preferably 1-10. It is preferably 1 to 8, more preferably 1 to 4, and particularly preferably 1 to 4.
- substituent of the divalent aliphatic group include a halogen atom (F, Cl, Br, I), a hydroxy group, a carboxy group, an amino group, a cyano group, an aryl group, an alkoxy group, an aryloxy group, and an acyl group. , Alkoxycarbonyl group, aryloxycarbonyl group, acyloxy group, monoalkylamino group, dialkylamino group, arylamino group and diarylamino group.
- Examples of the divalent aromatic group include a phenylene group, a substituted phenylene group, a naphthalene group, and a substituted naphthalene group, and a phenylene group is preferable.
- Examples of the substituent for the divalent aromatic group include an alkyl group in addition to the examples of the substituent for the divalent aliphatic group.
- the content of the repeating unit having a fluorine atom is preferably 2 mol% to 98 mol%, preferably 10 mol% to 90 mol%, based on all repeating units of the radical polymerizable oligomer having a fluorine atom. Is more preferable.
- repeating unit having a radical polymerizable functional group a repeating unit represented by the following formula (8) is preferable.
- R 801 to R 803 each independently represents a hydrogen atom, an alkyl group, or a halogen atom.
- Y 8 represents a single bond, or —CO—, —O—, — NH— represents a divalent linking group selected from the group consisting of a divalent aliphatic group, a divalent aromatic group, and combinations thereof, and 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 preferably represents a radical polymerizable functional group represented by the general formula (9).
- R 901 to R 903 each independently represents a hydrogen atom, an alkyl group or an aryl group.
- the dotted line represents a bond to a group linked to Y 8.
- alkyl group examples are preferably alkyl groups having 1 to 8 carbon atoms.
- the aryl group are preferably aryl groups having 6 to 12 carbon atoms, and examples thereof include a phenyl group, a 1-naphthyl group, and a 2-naphthyl group.
- R 901 to R 903 are particularly 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 combinations thereof. To express. Specific examples of comprising the combination Y 8 below. In the following examples, the left side is bonded to the main chain, and the right side is bonded to the formula (9).
- the divalent aliphatic group means an alkylene group, a substituted alkylene group, an alkenylene group, a substituted alkenylene group, an alkynylene group, a substituted alkynylene group or a polyalkyleneoxy group.
- an alkylene group, a substituted alkylene group, an alkenylene group, and a substituted alkenylene group are preferable, and an alkylene group and a substituted alkylene group are more preferable.
- the divalent aliphatic group preferably has a chain structure rather than a cyclic structure, and more preferably has a straight chain structure than a branched chain structure.
- the number of carbon atoms in the divalent aliphatic group is preferably 1-20, more preferably 1-15, still more preferably 1-12, and even more preferably 1-10. It is preferably 1 to 8, more preferably 1 to 4, and particularly preferably 1 to 4.
- substituent of the divalent aliphatic group include a halogen atom (F, Cl, Br, I), a hydroxy group, a carboxy group, an amino group, a cyano group, an aryl group, an alkoxy group, an aryloxy group, and an acyl group. , Alkoxycarbonyl group, aryloxycarbonyl group, acyloxy group, monoalkylamino group, dialkylamino group, arylamino group and diarylamino group.
- Examples of the divalent aromatic group include a phenylene group, a substituted phenylene group, a naphthalene group, and a substituted naphthalene group, and a phenylene group is preferable.
- Examples of the substituent for the divalent aromatic group include an alkyl group in addition to the examples of the substituent for the divalent aliphatic group.
- the content of the repeating unit having a radical polymerizable functional group is preferably 2 to 98 mol%, preferably 10 to 90 mol%, based on all repeating units of the radical polymerizable oligomer having a fluorine atom. More preferred.
- the weight average molecular weight in terms of polystyrene of the radically polymerizable oligomer having a fluorine atom as measured by gel permeation chromatography (GPC) is preferably 2000 to 20000, more preferably 2000 to 15000, and more preferably 2000 to 10,000. Most preferred.
- the weight average molecular weight in terms of polystyrene of the radically polymerizable oligomer having a fluorine atom as measured by gel permeation chromatography (GPC) method is preferably 2000 to 10,000, more preferably 8000 to 2000, and preferably 6000 to 2000. Most preferred.
- the content of the radically polymerizable monomer or oligomer having a fluorine atom is not particularly limited, and is preferably a release region.
- the content is preferably 0.01 to 15% by mass with respect to the total solid content of the forming composition. If it is 0.01 mass% or more, sufficient peelability is obtained. If it is 15 mass% or less, sufficient adhesive force will be obtained.
- the radically polymerizable monomer or oligomer having a silicon atom is preferably a silicone monomer or a silicone oligomer.
- at least one terminal of a polydimethylsiloxane bond is an ethylenically unsaturated group such as a (meth) acryloyl group and a styryl group.
- a compound having a (meth) acryloyl group is preferable.
- the number average molecular weight in terms of polystyrene of the radically polymerizable oligomer having a silicon atom as measured by gel permeation chromatography is preferably 1,000 to 10,000.
- the number average molecular weight in terms of polystyrene by a gel permeation chromatography method of a radically polymerizable oligomer having a silicon atom is less than 1,000 or 10,000 or more, properties such as releasability due to a silicon atom are hardly expressed.
- radical polymerizable monomer having a silicon atom a compound represented by the general formula (11) or (12) is preferable.
- R 11 to R 19 each independently represents a hydrogen atom, an alkyl group, an alkoxy group, an alkoxycarbonyl group, or an aryl group.
- Z 11 , Z 12 , and Z 13 each independently represents a radically polymerizable group,
- L 11 , L 12 and L 13 each independently represents a single bond or a divalent linking group, and
- n and m each independently represents 0 or more. Represents an integer.
- R 11 to R 19 each independently represents 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, specifically, methyl group, ethyl group, n-propyl group. Group, isopropyl group and the like.
- An alkoxy group means —OR 20 , wherein R 20 represents an alkyl group (preferably an alkyl group having 1 to 5 carbon atoms), specifically, a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group And a butoxy group.
- An alkoxycarbonyl group means —C ( ⁇ O) R 21 , where R 21 represents an alkoxy group (preferably an alkoxy group having 1 to 5 carbon atoms), and specifically includes methoxycarbonyl, ethoxycarbonyl, And propoxycarbonyl.
- R 21 represents an alkoxy group (preferably an alkoxy group having 1 to 5 carbon atoms), and specifically includes methoxycarbonyl, ethoxycarbonyl, And propoxycarbonyl.
- the aryl group include a phenyl group, a tolyl group, and a naphthyl group, which may have a substituent, such as phenylmethyl (benzyl) group, phenylethyl group, phenylpropyl group, phenylbutyl group, naphthylmethyl. Groups and the like.
- L 11 , L 12 and L 13 each independently represents 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 combinations thereof. .
- N and m each independently represent an integer of 0 or more, preferably an integer of 0 to 100, and more preferably an integer of 0 to 50.
- Z 11 , Z 12 , and Z 13 each independently represent a radical polymerizable group, and a functional group represented by any one of the following general formulas (i) to (iii) is particularly preferable.
- R 101 to R 103 each independently represents a hydrogen atom or a monovalent organic group.
- X 101 represents an oxygen atom, a sulfur atom, or —N (R 104 ) —, R 104 represents a hydrogen atom or a monovalent organic group.
- R 101 to R 103 each independently represents a hydrogen atom or a monovalent organic group.
- R 101 preferably includes a hydrogen atom or an alkyl group which may have a substituent. Among them, a hydrogen atom and a methyl group are preferable because of high radical reactivity.
- R 102 and R 103 are each independently preferably a hydrogen atom, halogen atom, amino group, carboxyl group, alkoxycarbonyl group, sulfo group, nitro group, cyano group, or optionally substituted alkyl.
- aryl group which may have a substituent alkoxy group which may have a substituent, aryloxy group which may have a substituent, alkylamino group which may have a substituent, substituent Represents an arylamino group which may have a substituent, an alkylsulfonyl group which may have a substituent, or an arylsulfonyl group which may have a substituent, among which a hydrogen atom, a carboxyl group, an alkoxycarbonyl group An alkyl group which may have a substituent and an aryl group which may have a substituent are preferable because of high radical reactivity.
- X 101 represents an oxygen atom, a sulfur atom, or —N (R 104 ) —
- R 104 represents a hydrogen atom or a monovalent organic group.
- the monovalent organic group include an alkyl group which may have a substituent.
- R 104 is preferably a hydrogen atom, a methyl group, an ethyl group, or an isopropyl group because of high radical reactivity.
- substituents examples include alkyl groups, alkenyl groups, alkynyl groups, aryl groups, alkoxy groups, aryloxy groups, halogen atoms, amino groups, alkylamino groups, arylamino groups, carboxyl groups, alkoxycarbonyl groups, sulfo groups, A nitro group, a cyano group, an amide group, an alkylsulfonyl group, an arylsulfonyl group and the like can be mentioned.
- R 201 to R 205 each independently represents a hydrogen atom or a monovalent organic group.
- Y 201 represents an oxygen atom, a sulfur atom, or —N (R 206 ) —.
- R 206 represents a hydrogen atom or a monovalent organic group.
- R 201 to R 205 each independently represents a hydrogen atom or a monovalent organic group.
- R 201 to R 205 each independently represents a hydrogen atom, a halogen atom, an amino group, a carboxyl group, an alkoxycarbonyl group, a sulfo group, a nitro group, a cyano group, an alkyl group that may have a substituent, or a substituent.
- An aryl group that may have, an alkoxy group that may have a substituent, an aryloxy group that may have a substituent, an alkylamino group that may have a substituent, and a substituent It is preferably a good arylamino group, an optionally substituted alkylsulfonyl group, or an optionally substituted arylsulfonyl group, having a hydrogen atom, a carboxyl group, an alkoxycarbonyl group, or a substituent. It is more preferably an alkyl group which may be substituted or an aryl group which may have a substituent.
- Y 201 represents an oxygen atom, a sulfur atom, or —N (R 206 ) —.
- R 206 has the same meaning as R 104 in formula (i), and preferred examples thereof are also the same.
- R 301 to R 303 each independently represents a hydrogen atom or a monovalent organic group.
- Z 301 represents an oxygen atom, a sulfur atom, —N (R 304 ) — or a substituent.
- R 304 has the same meaning as R 104 in formula (i).
- R 301 to R 303 each independently represents a hydrogen atom or a monovalent organic group.
- R 301 is preferably a hydrogen atom or an alkyl group which may have a substituent, and more preferably a hydrogen atom or a methyl group because of high radical reactivity.
- R 302 and R 303 are each independently a hydrogen atom, a halogen atom, an amino group, a carboxyl group, an alkoxycarbonyl group, a sulfo group, a nitro group, a cyano group, an alkyl group which may have a substituent, or a substituent.
- An alkyl group that may have a substituent or an aryl group that may have a substituent is more preferable because of high radical reactivity.
- Z 301 represents an oxygen atom, a sulfur atom, —N (R 304 ) — or an optionally substituted phenylene group.
- R 304 has the same meaning as R 104 in the general formula (i), and examples of the monovalent organic group include an alkyl group which may have a substituent. Among them, a methyl group, an ethyl group, and An isopropyl group is preferable because of high radical reactivity.
- the release region forming composition has a radical polymerizable monomer or oligomer having a silicon atom
- the content of the radical polymerizable monomer or oligomer having a silicon atom is based on the total solid content of the release region forming composition. 0.01 to 15% by mass is preferable. If it is 0.01 mass% or more, sufficient peelability is obtained. If it is 15 mass% or less, sufficient adhesive force will be obtained.
- radical polymerizable monomer having a fluorine atom or a silicon atom examples include RS-75, RS-72-K, RS-76-E, RS-72-K manufactured by DIC Corporation, and OPTOOL manufactured by Daikin Industries, Ltd.
- DAC-HP fluorine silane coupling agent
- Examples thereof include -22-164E, EBECRYL350, EBECRYL1360, manufactured by Daicel Cytec Co., Ltd., TEGORad2700, manufactured by Degussa, and UV-3500B (manufactured by BYK).
- the content of the release component is preferably 0.01 to 10% by mass, more preferably 0.05 to 5% by mass, based on the total solid content (excluding the solvent) of the temporary bonding composition. 1 to 1% by mass is particularly preferred.
- the temporary bonding composition preferably further contains a surfactant.
- a surfactant those described in the section of the adhesion region are preferably used, and the preferable range is also the same.
- the content of the surfactant is preferably 0.001 to 1% by mass, more preferably 0.01 to 0.5% by mass, based on the total solid content (excluding the solvent) of the temporary bonding composition. 0.05 to 0.1% by mass is particularly preferable. Only one type of surfactant may be used, or two or more types may be used. When two or more surfactants are used, the total is preferably in the above range.
- the temporary bonding composition preferably further contains an antioxidant.
- an antioxidant those described in the section of the adhesion region are preferably used, and the preferred range is also the same.
- the content of the antioxidant is preferably from 0.001 to 10% by mass, more preferably from 0.01 to 5% by mass, based on the total solid content (excluding the solvent) of the temporary bonding composition. 1 to 1% by mass is particularly preferred.
- One type of antioxidant may be sufficient and two or more types may be sufficient. When there are two or more kinds of antioxidants, the total is preferably within the above range.
- the temporary bonding composition preferably contains a plasticizer in order to enhance the deformability at high temperature and improve the adhesion flatness.
- a plasticizer phthalic acid esters, fatty acid esters, aromatic polycarboxylic acid esters, polyesters, and the like can be used.
- phthalic acid esters examples include DMP, DEP, DBP, # 10, BBP, DOP, DINP, DIDP (above, manufactured by Daihachi Chemical), PL-200, DOIP (above, made by CG Esther), Sunsizer DUP (new) Nippon Rika).
- fatty acid esters examples include butyl stearate, Unistar M-9676, Unistar M-2222SL, Unistar H-476, Unistar H-476D, Panaceto 800B, Panaceto 875, Panaceto 810 (above, NOF Corporation), DBA, DIBA, DBS, DOA, DINA, DIDA, DOS, BXA, DOZ, DESU (manufactured by Daihachi Chemical Co., Ltd.), and the like.
- aromatic polycarboxylic acid ester examples include TOTM (manufactured by Daihachi Chemical), monosizer W-705 (manufactured by Daihachi Chemical), UL-80, UL-100 (manufactured by ADEKA), and the like.
- polyester examples include Polycizer TD-1720, Polycizer S-2002, Polycizer S-2010 (above, manufactured by DIC), BAA-15 (produced by Daihachi Chemical).
- plasticizers DIDP, DIDA, TOTM, Unistar M-2222SL and Polycizer TD-1720 are preferable, DIDA and TOTM are more preferable, and TOTM is particularly preferable. Only one type of plasticizer may be used, or two or more types may be combined.
- the molecular weight of the plasticizer is preferably 250 ° C. or higher when the weight is reduced by 1% by mass when measured under a nitrogen stream under a constant rate of temperature increase at 20 ° C./min. 270 ° C. or higher is more preferable, and 300 ° C. or higher is particularly preferable.
- the upper limit is not particularly defined, but can be, for example, 500 ° C. or less.
- the content of the plasticizer is preferably 1 to 50.0% by mass and more preferably 5 to 20.0% by mass with respect to the total mass of the temporary bonding composition. Only one type of plasticizer may be used, or two or more types may be used. When two or more plasticizers are used, the total is preferably within the above range.
- composition for temporary bonding in the present invention is blended with various additives such as a curing agent, a curing catalyst, a filler, an ultraviolet absorber, an anti-aggregation agent, etc. can do.
- blending these additives it is preferable that the total compounding quantity shall be 3 mass% or less of solid content of the composition for temporary adhesion
- the adhesion region in the temporary adhesive film of the present invention supports the above-described temporary adhesion composition using a conventionally known spin coating method, spray method, roller coating method, flow coating method, doctor coating method, dipping method, or the like. It can be formed by coating on a substrate and then drying.
- the spin coat method, the spray method, and the screen printing method are preferable, the spin coat method and the spray method are more preferable, and the spin coat method is particularly preferable.
- the composition for forming a release region preferably contains a release component and a solvent.
- the release component is preferably a material containing at least one selected from fluorine atoms and silicon atoms.
- the material containing at least one selected from a fluorine atom and a silicon atom include polymerizable monomers having a fluorine atom or a silicon atom.
- a fluorine-based silane coupling agent is more preferable. With the fluorine-based silane coupling agent, the release region layer can be firmly formed on the surface of the adhesion region. For this reason, it becomes difficult for a solvent to permeate into the interface between the layer in the adhesion region and the layer in the release region, and a temporary adhesive film having excellent chemical resistance can be formed.
- the content of the mold release component is preferably 5 to 100% by mass, more preferably 50 to 100% by mass, more preferably 90 to 90% by mass with respect to the total solid content of the mold release region forming composition, from the viewpoint of good releasability. 100 mass% is more preferable.
- 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.
- Perfluoroalkanes can also be used. Among them, N-methyl-2-pyrrolidone, 2-butanone, methyl amyl ketone, limonene, 1-methoxy-2-propyl acetate, perfluoroalkane, and methyl ethyl ketone are preferable. N-methyl-2-pyrrolidone, 2-butanone, methyl More preferred are amyl ketone, limonene and 1-methoxy-2-propyl acetate. These solvents are also preferably in a form of mixing two or more kinds from the viewpoint of improving the coated surface.
- the release region-forming composition can contain various compounds depending on the purpose within a range that does not impair the effects of the present invention.
- a thermal polymerization initiator, a sensitizing dye, a chain transfer agent, an antioxidant, and a surfactant can be preferably used.
- those described above with reference to the temporary bonding composition can be used.
- the solid content concentration of the release region forming composition is preferably 3 to 40% by mass, and more preferably 5 to 40% by mass.
- the above-described composition for forming a release region is applied onto a supporting substrate using a conventionally known spin coating method, spray method, roller coating method, flow coating method, doctor coating method, dipping method, or the like. And then dried.
- a conventionally known spin coating method, spray method, roller coating method, flow coating method, doctor coating method, dipping method, or the like is preferable, the spin coat method and the spray method are more preferable, and the spin coat method is particularly preferable.
- the kit of this invention contains the composition for temporary adhesion mentioned above, and the composition for mold release area
- the temporary adhesive film of the present invention can be produced by sequentially applying the temporary bonding composition and the release region forming composition onto the support substrate.
- the temporary adhesive film of the present invention can also be produced by sequentially applying a release region forming composition and a temporary bonding composition to a device wafer.
- the respective compositions and preferred ranges of the temporary bonding composition and the release region forming composition are the same as those described above.
- the laminate of the present invention is obtained by laminating a device wafer on the surface of the release region of the temporary adhesive film of the present invention described above.
- a known device wafer can be used without limitation, and examples thereof include a silicon substrate and a compound semiconductor substrate.
- the compound semiconductor substrate include a SiC substrate, a SiGe substrate, a ZnS substrate, a ZnSe substrate, a GaAs substrate, an InP substrate, and a GaN substrate.
- a mechanical structure or a circuit may be formed on the surface of the device wafer. Examples of device wafers on which mechanical structures and circuits are formed include MEMS (Micro Electro Mechanical Systems), power devices, image sensors, micro sensors, LEDs, optical devices, interposers, embedded devices, and micro devices. .
- the device wafer preferably has a structure such as a metal bank.
- the temporary adhesive film of the present invention can be stably temporarily bonded even to a device wafer having a structure on the surface, and can be easily released from temporary bonding to the device wafer.
- the height of the structure is not particularly limited, but is preferably 5 to 100 ⁇ m, for example.
- the film thickness of the device wafer before the mechanical or chemical treatment is preferably 500 ⁇ m or more, more preferably 600 ⁇ m or more, and still more preferably 700 ⁇ m or more.
- the film thickness of the device wafer after thinning by mechanical or chemical treatment is preferably less than 500 ⁇ m, more preferably 400 ⁇ m or less, and even more preferably 300 ⁇ m or less.
- a support substrate is disposed on the surface of the temporary adhesive film on the side opposite to the laminated surface of the device wafer.
- the material of the support substrate is not particularly limited, and examples thereof include a silicon substrate, a glass substrate, a metal substrate, and a compound semiconductor substrate.
- it may be a silicon substrate.
- the thickness of the support substrate is not particularly limited, but is preferably 300 ⁇ m to 5 mm, for example.
- the method for producing a device of the present invention includes a step of applying the above-described temporary bonding composition of the present invention.
- the device manufacturing method of the present invention will be described in more detail.
- a support substrate-temporary adhesive film-device wafer laminate (hereinafter also referred to as a laminate) can be produced by any of the following methods (1) to (4).
- the temporary adhesion composition of the present invention is applied to a support substrate and heated (baked) to form a layer of an adhesion region.
- Examples of the method for applying the temporary bonding composition include conventionally known methods such as spin coating, spraying, roller coating, flow coating, doctor coating, and dipping.
- the release region forming composition described above is applied on the layer of the adhesive region, and heated (baked) to form a layer of the release region, thereby forming the temporary adhesive film of the present invention.
- the application method of the release region forming composition include conventionally known methods such as spin coating, spraying, roller coating, flow coating, doctor coating, and dipping.
- the device wafer is pressure-bonded to the surface opposite to the surface on which the support substrate of the temporary adhesive film is disposed (that is, the surface of the temporary adhesive film on the release region side) to manufacture a laminate.
- the pressure bonding conditions are preferably, for example, a temperature of 100 to 200 ° C., a pressure of 0.01 to 1 MPa, and a time of 1 to 15 minutes.
- release region forming composition is applied to a device wafer and heated (baked) to form a release region layer.
- the temporary adhesion composition of the present invention is applied on the release area layer, and heated (baked) to form the adhesion area layer, thereby forming the temporary adhesion film of the present invention.
- the surface opposite to the surface on which the device wafer of the temporary adhesive film is disposed is pressure-bonded to the support substrate to produce a laminate.
- the pressure bonding conditions are preferably the above-described conditions.
- the temporary bonding composition of the present invention containing a release component is applied to the surface of either the support substrate or the device wafer, and heated (baked), so that the release area is unevenly distributed on the surface layer of the adhesive area.
- a temporary adhesive film is formed.
- a support substrate or a device wafer is pressure-bonded to the surface of the temporary adhesive film to produce a laminate.
- the pressure bonding conditions are preferably the above-described conditions.
- the mold release region forming composition described above is applied to a device wafer and heated (baked) to form a mold release layer layer on the device wafer.
- the above-described temporary adhesion composition of the present invention is applied to a support substrate and heated (baked) to form a layer of an adhesion region on the support substrate.
- the release area on the device wafer and the adhesion area on the support substrate are pressure-bonded to form a temporary adhesion film, and a laminate is manufactured.
- the pressure bonding conditions are preferably the above-described conditions.
- FIG. 1A, FIG. 1B, and FIG. 1C are respectively a schematic cross-sectional view illustrating temporary bonding between a support substrate and a device wafer, a schematic view illustrating a device wafer temporarily bonded by a support substrate, and temporary bonding by a support substrate. It is a schematic sectional drawing which shows the state by which the made device wafer was thinned.
- the device wafer 60 is formed by providing a plurality of device chips 62 on a surface 61a of a silicon substrate 61. Further, a release region 71 is provided on the surface of the device wafer 60 on the structure 62 side.
- the device wafer 60 preferably has an average film thickness of 500 ⁇ m or more.
- the structure 62 is called a device chip or a bump, and the average height is preferably in the range of 5 to 100 ⁇ m.
- an adhesive support 100 in which an adhesive region 11 is provided on a support substrate 12 is prepared.
- the adhesive support 100 is formed on the support substrate 12 using the conventionally known spin coating method, spray method, roller coating method, flow coating method, doctor coating method, dipping method, or the like. It can be formed by applying to and then drying.
- the surface of the release area 71 provided on the device wafer is pressed against the adhesion area 11 of the adhesive support 100. Thereby, as shown in FIG. 1B, the release region 71 and the adhesion region 11 are bonded to each other, and a temporary adhesive film 80 having the release region 71 and the adhesion region 11 is formed.
- the back surface 61b of the silicon substrate 61 is subjected to mechanical or chemical treatment (not particularly limited, for example, thinning treatment such as gliding or chemical mechanical polishing (CMP), high temperature / vacuum such as CVD or PVD. Treatment with chemicals such as organic solvent, acidic treatment solution or basic treatment solution, plating treatment, actinic ray irradiation, heating / cooling treatment, etc.), as shown in FIG.
- the thickness of 61 is reduced (for example, the average thickness is preferably less than 500 ⁇ m, more preferably 1 to 200 ⁇ m) to obtain a thin device wafer 60a.
- a through hole (not shown) penetrating the silicon substrate is formed from the back surface 61c of the thin device wafer 60a after the thinning process, and a silicon through electrode ( A process of forming (not shown) may be performed.
- the highest temperature achieved in the heat treatment is preferably 130 ° C. to 400 ° C., more preferably 180 ° C. to 350 ° C.
- the maximum temperature reached in the heat treatment is set to a temperature lower than the softening point of the adhesion region.
- the heat treatment is preferably performed for 30 seconds to 30 minutes at the highest temperature, and more preferably for 1 minute to 10 minutes at the highest temperature.
- the temporary adhesive film 80 is peeled from the surface 61a of the thin device wafer 60a.
- the temporary adhesive film 80 is preferably peeled off by a physical action such as peeling. That is, it is preferable to slide the thin device wafer 60 a against the adhesive support 100 or peel the thin device wafer 60 a from the adhesive support 100.
- the temporary adhesive film 80 can be peeled from the surface 61a of the thin device wafer 60a.
- the surface 61a of the thin device wafer 60a may be treated with a stripping solution or the like as necessary.
- a stripping solution for example, stripping solutions described in paragraph numbers 0203 to 0212 of JP-A-2014-80570 can be used.
- the temporary adhesive film 80 of the present invention does not necessarily require treatment with a stripping solution or the like.
- the temporary adhesive film 80 can be removed from the surface 61a of the thin device wafer 60a only by mechanical peeling and without causing peeling residue.
- the release layer has a single layer structure, but the release layer may have a multilayer structure.
- the silicon substrate is exemplified as the member to be processed.
- the present invention is not limited to this, and any member that can be subjected to mechanical or chemical treatment in the device manufacturing method is used. It may be a processing member.
- a compound semiconductor substrate can also be mentioned, and specific examples of the compound semiconductor substrate include a SiC substrate, a SiGe substrate, a ZnS substrate, a ZnSe substrate, a GaAs substrate, an InP substrate, and a GaN substrate.
- the silicon substrate thinning process and the silicon through electrode forming process are exemplified as the mechanical or chemical process for the silicon substrate supported by the support substrate.
- the present invention is not limited thereto. Any processing required in the device manufacturing method is included.
- the shape, size, number, arrangement location, and the like of the device chip in the device wafer exemplified in the above-described embodiment are arbitrary and are not limited.
- Example 1 ⁇ Formation of adhesion area> After applying the adhesive region forming composition 1 having the composition shown in Table 1 to a 4-inch Si wafer with a spin coater (Optical MS-A100, 1200 rpm, 30 seconds, manufactured by Mikasa), 120 ° C. for 3 minutes, 250 ° C. for 3 minutes. Baking was performed to form a wafer 1 provided with an adhesive region having a thickness of 5 ⁇ m.
- a spin coater Optical MS-A100, 1200 rpm, 30 seconds, manufactured by Mikasa
- ⁇ Formation of release area> After applying the release region forming composition 1 having the composition shown in Table 2 to the adhesion region of the wafer 1 using a spin coater (Optical MS-A100, 1200 rpm, 30 seconds, manufactured by Mikasa) at 120 ° C. on a hot plate. Then, the wafer 1 was baked at 190 ° C. for 3 minutes to form a release region having a thickness of 0.1 ⁇ m on the adhesion region, and a wafer 1 provided with a temporary adhesion film was formed.
- a spin coater Optical MS-A100, 1200 rpm, 30 seconds, manufactured by Mikasa
- test piece was prepared by thermocompression bonding of wafer 1 and a 4-inch Si wafer (wafer 2) having nothing applied to the surface.
- Wafer 2 a 4-inch Si wafer
- the surface of the wafer 1 having the temporary adhesive film and the surface of the wafer 2 on which nothing was applied were overlapped and pressure-bonded at 190 ° C. and 0.20 MPa for 3 minutes.
- pressure bonding After pressure bonding, it was heated at 280 ° C. for 30 minutes.
- Example 1 (Examples 2 to 32, 35) In Example 1, the adhesive region forming composition and the release region forming composition were formed in the combinations shown in Table 3 to form the adhesive region and the release region, respectively. The provided test piece was produced.
- Example 33 A composition prepared by mixing 99% by mass of the adhesive region forming composition 19 and 1% by mass of the release region forming composition 1 was mixed with a spin coater (Opticaat MS-A100 manufactured by Mikasa) on a 4-inch Si wafer. And then baked at 120 ° C. for 3 minutes and at 250 ° C. for 3 minutes to form a wafer 1 having a 5 ⁇ m-thick adhesive region, and a temporary adhesive film is provided according to Example 1. The obtained test piece was produced.
- a spin coater Opticaat MS-A100 manufactured by Mikasa
- Example 34 A composition prepared by mixing 99% by mass of the adhesive region forming composition 19 and 1% by mass of the release region forming composition 2 was mixed with a spin coater (Opticaat MS-A100 made by Mikasa) on a 4-inch Si wafer. And then baked at 120 ° C. for 3 minutes and at 250 ° C. for 3 minutes to form a wafer 1 having a 5 ⁇ m-thick adhesive region, and a temporary adhesive film is provided according to Example 1. The obtained test piece was produced.
- a spin coater Opticaat MS-A100 made by Mikasa
- Example 1 a test piece provided with a temporary adhesive film was prepared in the same manner as in Example 1 except that the release region forming composition 1 was not used.
- Example 2 In Example 1, a test piece provided with a temporary adhesive film was prepared in the same manner as in Example 1 except that the composition 1 for forming an adhesive region was not used.
- Comparative Examples 3 to 7 A test piece provided with a temporary adhesive film was prepared in the same manner as in Example 1 except that Comparative Compositions 1 to 7 were used in place of the adhesive region forming composition 1.
- Adhesive force of 80N or more 4 Adhesive force of 60N or more and less than 80N 3: Adhesive force of 40N or more and less than 60N 2: Adhesive force of 20N or more and less than 40N 1: Adhesive force of less than 20N
- ⁇ Chemical resistance> The prepared test piece is put in a glass container filled with N-methyl-2-pyrrolidone at 25 ° C., and the sample after applying ultrasonic waves for 15 minutes using an ultrasonic cleaner is observed. evaluated. In the following evaluation criteria, 2 to 5 is practical, and 3 to 5 is preferable. 5: There is no peeling of the wafer, and the surface of the temporary adhesive film after peeling is not affected by the solvent. 4: Although there is no peeling of the wafer, a range of less than 1 mm from the side surface in contact with the solvent of the temporary adhesive film after peeling is affected by the solvent.
- ⁇ Void> When the wafer 1 is formed, there is no change except that a 4-inch glass wafer is used instead of the 4-inch Si wafer, and the temporary adhesive layers of Examples 1 to 35 and Comparative Examples 1 to 9 are formed, and the 4-inch Si is formed. Bonded to the wafer.
- the obtained sample was heated in an oven at 400 ° C. for 3 hours under a nitrogen atmosphere. Thereafter, the temporary adhesive 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 is practical, and 3 to 5 is preferable.
- the void is a void generated at the interface between the temporary adhesive layer and the glass. 5: Void was not seen at all. 4: Less than 5 voids were observed. 3: 5 or more and less than 10 voids were observed. 2: 10 or more and less than 15 voids were observed. 1: 15 or more voids were observed.
- Comparative compositions 1 to 8 in Table 1 were prepared by the following method.
- Comparative composition 1 A composition of Example 1 of JP-A-2014-29999 was prepared.
- Comparative composition 2 The composition of Example 2 of JP-A-2014-29999 was prepared.
- Comparative composition 3 A composition of Example 3 of JP-A-2014-29999 was prepared.
- Comparative composition 4 A composition of Example 4 of JP-A-2014-29999 was prepared.
- Comparative composition 5 A composition of Example 5 of JP 2014-29999 A was prepared.
- Comparative composition 6 A composition of Example 6 of JP-A-2014-29999 was prepared.
- Comparative composition 7 The temporary bonding composition 1 did not contain the crosslinking component C-1.
- decrease rate in Table 1 was measured with the following method. ⁇ 400 ° C mass reduction rate> Using a thermogravimetric analyzer Q500 (TA), a 2-3 mg sample was heated on an aluminum pan under a nitrogen stream of 60 mL / min to an initial temperature of 25 ° C. to 400 ° C. under a constant temperature increase condition of 10 ° C./min. The residual mass when reaching 400 ° C. was measured.
- TA thermogravimetric analyzer Q500
- the solubility in Table 1 was measured by the following method. ⁇ Solubility> A fixed amount of the sample was added to 100 g of N-methyl-2-pyrrolidone while stirring to confirm the solubility. When the sample was completely dissolved, the operation of adding a certain amount of the sample while stirring was repeated, and the amount immediately before the sample was not dissolved when finally stirred at 25 ° C. for 1 hour was defined as the solubility.
- A-1 OPTOOL DSX (Daikin Kogyo Co., Ltd., fluorine-based silane coupling agent)
- A-2 RS-72-K (DIC Corporation, fluorine compound)
- A-3 RS-76-E (DIC Corporation, fluorine compound)
- A-4 UV-3500B (manufactured by BYK, silicon-based compound)
- A-5 (Heptadecafluoro-1,1,2,2-tetrahydrodecyl) trichlorosilane (manufactured by TCI)
- A-7 TEFLON (registered trademark) AF (made by Mitsui DuPont Fluorochemical Co., Ltd., fluorine-based compound)
- A-8 CYTOP (A
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Adhesive Tapes (AREA)
Abstract
Description
電子機器の更なる小型化および高性能化のニーズに伴い、電子機器に搭載されるICチップについても更なる小型化および高集積化が求められているが、デバイスウエハの面方向における集積回路の高集積化は限界に近づいている。 In a manufacturing process of a semiconductor device such as an IC (Integrated Circuit) or an LSI (Large Scale Integrated Circuit), a large number of IC chips are formed on a device wafer and separated into pieces by dicing.
With the need for further miniaturization and higher performance of electronic equipment, further miniaturization and higher integration are required for IC chips mounted on electronic equipment. High integration is approaching its limit.
しかしながら、厚さ200μm以下のデバイスウエハは非常に薄く、これを基材とする半導体デバイス製造用部材も非常に薄いため、このような部材に対して更なる処理を施したり、あるいは、このような部材を単に移動したりする場合等において、部材を安定的に、かつ、損傷を与えることなく支持することは困難である。 A device wafer having a thickness of about 700 to 900 μm is widely known, but in recent years, for the purpose of reducing the size of an IC chip or the like, the thickness of the device wafer can be reduced to 200 μm or less. Has been tried.
However, since a device wafer having a thickness of 200 μm or less is very thin and a semiconductor device manufacturing member based on the device wafer is very thin, such a member may be further processed, or When the member is simply moved, it is difficult to support the member stably and without damage.
例えば、特許文献1には、支持部材およびデバイスウエハの間に、特定のポリイミド樹脂を含んでなる仮固定用フィルムを介在させ、支持部材にデバイスウエハを仮固定する工程と、支持部材に仮固定されたデバイスウエハに所定の加工を施す工程と、有機溶剤を仮固定用フィルムに接触させて仮固定用フィルムの一部又は全部を溶解し、支持部材から加工されたデバイスウエハを分離する工程と、加工されたデバイスウエハを個片化する工程とを有する、半導体装置の製造方法が開示されている。 In order to solve the above problems, the device wafer before thinning and the support substrate (carrier substrate) are temporarily fixed (temporary bonding) with a temporary adhesive, and the back surface of the device wafer is ground and thinned. A technique for removing the support substrate from the device wafer later is known.
For example, in Patent Document 1, a temporary fixing film including a specific polyimide resin is interposed between a support member and a device wafer, and a device wafer is temporarily fixed to the support member, and temporarily fixed to the support member. A step of subjecting the device wafer to predetermined processing, a step of bringing the organic solvent into contact with the temporary fixing film, dissolving a part or all of the temporary fixing film, and separating the processed device wafer from the support member; And a method of manufacturing a semiconductor device, including a step of dividing a processed device wafer into individual pieces.
特許文献1では、仮固定用フィルムとして有機溶剤に可溶なものを用い、有機溶剤を仮固定用フィルムに接触させることで、デバイスウエハに対する仮支持を解除している。しかしながら、本発明者らの検討によれば、特許文献1に開示された仮固定用フィルムは、耐薬性が劣ることが分かった。
デバイスの製造プロセスでは、種々の薬品が使用されることがある。例えば、デバイスウエハを湿式プロセスで薄膜化する場合には、エッチング液が使用される。このため、デバイスの製造プロセスにおいて、種々の薬品に曝されることがある仮接着膜は、耐薬性の向上が求められている。 When temporarily bonding the surface of the device wafer to the support substrate, the temporary adhesive film between the surface of the device wafer and the support substrate must have a certain level of adhesive strength in order to stably support the device wafer. In addition, there is a demand for characteristics that can easily release the temporarily bonded state between the device wafer and the support substrate.
In Patent Document 1, a film that is soluble in an organic solvent is used as a temporary fixing film, and the temporary support for the device wafer is released by bringing the organic solvent into contact with the temporary fixing film. However, according to studies by the present inventors, it has been found that the temporary fixing film disclosed in Patent Document 1 has poor chemical resistance.
Various chemicals may be used in the device manufacturing process. For example, when a device wafer is thinned by a wet process, an etching solution is used. For this reason, the temporary adhesive film that may be exposed to various chemicals in the device manufacturing process is required to have improved chemical resistance.
<1> 接着領域と、接着領域の表面上の離型領域とを有し、接着領域は、25℃から10℃/分で昇温したときの400℃における質量減少率が1質量%以下であり、25℃のN-メチルピロリドンに対する溶解度が1g/100gSolvent以下である、仮接着膜。
<2> 接着領域は、ポリイミド樹脂、ポリアミドイミド樹脂、ポリベンズイミダゾール樹脂およびポリベンゾオキサゾール樹脂から選ばれる少なくとも1種を含む複素環含有樹脂と、マレイミド樹脂とを含有する、<1>に記載の仮接着膜。
<3> 複素環含有樹脂が、γ-ブチロラクトン、シクロペンタノン、N-メチルピロリドン、シクロヘキサノン、グリコールエーテル、ジメチルスルホキシドおよびテトラメチルウレアから選ばれる少なくとも1種の溶剤に対する25℃での溶解度が10g/100gSolvent以上のポリイミド樹脂である、<2>に記載の仮接着膜。
<4> マレイミド樹脂が、ビスマレイミド樹脂である<2>または<3>に記載の仮接着膜。
<5> 接着領域に含まれる架橋成分の50~100質量%がマレイミド樹脂である、<1>~<4>のいずれかに記載の仮接着膜。
<6> 接着領域は、更に熱重合開始剤を含有する、<1>~<5>のいずれかに記載の仮接着膜。
<7> 熱重合開始剤は、1分間半減期温度が130~300℃である、<6>に記載の仮接着膜。
<8> 熱重合開始剤は、有機過酸化物である、<6>または<7>に記載の仮接着膜。
<9> 離型領域は、フッ素原子およびケイ素原子から選ばれる少なくとも一種を含有する化合物を含む、<1>~<8>のいずれかに記載の仮接着膜。
<10> 離型領域は、フッ素系シランカップリング剤を含有する、<1>~<9>のいずれかに記載の仮接着膜。
<11> <1>~<10>のいずれかに記載の仮接着膜の離型領域側の表面に、デバイスウエハを有する、積層体。
<12> ポリイミド樹脂、ポリアミドイミド樹脂、ポリベンズイミダゾール樹脂およびポリベンゾオキサゾール樹脂から選ばれる少なくとも1種を含む複素環含有樹脂と、架橋成分と、溶剤とを含有し、架橋成分の50~100質量%がマレイミド樹脂である、仮接着用組成物。
<13> 複素環含有樹脂は、γ-ブチロラクトン、シクロペンタノン、N-メチルピロリドン、シクロヘキサノン、グリコールエーテル、ジメチルスルホキシドおよびテトラメチルウレアから選ばれる少なくとも1種の溶剤に対する25℃での溶解度が10g/100gSolvent以上のポリイミド樹脂である、<12>に記載の仮接着用組成物。
<14> マレイミド樹脂が、ビスマレイミド樹脂である<12>または<13>に仮接着用組成物。
<15> 更に熱重合開始剤を含有する、<12>~<14>のいずれかに記載の仮接着用組成物。
<16> 熱重合開始剤は、1分間半減期温度が130~300℃である、<15>に記載の仮接着用組成物。
<17> 熱重合開始剤は、有機過酸化物である、<16>に記載の仮接着用組成物。
<18> 更に、離型成分を含有する、<12>~<17>のいずれかに記載の仮接着用組成物。
<19> 離型成分は、フッ素原子およびケイ素原子から選ばれる少なくとも一種を含有する化合物を含む、<18>に記載の仮接着用組成物。
<20> 離型成分は、フッ素系シランカップリング剤である、<18>または<19>に記載の仮接着用組成物。
<21> <12>~<20>のいずれかに記載の仮接着用組成物を塗布する工程を含む、デバイスの製造方法。
<22> <1>~<10>のいずれかに記載の仮接着膜を形成するためのキットであって、<12>~<20>のいずれかに記載の仮接着用組成物と、離型成分および溶剤を含む離型領域形成用組成物と、を含むキット。 As a result of intensive studies to solve the above problems, the present inventors have found that the mass decrease rate at 400 ° C. when heated from 25 ° C. at 10 ° C./min is 1% by mass or less, and N-methyl at 25 ° C. A temporary adhesive film having an adhesion region having a solubility in pyrrolidone of 1 g / 100 g Solvent or less and a release region on the surface of the adhesion region can stably and temporarily bond a device wafer, and easily allows temporary adhesion to a device wafer. Based on these findings, the present invention has been completed. The present invention provides the following.
<1> It has an adhesive region and a release region on the surface of the adhesive region, and the adhesive region has a mass reduction rate of 1% by mass or less at 400 ° C. when heated from 25 ° C. at 10 ° C./min. A temporary adhesive film having a solubility in N-methylpyrrolidone at 25 ° C. of 1 g / 100 g Solvent or less.
<2> The adhesive region contains a heterocyclic-containing resin containing at least one selected from a polyimide resin, a polyamideimide resin, a polybenzimidazole resin, and a polybenzoxazole resin, and a maleimide resin, according to <1>. Temporary adhesive film.
<3> The solubility at 25 ° C. in a heterocyclic ring-containing resin in at least one solvent selected from γ-butyrolactone, cyclopentanone, N-methylpyrrolidone, cyclohexanone, glycol ether, dimethyl sulfoxide and tetramethylurea is 10 g / The temporary adhesive film according to <2>, which is a polyimide resin of 100 g Solvent or more.
<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 adhesion region is a maleimide resin.
<6> The temporary adhesive film according to any one of <1> to <5>, wherein the adhesion region further contains a thermal polymerization initiator.
<7> The temporary adhesive film according to <6>, wherein the thermal polymerization initiator has a one-minute half-life temperature of 130 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 laminate having a device wafer on the surface of the release region side of the temporary adhesive film according to any one of <1> to <10>.
<12> A heterocyclic-containing resin containing at least one selected from a polyimide resin, a polyamide-imide resin, a polybenzimidazole resin, and a polybenzoxazole resin, a crosslinking component, and a solvent. The composition for temporary adhesion whose% is maleimide resin.
<13> The heterocyclic ring-containing resin has a solubility at 25 ° C. of 10 g / in at least one solvent selected from γ-butyrolactone, cyclopentanone, N-methylpyrrolidone, cyclohexanone, glycol ether, dimethyl sulfoxide and tetramethylurea. The composition for temporary adhesion according to <12>, which is a polyimide resin of 100 g Solvent or more.
<14> The temporary bonding composition according to <12> or <13>, wherein the maleimide resin is a bismaleimide resin.
<15> The temporary adhesive composition according to any one of <12> to <14>, further comprising a thermal polymerization initiator.
<16> The composition for temporary bonding according to <15>, wherein the thermal polymerization initiator has a half-life temperature of 1 minute for 130 to 300 ° C.
<17> The composition for temporary bonding according to <16>, wherein the thermal polymerization initiator is an organic peroxide.
<18> The temporary adhesive composition according to any one of <12> to <17>, further comprising a release component.
The <19> mold release component is a composition for temporary adhesion as described in <18> containing the compound containing at least 1 type chosen from a fluorine atom and a silicon atom.
<20> The temporary release composition according to <18> or <19>, wherein the release component is a fluorine-based silane coupling agent.
<21> A device manufacturing method comprising a step of applying the temporary bonding composition according to any one of <12> to <20>.
<22> A kit for forming the temporary adhesive film according to any one of <1> to <10>, and the temporary adhesive composition according to any one of <12> to <20> A release region forming composition containing a mold component and a solvent.
本明細書における基(原子団)の表記において、置換および無置換を記していない表記は、置換基を有さないものと共に置換基を有するものをも包含するものである。例えば、「アルキル基」とは、置換基を有さないアルキル基(無置換アルキル基)のみならず、置換基を有するアルキル基(置換アルキル基)をも包含するものである。
本明細書中における「活性光線」または「放射線」は、例えば、可視光線、紫外線、遠紫外線、電子線、X線等を含むものを意味する。
本明細書において、「光」とは、活性光線または放射線を意味している。
本明細書において、「露光」とは、特に断らない限り、水銀灯、紫外線、エキシマレーザーに代表される遠紫外線、X線、EUV光等による露光のみならず、電子線およびイオンビーム等の粒子線による描画をも意味している。
本明細書において、「(メタ)アクリレート」は、アクリレートおよびメタアクリレートを表し、「(メタ)アクリル」は、アクリルおよびメタアクリルを表し、「(メタ)アクリロイル」は、「アクリロイル」および「メタクリロイル」を表す。
本明細書において、重量平均分子量および数平均分子量は、ゲルパーミエーションクロマトグラフィー(GPC)測定によるポリスチレン換算値として定義される。本明細書において、重量平均分子量(Mw)および数平均分子量(Mn)は、例えば、HLC-8220(東ソー(株)製)を用い、カラムとしてTSKgel Super AWM―H(東ソー(株)製、6.0mmID×15.0cmを、溶離液として10mmol/L リチウムブロミドNMP(N-メチルピロリジノン)溶液を用いることによって求めることができる。
本明細書において、「単量体」と「モノマー」とは同義である。本発明における単量体は、オリゴマーおよびポリマーと区別され、重量平均分子量が2,000以下の化合物をいう。
本発明における高分子化合物とは、重量平均分子量が2000を超える化合物をいう。
なお、以下に説明する実施の形態において、既に参照した図面において説明した部材等については、図中に同一符号あるいは相当符号を付すことにより説明を簡略化あるいは省略化する。 Hereinafter, embodiments of the present invention will be described in detail.
In the description of the group (atomic group) in this specification, the description which does not describe substitution and non-substitution includes what does not have a substituent and what has a substituent. For example, the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
“Actinic light” or “radiation” in the present specification means, for example, those including visible light, ultraviolet rays, far ultraviolet rays, electron beams, X-rays and the like.
In this specification, “light” means actinic rays or radiation.
In this specification, unless otherwise specified, “exposure” is not limited to exposure with far-ultraviolet rays such as mercury lamps, ultraviolet rays, and excimer lasers, X-rays, EUV light, etc., but also particle beams such as electron beams and ion beams. It also means drawing with.
In the present specification, “(meth) acrylate” represents acrylate and methacrylate, “(meth) acryl” represents acrylic and methacryl, “(meth) acryloyl” represents “acryloyl” and “methacryloyl”. Represents.
In this specification, a weight average molecular weight and a number average molecular weight are defined as a polystyrene conversion value by gel permeation chromatography (GPC) measurement. In this specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are, for example, HLC-8220 (manufactured by Tosoh Corporation), and TSKgel Super AWM-H (manufactured by Tosoh Corporation, 6) as a column. 0.0 mm ID × 15.0 cm can be determined by using a 10 mmol / L lithium bromide NMP (N-methylpyrrolidinone) solution as the eluent.
In the present specification, “monomer” and “monomer” are synonymous. The monomer in the present invention is distinguished from an oligomer and a polymer and refers to a compound having a weight average molecular weight of 2,000 or less.
The polymer compound in the present invention refers to a compound having a weight average molecular weight exceeding 2000.
In the embodiments described below, the members and the like described in the drawings already referred to are denoted by the same or corresponding reference numerals in the drawings, and the description is simplified or omitted.
本発明の仮接着膜は、接着領域と、接着領域の表面上の離型領域とを有し、接着領域は、25℃から10℃/分で昇温したときの400℃における質量減少率が1質量%以下であり、25℃のN-メチルピロリドンに対する溶解度が1g/100gSolvent以下である。
本発明の仮接着膜は、接着領域の表面上に、離型領域を有するので、仮接着膜における離型領域の表面に、デバイスウエハを積層させると共に、仮接着膜におけるデバイスウエハの積層面の反対側の面に支持基板を配置することにより、バンプ等の構造を有するデバイスウェハを適切に保護しつつ、デバイスウエハに機械的または化学的な処理を施した後のデバイスウェハから仮接着膜を機械剥離等の方法で簡単に剥離できる。
また、接着領域は、25℃から10℃/分で昇温したときの400℃における質量減少率が1質量%以下であるので、耐熱性に優れ、高温でのプロセスを経た場合においても、デバイスウエハを安定して仮接着できる。さらに、仮接着膜が熱劣化しにくいため、高温プロセスを経たのちでも、デバイスウェハから仮接着膜を機械剥離等の方法で簡単に剥離できる。
そして、本発明におけるデバイスウエハと支持基板の剥離は、機械剥離でおこなうことができるので、接着領域の25℃のN-メチルピロリドンに対する溶解度を1g/100gSolvent以下とすることができ、耐薬性に優れる。このため、例えば、デバイスウエハの処理時に、エッチング液などの薬品が仮接着膜に付着しても、デバイスウエハを安定して仮接着できる。
このように、本発明の仮接着膜は、デバイスウエハに対し、高温処理や、薬品処理などの様々な処理を行う場合においても、安定して仮接着することができると共に、処理後のデバイスから容易に剥離することができる。
なお、本発明において、質量減少率は、熱量計測定装置(TGA)により、窒素気流下において、上記昇温条件で測定した値である。
また、本発明において、溶解度は、溶剤100gに対して試料を撹拌しながら一定量添加し、溶解性を確認し、完全に溶解した場合にはさらに試料を撹拌下、一定量添加する作業を繰り返し、最終的に25℃で1時間攪拌したときに試料が溶けなくなる直前の量を溶解度とした。 <Temporary adhesive film>
The temporary adhesive film of the present invention has an adhesive region and a release region on the surface of the adhesive region, and the adhesive region has a mass reduction rate at 400 ° C. when the temperature is increased from 25 ° C. at 10 ° C./min. The solubility in N-methylpyrrolidone at 25 ° C. is 1 g / 100 g Solvent or less.
Since the temporary adhesive film of the present invention has a release region on the surface of the adhesive region, the device wafer is laminated on the surface of the release region in the temporary adhesive film, and the laminated surface of the device wafer in the temporary adhesive film By disposing a support substrate on the opposite surface, the device wafer having a structure such as a bump is appropriately protected, and a temporary adhesive film is applied from the device wafer after mechanical or chemical treatment is applied to the device wafer. It can be easily peeled off by mechanical peeling.
In addition, since the mass reduction rate at 400 ° C. when the temperature is raised from 25 ° C. to 10 ° C./min is 1% by mass or less, the adhesion region is excellent in heat resistance, and even when subjected to a process at high temperature, The wafer can be temporarily bonded stably. Further, since the temporary adhesive film is not easily deteriorated by heat, the temporary adhesive film can be easily peeled from the device wafer by a method such as mechanical peeling even after a high temperature process.
The device wafer and the support substrate in the present invention can be peeled off by mechanical peeling, so that the solubility in N-methylpyrrolidone at 25 ° C. in the adhesion region can be 1 g / 100 g Solvent or less, and the chemical resistance is excellent. . For this reason, for example, even when a chemical such as an etching solution adheres to the temporary adhesive film during processing of the device wafer, the device wafer can be stably temporarily bonded.
As described above, the temporary adhesive film of the present invention can be stably temporarily bonded to a device wafer even when various processes such as high temperature processing and chemical processing are performed, and from the device after processing. It can be easily peeled off.
In the present invention, the mass reduction rate is a value measured by the calorimeter measuring device (TGA) under the above temperature rising condition under a nitrogen stream.
In the present invention, the solubility is added to a solvent in 100 g of a sample while stirring the sample, and the solubility is confirmed. If the sample is completely dissolved, the sample is further added to the solution with stirring. The amount immediately before the sample was not dissolved when finally stirred at 25 ° C. for 1 hour was defined as the solubility.
本発明の仮接着膜は、接着領域の、25℃から10℃/分で昇温したときの400℃における質量減少率が1質量%以下であり、0.90質量%以下が好ましく、0.8質量%以下がより好ましく、0.7質量%以下が更に好ましく、0.6質量%以下が特に好ましく、0.5質量%以下が最も好ましい。この範囲であれば、400℃までの高温プロセスを場合においても、デバイスウエハを安定して仮接着できる。また、仮接着膜が熱劣化しにくいため、高温プロセスを経たのちでも、デバイスウェハから仮接着膜を機械剥離等の方法で簡単に剥離できる。
本発明の仮接着膜は、接着領域の、25℃のN-メチルピロリドンに対する溶解度は、1g/100gSolvent以下であり、0.8g/100gSolvent以下が好ましく、0.5g/100gSolvent以下がより好ましく、0.1g/100gSolvent以下が更に好ましい。この態様によれば、デバイスの製造プロセス中に用いられる薬液が、仮接着膜に接触した場合においても、デバイスウエハを安定して仮接着できる。 The temporary adhesive film of the present invention has an adhesive region and a release region on the surface of the adhesive region.
In the temporary adhesive film of the present invention, the mass reduction rate at 400 ° C. when the temperature is increased from 25 ° C. to 10 ° C./min in the adhesion region is 1% by mass or less, preferably 0.90% by mass or less. 8 mass% or less is more preferable, 0.7 mass% or less is more preferable, 0.6 mass% or less is especially preferable, and 0.5 mass% or less is the most preferable. Within this range, the device wafer can be stably and temporarily bonded even when a high temperature process up to 400 ° C. is performed. In addition, since the temporary adhesive film is unlikely to be thermally deteriorated, the temporary adhesive film can be easily peeled from the device wafer by a method such as mechanical peeling even after a high temperature process.
In the temporary adhesive film of the present invention, the solubility of the adhesive region in N-methylpyrrolidone at 25 ° C. is 1 g / 100 g Solvent or less, preferably 0.8 g / 100 g Solvent or less, more preferably 0.5 g / 100 g Solvent or less, 0 .1 g / 100 g Solvent or less is more preferable. According to this aspect, the device wafer can be stably temporarily bonded even when the chemical used during the device manufacturing process comes into contact with the temporary adhesive film.
以下、本発明の仮接着膜について具体的に説明する。 In the temporary adhesive film of the present invention, the adhesive region and the release region may exist as independent adhesive layers and release layers, respectively, or the boundary between the adhesive region and the release region may not be clear. . As an example of an aspect in which the boundary between the adhesive region and the release region is not clear, an aspect in which the release component is unevenly distributed in the surface layer in the temporary adhesive layer to form the release region. The adhesive region may be composed of two or more types of adhesive layers, and the release region may be composed of two or more release layers.
Hereinafter, the temporary adhesive film of the present invention will be specifically described.
本発明の仮接着膜は、接着領域を有する。接着領域は、デバイスウエハと支持基板とを接着するものである。
接着領域は、25℃から10℃/分で昇温したときの400℃における質量減少率が1質量%以下で、かつ、25℃のN-メチルピロリドンに対する溶解度は、1g/100gSolvent以下であるものが用いられる。
接着領域の平均厚みは、0.1~500μmが好ましく、0.5~500μmが好ましく、0.5~50μmがより好ましく、0.5~10μmが特に好ましい。また、本発明の仮接着膜を、表面に構造を有するデバイスウエハに適用する場合は、接着領域の平均厚みは、後述するデバイスウエハの構造の高さより厚いことが好ましい。
本発明の仮接着膜が、接着領域をなす層の表層に、離型領域をなす層が積層して構成された積層構造からなる場合、接着領域をなす層の平均厚みは、1~50μmが好ましく、2~20μmがより好ましい。
本発明の仮接着膜が、仮接着層中に離型成分が表層に偏在して離型領域を形成している態様の場合、接着領域の平均厚みは、1~50μmが好ましく、2~20μmがより好ましい。
なお、本発明において、接着領域の平均厚みは、エリプソメトリーにより5点測定した点の平均値と定義する。
接着領域は、上記質量減少率および溶解度を達成しうるものであれば、何れも好ましく用いることができるが、後述する樹脂成分Aと、マレイミド樹脂とを含むことが好ましい。接着領域が、後述する樹脂成分Aとマレイミド樹脂とを含む場合、三次元架橋したマレイミド樹脂の間に樹脂成分Aが介在でき、耐熱性および耐薬性に優れた接着領域が得られやすい。 << Adhesion area >>
The temporary adhesive film of the present invention has an adhesive region. The adhesion region is for bonding the device wafer and the support substrate.
The bonding area has a mass reduction rate at 400 ° C. of 1% by mass or less when the temperature is raised from 25 ° C. at 10 ° C./min, and the solubility in N-methylpyrrolidone at 25 ° C. is 1 g / 100 g Solvent or less. Is used.
The average thickness of the adhesion region is preferably 0.1 to 500 μm, preferably 0.5 to 500 μm, more preferably 0.5 to 50 μm, and particularly preferably 0.5 to 10 μm. When the temporary adhesive film of the present invention is applied to a device wafer having a structure on the surface, the average thickness of the adhesion region is preferably thicker than the height of the structure of the device wafer described later.
When the temporary adhesive film of the present invention has a laminated structure in which the layer forming the release region is laminated on the surface layer of the layer forming the bonding region, the average thickness of the layer forming the bonding region is 1 to 50 μm. 2 to 20 μm is more preferable.
When the temporary adhesive film of the present invention is an embodiment in which a release component is unevenly distributed on the surface layer in the temporary adhesive layer to form a release region, the average thickness of the adhesive region is preferably 1 to 50 μm, and preferably 2 to 20 μm. Is more preferable.
In the present invention, the average thickness of the adhesion region is defined as the average value of five points measured by ellipsometry.
Any adhesive region can be used as long as it can achieve the above-described mass reduction rate and solubility, but it preferably contains a resin component A and a maleimide resin described later. When the adhesion region includes a resin component A and a maleimide resin, which will be described later, the resin component A can be interposed between the three-dimensionally cross-linked maleimide resins, and an adhesion region excellent in heat resistance and chemical resistance can be easily obtained.
本発明においては、接着領域が含みうる樹脂成分Aとして、上記質量減少率および溶解度を満たすものであれば、任意のものを使用できる。なお、本発明において、樹脂成分Aには、マレイミド樹脂は含まれないこととする。
樹脂成分Aとしては、例えば、複素環含有樹脂(好ましくは、ポリイミド樹脂、ポリアミドイミド樹脂、ポリベンズイミダゾール樹脂、ポリベンゾオキサゾール樹脂)、テルペン樹脂、テルペンフェノール樹脂、変性テルペン樹脂、水添テルペン樹脂、水添テルペンフェノール樹脂、ロジン、ロジンエステル、水添ロジン、水添ロジンエステル、重合ロジン、重合ロジンエステル、変性ロジン、ロジン変性フェノール樹脂、アルキルフェノール樹脂、脂肪族石油樹脂、芳香族石油樹脂、水添石油樹脂、変性石油樹脂、脂環族石油樹脂、クマロン石油樹脂、インデン石油樹脂、オレフィンコポリマー(例えば、メチルペンテン共重合体)、シクロオレフィンコポリマー(例えば、ノルボルネン共重合体、ジシクロペンタジエン共重合体、テトラシクロドデセン共重合体)、ノボラック樹脂、フェノール樹脂、エポキシ樹脂、メラミン樹脂、ユリア樹脂、不飽和ポリエステル樹脂、アルキド樹脂、ポリウレタン樹脂、ポリエチレン樹脂、ポリプロピレン樹脂、エチレンプロピレン共重合体(EPDMゴム)、ポリ塩化ビニル樹脂、ポリスチレン樹脂、ポリスチレン共重合樹脂(例えば、アクリロニトリル-ブタジエン-スチレン共重合体(ABS樹脂)、アクリルニトリルスチレン共重合体(AS樹脂)、メタクリル酸メチルスチレン共重合樹脂(MS樹脂))、ポリ酢酸ビニル樹脂、四フッ化エチレン樹脂(PTFE樹脂)、四フッ化エチレンとパーフルオロアルコキシエチレンとの共重合体(PFA樹脂)、テトラフルオロエチレン・ヘキサフルオロプロピレン共重合体(FEP樹脂)、エチレン-TFE共重合樹脂、ポリフッ化ビニリデン(PVDF樹脂)、ポリクロロトリフルオロエチレン(PCTFE樹脂)、エチレン-クロロトリフルオロエチレン樹脂(CTFE樹脂)、TFE-パーフルオロジメチルジオキソール共重合樹脂、フッ化ビニル樹脂(PVF樹脂)、アクリル樹脂、セルロース樹脂、ポリアミド樹脂、ポリアセタール樹脂、ポリカーボネート樹脂、ポリフェニレンエーテル樹脂、ポリブチレンテラフタレート樹脂、ポリエチレンテレフタラート樹脂、環状ポリオレフィン樹脂、ポリフェニレンスルフィド樹脂、ポリスルホン樹脂、ポリエーテルスルホン樹脂、ポリアリレート樹脂、ポリエーテルケトン樹脂などの合成樹脂や、天然ゴムなどの天然樹脂が挙げられる。
中でも、ポリイミド樹脂、ポリアミドイミド樹脂、ポリベンズイミダゾール樹脂、ポリベンゾオキサゾール樹脂、ポリカーボネート樹脂、ポリエーテルスルホン樹脂、ポリエステル樹脂が好ましく、ポリイミド樹脂、ポリアミドイミド樹脂、ポリベンズイミダゾール樹脂、ポリベンゾオキサゾール樹脂がより好ましく、ポリイミド樹脂またはポリアミドイミド樹脂がさらに好ましく、ポリイミド樹脂が特に好ましい。これらの樹脂は、耐熱性に優れるので、上記質量減少率を達成しやすい。
また、ポリイミド樹脂は、γ-ブチロラクトン、シクロペンタノン、N-メチルピロリドン、シクロヘキサノン、グリコールエーテル、ジメチルスルホキシドおよびテトラメチルウレアから選ばれる少なくとも1種の溶剤に対する25℃での溶解度が10g/100gSolvent以上のポリイミド樹脂が好ましい。この態様によれば、接着領域を塗布法で形成することができる。 <<< resin component A >>>
In the present invention, any resin component A that can be contained in the adhesive region can be used as long as it satisfies the mass reduction rate and solubility. In the present invention, the resin component A does not include a maleimide resin.
Examples of the resin component A include a heterocyclic ring-containing resin (preferably, a polyimide resin, a polyamideimide resin, a polybenzimidazole resin, a polybenzoxazole resin), a terpene resin, a terpene phenol resin, a modified terpene resin, a hydrogenated terpene resin, Hydrogenated terpene phenol resin, rosin, rosin ester, hydrogenated rosin, hydrogenated rosin ester, polymerized rosin, polymerized rosin ester, modified rosin, rosin modified phenolic resin, alkylphenol resin, aliphatic petroleum resin, aromatic petroleum resin, hydrogenated Petroleum resin, modified petroleum resin, alicyclic petroleum resin, coumarone petroleum resin, indene petroleum resin, olefin copolymer (for example, methylpentene copolymer), cycloolefin copolymer (for example, norbornene copolymer, dicyclopentadiene copolymer) Tetra Clododecene copolymer), novolac 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), polychlorinated Vinyl resin, polystyrene resin, polystyrene copolymer resin (for example, acrylonitrile-butadiene-styrene copolymer (ABS resin), acrylonitrile styrene copolymer (AS resin), methyl methacrylate styrene copolymer resin (MS resin)), Polyvinyl acetate resin, tetrafluoroethylene resin (PTFE resin), copolymer of tetrafluoroethylene and perfluoroalkoxyethylene (PFA resin), tetrafluoroethylene / hexafluoropropylene copolymer (FEP tree) ), Ethylene-TFE copolymer resin, polyvinylidene fluoride (PVDF resin), polychlorotrifluoroethylene (PCTFE resin), ethylene-chlorotrifluoroethylene resin (CTFE resin), TFE-perfluorodimethyldioxole copolymer resin , Vinyl 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, polysulfone resin And synthetic resins such as polyethersulfone resin, polyarylate resin and polyetherketone resin, and natural resins such as natural rubber.
Among them, polyimide resin, polyamideimide resin, polybenzimidazole resin, polybenzoxazole resin, polycarbonate resin, polyethersulfone resin, and polyester resin are preferable, and polyimide resin, polyamideimide resin, polybenzimidazole resin, and polybenzoxazole resin are more preferable. Preferably, a polyimide resin or a polyamideimide resin is more preferable, and a polyimide resin is particularly preferable. Since these resins are excellent in heat resistance, it is easy to achieve the mass reduction rate.
The polyimide resin has a solubility at 25 ° C. of 10 g / 100 g Solvent or more in at least one solvent selected from γ-butyrolactone, cyclopentanone, N-methylpyrrolidone, cyclohexanone, glycol ether, dimethyl sulfoxide and tetramethylurea. A polyimide resin is preferred. According to this aspect, the adhesion region can be formed by a coating method.
ポリイミド樹脂は、テトラカルボン酸二無水物とジアミンを公知の方法で縮合反応させて得られるものを用いることができる。
公知の方法としては、例えば、有機溶剤中で、テトラカルボン酸二無水物とジアミンを略等モル混合し、反応温度80℃以下で反応させて得られたポリアミック酸を脱水閉環させる方法などが挙げられる。ここで、略等モルとは、テトラカルボン酸二無水物とジアミンのモル量比が1:1近傍であることを言う。なお、必要に応じて、テトラカルボン酸二無水物とジアミンの組成比が、テトラカルボン酸二無水物の合計1.0モルに対して、ジアミンの合計が0.5~2.0モルとなるように調整してもよい。テトラカルボン酸二無水物とジアミンの組成比を上記の範囲内で調整することによって、ポリイミド樹脂の重量平均分子量を調整することができる。 <<<<< Polyimide resin >>>>
As the polyimide resin, a resin obtained by subjecting tetracarboxylic dianhydride and diamine to a condensation reaction by a known method can be used.
Known methods include, for example, a method of dehydrating and ring-closing the polyamic acid obtained by mixing approximately equimolar amounts of tetracarboxylic dianhydride and diamine in an organic solvent and reacting at a reaction temperature of 80 ° C. or lower. It is done. Here, “substantially equimolar” means that the molar ratio of tetracarboxylic dianhydride and diamine is close to 1: 1. If necessary, the composition ratio of tetracarboxylic dianhydride and diamine is 0.5 to 2.0 mol of diamine with respect to 1.0 mol of tetracarboxylic dianhydride in total. You may adjust as follows. By adjusting the composition ratio of tetracarboxylic dianhydride and diamine within the above range, the weight average molecular weight of the polyimide resin can be adjusted.
これらのジアミンの中でも、3-(4-アミノフェニル)-1,1,3-トリメチル-5-アミノインダン、1,3-ビス(3-アミノプロピル)テトラメチルジシロキサン、ポリオキシプロピレンジアミン、2,2-ビス(4-アミノフェノキシフェニル)プロパン、4,9-ジオキサデカン-1,12-ジアミン、1,6-ジアミノヘキサン、及び、4,9,14-トリオキサへプタデカン-1,17-ジアミンからなる群から選択される1種以上が好ましく、3-(4-アミノフェニル)-1,1,3-トリメチル-5-アミノインダンがより好ましい。 The diamine is not particularly limited and includes, for example, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 3,3′-diaminodiphenyl ether, 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'-diaminodiphenylsulfone, 3,4'-diaminodiphenylsulfone, 4,4'-diaminodiphenyl Sulfone, 3,3'-diamy Diphenyl sulfide, 3,4'-diaminodiphenyl 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-aminoindane, 2,2-bis (3-aminophenyl) propane, 2,2 '-(3,4'-diaminodiphenyl) propane, 2 , 2-bis (4-aminophenyl) propane, 2,2-bis (3-aminophenyl) hexafluoropropane, 2,2- (3,4'-diaminodiphenyl) hexafluoropropane, 2,2-bis ( 4-aminophenyl) hexafluoropropane, 1,3-bis (3-aminophenoxy) benzene, 1,4-bis (3-aminophen Noxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 3,3 '-(1,4-phenylenebis (1-methylethylidene)) bisaniline, 3,4'-(1,4-phenylenebis (1-methylethylidene)) bisaniline, 4,4 ′-(1,4-phenylenebis (1-methylethylidene)) 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-aminoenoxy) phenyl) sulfide Bis (4- (4-aminoenoxy) phenyl) sulfide, bis (4- (3-aminoenoxy) phenyl) sulfone, bis (4 (4-aminoenoxy) phenyl) sulfone, 3,3′-dihydroxy-4,4′-diaminobiphenyl, aromatic diamines such as 3,5-diaminobenzoic acid, 1,3-bis (aminomethyl) cyclohexane, 2, 2-bis (4-aminophenoxyphenyl) propane, polyoxypropylenediamine, 4,9-dioxadecane-1,12-diamine, 4,9,14-trioxaheptadecane-1,17-diamine, 1,2-diamino Ethane, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, 1,12-diaminododecane, 1,2-di Examples include aminocyclohexane and 1,3-bis (3-aminopropyl) tetramethyldisiloxane.
Among these diamines, 3- (4-aminophenyl) -1,1,3-trimethyl-5-aminoindane, 1,3-bis (3-aminopropyl) tetramethyldisiloxane, polyoxypropylene diamine, 2 , 2-bis (4-aminophenoxyphenyl) propane, 4,9-dioxadecane-1,12-diamine, 1,6-diaminohexane, and 4,9,14-trioxaheptadecane-1,17-diamine One or more selected from the group is preferred, and 3- (4-aminophenyl) -1,1,3-trimethyl-5-aminoindane is more preferred.
上記テトラカルボン酸二無水物とジアミンとの反応温度は、好ましくは100℃未満、さらに好ましくは90℃未満である。また、ポリアミック酸のイミド化は、代表的には不活性雰囲気(代表的には、真空または窒素雰囲気)下で加熱処理することにより行われる。加熱処理温度は、好ましくは150℃以上、さらに好ましくは180~450℃である。 Examples of the solvent used for the reaction of the tetracarboxylic dianhydride and diamine include N, N-dimethylacetamide, N-methyl-2-pyrrolidone and N, N-dimethylformamide. In order to adjust the solubility of raw materials and the like, a nonpolar solvent (for example, toluene or xylene) may be used in combination.
The reaction temperature of the tetracarboxylic dianhydride and the diamine is preferably less than 100 ° C, more preferably less than 90 ° C. Moreover, imidation of polyamic acid is typically performed by heat treatment under an inert atmosphere (typically a vacuum or nitrogen atmosphere). The heat treatment temperature is preferably 150 ° C. or higher, more preferably 180 to 450 ° C.
このような溶解度を有するポリイミド樹脂は、例えば、3,4,3',4'-ベンゾフェノンテトラカルボン酸二無水物と、3-(4-アミノフェニル)-1,1,3-トリメチル-5-アミノインダンとを反応させて得られるポリイミド樹脂などが挙げられる。このポリイミド樹脂は、耐熱性が特に優れる。 In the present invention, the polyimide resin has a solubility at 25 ° C. of 10 g / 100 g Solvent in at least one solvent selected from γ-butyrolactone, cyclopentanone, N-methylpyrrolidone, cyclohexanone, glycol ether, dimethyl sulfoxide and tetramethylurea. The above polyimide resins are preferred.
Polyimide resins having such solubility include, for example, 3,4,3 ′, 4′-benzophenonetetracarboxylic dianhydride and 3- (4-aminophenyl) -1,1,3-trimethyl-5- Examples thereof include a polyimide resin obtained by reacting with aminoindane. This polyimide resin is particularly excellent in heat resistance.
ポリアミドイミド樹脂は、例えば、ポリカルボン酸あるいはその誘導体などの酸成分とジアミンまたはジイソシアネートとを極性溶剤中で反応させて得られるものを用いることができる。
極性溶剤としては、N-メチル-2-ピロリドン(NMP)や、N,N’-ジメチルアセトアミドなどが挙げられる。上記反応は、所定温度(通常、60~200℃程度)に加熱しながら撹拌することにより行うことができる。 <<<<< Polyamideimide resin >>>>
As the polyamideimide resin, for example, a resin obtained by reacting an acid component such as polycarboxylic acid or a derivative thereof with diamine or diisocyanate in a polar solvent can be used.
Examples of the polar solvent include N-methyl-2-pyrrolidone (NMP) and N, N′-dimethylacetamide. The above reaction can be performed by stirring while heating to a predetermined temperature (usually about 60 to 200 ° C.).
これらの酸成分は、単独で用いても良いし、2種以上組み合わせて用いても良い。これらのなかでは、反応性、耐熱性、溶解性などの観点から、トリメリット酸無水物が好ましい。 Acid components used in the production of polyamideimide resin include trimellitic acid, trimellitic anhydride, trimellitic acid chloride; pyromellitic acid (benzene-1,2,4,5-tetracarboxylic acid), biphenyltetra Tetracarboxylic acids such as carboxylic acid, biphenylsulfone tetracarboxylic acid, benzophenone tetracarboxylic acid, biphenyl ether tetracarboxylic acid, ethylene glycol bis trimellitate, propylene glycol bis trimellitate and their acid anhydrides or acid chlorides; oxalic acid, Aliphatic dicarboxylic acids such as adipic acid, malonic acid, sebacic acid, azelaic acid, dodecanedicarboxylic acid, dicarboxypolybutadiene, dicarboxypoly (acrylonitrile-butadiene), dicarboxypoly (styrene-butadiene) Alicyclic dicarboxylic acids such as 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 4,4′-dicyclohexylmethane dicarboxylic acid, dimer acid; terephthalic acid, isophthalic acid, diphenylsulfone dicarboxylic acid, diphenyl ether dicarboxylic acid Examples thereof include aromatic dicarboxylic acids such as acids and naphthalenedicarboxylic acids.
These acid components may be used alone or in combination of two or more. Among these, trimellitic anhydride is preferable from the viewpoints of reactivity, heat resistance, solubility, and the like.
エチレンジアミン、プロピレンジアミン,ヘキサメチレンジアミンなどの脂肪族ジアミンおよびこれらのジイソシアネート;1,4-シクロヘキサンジアミン、1,3-シクロヘキサンジアミン、イソホロンジアミン、4,4’-ジシクロヘキシルメタンジアミンなどの脂環族ジアミンおよびこれらのジイソシアネート;m-フェニレンジアミン、p-フェニレンジアミン、4,4’-ジアミノジフェニルメタン、4’-ジアミノジフェニルエーテル、4,4’-ジアミノジフェニルスルホン、ベンジジン、o-トリジン、2,4-トリレンジアミン、2,6-トリレンジアミン、キシリレンジアミンなどの芳香族ジアミンおよびこれらのジイソシアネートなどが挙げられる。
これらは単独で用いても良いし、2種以上組み合わせて用いても良い。なかでも、耐熱性、機械特性、溶解性などの点から、4,4’-ジアミノジフェニルメタンおよびそのジイソシアネート、2,4-トリレンジアミンおよびそのジイソシアネート、o-トリジンおよびそのジイソシアネート、イソホロンジアミンおよびそのジイソシアネート、p-フェニレンジアミンおよびこれらのジイソシアネートが好ましく、p-フェニレンジアミンが特に好ましい。 As the diamine or diisocyanate used for the production of polyamideimide resin,
Aliphatic diamines such as ethylenediamine, propylenediamine, hexamethylenediamine and their diisocyanates; alicyclic diamines such as 1,4-cyclohexanediamine, 1,3-cyclohexanediamine, isophoronediamine, 4,4′-dicyclohexylmethanediamine, and These diisocyanates: m-phenylenediamine, p-phenylenediamine, 4,4'-diaminodiphenylmethane, 4'-diaminodiphenyl ether, 4,4'-diaminodiphenylsulfone, benzidine, o-tolidine, 2,4-tolylenediamine , Aromatic diamines such as 2,6-tolylenediamine and xylylenediamine and diisocyanates thereof.
These may be used alone or in combination of two or more. Of these, 4,4′-diaminodiphenylmethane and its diisocyanate, 2,4-tolylenediamine and its diisocyanate, o-tolidine and its diisocyanate, isophorone diamine and its diisocyanate in terms of heat resistance, mechanical properties, solubility and the like. P-phenylenediamine and diisocyanates thereof are preferred, and p-phenylenediamine is particularly preferred.
ポリアミドイミド樹脂の数平均分子量(Mn)が5,000以上であれば、耐久性が良億である。ポリアミドイミド樹脂の数平均分子量(Mn)が100,000以下であれば、溶液粘度が低く、接着領域を塗布形成しやすい。 The number average molecular weight (Mn) of the polyamideimide resin is preferably 5,000 to 100,000. More preferably, it is 10,000 to 50,000.
If the number average molecular weight (Mn) of the polyamideimide resin is 5,000 or more, the durability is good. When the number average molecular weight (Mn) of the polyamide-imide resin is 100,000 or less, the solution viscosity is low and the adhesive region is easily formed by coating.
ポリベンズイミダゾール樹脂は、例えば、芳香族テトラアミンとジカルボン酸成分とを反応させて得られるものを用いることができる。 <<<<< Polybenzimidazole Resin >>>>
As the polybenzimidazole resin, for example, a resin obtained by reacting an aromatic tetraamine and a dicarboxylic acid component can be used.
ジカルボン酸成分は、例えば、イソフタル酸、テレフタル酸、4,4'-ビフェニルジカルボン酸、1,4-ナフタレンジカルボン酸、ジフェニック酸(2,2'-ビフェニルジカルボン酸)、フェニルインダンジカルボン酸、1,6-ナフタレンジカルボン酸、2,6-ナフタレンジカルボン酸、4,4'-ジフェニルチオエーテルジカルボン酸、4,4'-ジフェニルスルホンジカルボン酸、4,4'-ジフェニルチオエーテルジカルボン酸が挙げられる。
ジカルボン酸成分は、芳香族テトラアミンのモル当り、約1モルのジカルボン酸成分比率で導入することが好ましい。なお、重合系の反応物の最適な割合は、当業者によって容易に決められる。 Aromatic tetraamines include, for example, 1,2,4,5-tetraaminobenzene, 1,2,5,6-tetraamononaphthalate, 2,3,6,7-tetraaminonaphthalate, 3,3 ′, 4,4′-tetraaminodiphenylmethane, 3,3 ′, 4,4′-tetraaminodiphenylethane, 3,3 ′, 4,4′-tetraaminodiphenyl-2,2-propane, 3,3′4 Examples include 4'-tetraaminodiphenyl thioether and 3,3 ', 4,4'-tetraaminodiphenyl sulfone. A 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, diphenic acid (2,2′-biphenyldicarboxylic acid), phenylindanedicarboxylic acid, 1, Examples thereof include 6-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 4,4′-diphenylthioether dicarboxylic acid, 4,4′-diphenylsulfone dicarboxylic acid, and 4,4′-diphenylthioether dicarboxylic acid.
The dicarboxylic acid component is preferably introduced at a ratio of about 1 mole of dicarboxylic acid component per mole of aromatic tetraamine. Note that the optimum ratio of the reactants in the polymerization system can be easily determined by those skilled in the art.
ポリベンゾオキサゾール樹脂は、ビスアミノフェノール化合物と、ジカルボン酸誘導体とから合成されるポリヒドロキシアミドを溶剤に溶解し、脱水閉環反応を経ることで得られるものなどが用いられる。 <<<<< Polybenzoxazole resin >>>>
As the polybenzoxazole resin, a resin obtained by dissolving polyhydroxyamide synthesized from a bisaminophenol compound and a dicarboxylic acid derivative in a solvent and undergoing a dehydration ring closure reaction is used.
また、仮接着膜は、樹脂成分Aを、仮接着膜の全固形分量(溶剤を除いた量)に対し、1~99質量%含有することが好ましく、10~90質量%がより好ましく、25~75質量%が特に好ましい。
樹脂成分Aは1種類のみでもよいし、2種類以上であってもよい。樹脂成分Aが2種類以上の場合は、その合計が上記範囲であることが好ましい。 The adhesion region preferably contains 1 to 99% by mass, more preferably 10 to 90% by mass, and 25 to 75% by mass of the resin component A with respect to the total solid content of the adhesion region (excluding the solvent). Is particularly preferred.
Further, the temporary adhesive film preferably contains 1 to 99% by mass of resin component A with respect to the total solid content (excluding the solvent) of the temporary adhesive film, more preferably 10 to 90% by mass, and 25 Particularly preferred is ˜75% by weight.
Only one type of resin component A may be used, or two or more types may be used. When there are two or more types of resin components A, the total is preferably in the above range.
本発明においては、接着領域は、架橋成分としてマレイミド樹脂を含むことが好ましい。マレイミド樹脂として、硬化後の生成物が、上記質量減少率および溶解度を満たすものであれば、任意のものを使用できる。
なお、本発明において、マレイミド基を有する化合物、および、かかる化合物が架橋してなる架橋物を合わせてマレイミド樹脂という。架橋物は、マレイミド基を有する化合物を用いてなる三次元架橋物であることが好ましい。また、マレイミド基を有する化合物は、モノマーであってもよく、ポリマーであってもよい。
本発明では、マレイミド樹脂として、ビスマレイミド樹脂が好ましい。
ビスマレイミド樹脂としては、例えば、下記一般式(III)で表されるビスマレイミド樹脂、下記一般式(IV)で表されるノボラック型マレイミド樹脂から選ばれる少なくとも1種であることがより好ましい。 <<< Crosslinking component >>>
In the present invention, the adhesion region preferably contains a maleimide resin as a crosslinking component. Any maleimide resin can be used as long as the cured product satisfies the mass reduction rate and solubility.
In the present invention, a compound having a maleimide group and a crosslinked product obtained by crosslinking such a compound are collectively referred to as maleimide resin. The cross-linked product is preferably a three-dimensional cross-linked product using a compound having a maleimide group. The compound having a maleimide group may be a monomer or a polymer.
In the present invention, bismaleimide resin is preferable as the maleimide resin.
The bismaleimide resin is more preferably at least one selected from, for example, a bismaleimide resin represented by the following general formula (III) and a novolac maleimide resin represented by the following general formula (IV).
Rは、好ましくは、ベンゼン基、トルエン基、キシレン基、ナフタレン基、若しくは直鎖、分岐鎖若しくは環状飽和炭化水素基、又はこれらの組み合わせから構成される2価の基であることが好ましい。
Rは、下記式(v)、(vi)若しくは(vii)で表される2価の基であることが好ましい。
R is preferably a divalent group composed of a benzene group, a toluene group, a xylene group, a naphthalene group, a linear, branched or cyclic saturated hydrocarbon group, or a combination thereof.
R is preferably a divalent group represented by the following formula (v), (vi) or (vii).
マレイミド樹脂の市販品としては、BMI-1000、2000、3000、4000、5000、5100、7000(大和化成工業製、ビスマレイミド樹脂)、BANI-X(新中村化学製、ビスマレイミド樹脂)、BANI-M(新中村化学製、ビスマレイミド樹脂)などが挙げられる。 In the present invention, as the maleimide resin, those described in paragraph Nos. 0020 to 0023 of JP-A No. 2003-321608 may be used.
Commercially available maleimide resins include BMI-1000, 2000, 3000, 4000, 5000, 5100, 7000 (manufactured by Daiwa Kasei Kogyo, bismaleimide resin), BANI-X (manufactured by Shin-Nakamura Chemical, bismaleimide resin), BANI- M (manufactured by Shin-Nakamura Chemical Co., Ltd., bismaleimide resin).
また、仮接着膜は、マレイミド樹脂を、仮接着膜の全固形分量(溶剤を除いた量)に対し、1~99質量%含有することが好ましく、10~90質量%がより好ましく、25~75質量%が特に好ましい。
マレイミド樹脂は、接着領域に含まれる架橋成分の全質量中、10~100質量%含有することが好ましく、20~100質量%がより好ましく、50~100質量%がさらに好ましく、80~100質量%が特に好ましい。最も好ましくは架橋成分が実質的にマレイミド樹脂のみで構成されることである。なお、実質的にマレイミド樹脂のみで構成されるとは、架橋成分の全量中にマレイミド樹脂以外の架橋成分の含有量が、例えば1質量%以下が好ましく、0.5質量%以下がより好ましく、0.1質量%以下が特に好ましい。この態様によれば、接着領域の耐熱性をより向上できる。 The adhesion region preferably contains maleimide resin in an amount of 1 to 99% by mass, more preferably 10 to 90% by mass, and more preferably 25 to 75% by mass with respect to the total solid content of the adhesion region (excluding the solvent). Particularly preferred. If content of maleimide resin is the said range, the heat resistance of an adhesion | attachment area | region can be improved more.
The temporary adhesive film preferably contains maleimide resin in an amount of 1 to 99% by weight, more preferably 10 to 90% by weight, more preferably 25 to 25% by weight based on the total solid content (excluding the solvent) of the temporary adhesive film. 75% by mass is particularly preferred.
The maleimide resin is preferably contained in an amount of 10 to 100% by mass, more preferably 20 to 100% by mass, further preferably 50 to 100% by mass, based on the total mass of the crosslinking component contained in the adhesion region, and 80 to 100% by mass. Is particularly preferred. Most preferably, the crosslinking component is substantially composed only of maleimide resin. The fact that it is substantially composed only of a maleimide resin means that the content of the crosslinking component other than the maleimide resin in the total amount of the crosslinking component is preferably, for example, 1% by mass or less, more preferably 0.5% by mass or less, 0.1 mass% or less is especially preferable. According to this aspect, the heat resistance of the adhesion region can be further improved.
エチレン性不飽和結合を有する基を有する化合物としては、例えば、炭素数3~35の(メタ)アクリルアミド化合物、炭素数4~35の(メタ)アクリレート化合物、炭素数6~35の芳香族ビニル化合物、炭素数3~20のビニルエーテル化合物等が挙げられる。
エポキシ基を有する化合物としては、例えば、ビスフェノールA型(又はAD型、S型、F型)のグリシジルエーテル、水添加ビスフェノールA型のグリシジルエーテル、エチレンオキシド付加体ビスフェノールA型のグリシジルエーテル、プロピレンオキシド付加体ビスフェノールA型のグリシジルエーテル、フェノールノボラック樹脂のグリシジルエーテル、クレゾールノボラック樹脂のグリシジルエーテル、ビスフェノールAノボラック樹脂のグリシジルエーテル、ナフタレン樹脂のグリシジルエーテル、3官能型(又は4官能型)のグリシジルエーテル、ジシクロペンタジエンフェノール樹脂のグリシジルエーテル、ジアリルビスフェノールAジグリシジルエーテル、アリル化ビスフェノールAとエピクロルヒドリンの重縮合物、ダイマー酸のグリシジルエステル、3官能型(又は4官能型)のグリシジルアミン、ナフタレン樹脂のグリシジルアミン等が挙げられる。
本発明においては、架橋成分としてエポキシ基を有する化合物を含有してもよいが、耐熱性をより向上できるという理由から、架橋成分100質量部中におけるエポキシ基を有する化合物の含有量は、10質量%以下とすることもでき、さらには好ましく、5質量%以下とすることもでき、特には実質的に含有しないこともできる。なお、実質的に含有しないとは、例えば、エポキシ基を有する化合物の含有量が1質量%以下が好ましく、0.5質量%以下がより好ましく、0.1質量%以下が特に好ましく、含有しないことが特に好ましい。 The adhesion area | region of this invention may contain crosslinking components (other crosslinking components) other than maleimide resin. As the other crosslinking component, a compound having two or more polymerizable groups, which can be polymerized 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. As the ethylenically unsaturated bond group, a vinyl group, an acrylic group, a methacryl group, and an allyl group are preferable.
Examples of the compound having a group having an ethylenically unsaturated bond include a (meth) acrylamide compound having 3 to 35 carbon atoms, a (meth) acrylate compound having 4 to 35 carbon atoms, and an aromatic vinyl compound having 6 to 35 carbon atoms. And vinyl ether compounds having 3 to 20 carbon atoms.
Examples of the compound having an epoxy group include bisphenol A type (or AD type, S type, F type) glycidyl ether, water-added bisphenol A type glycidyl ether, ethylene oxide adduct bisphenol A type glycidyl ether, and propylene oxide addition. Bisphenol A type glycidyl ether, phenol novolac resin glycidyl ether, cresol novolac resin glycidyl ether, bisphenol A novolak resin glycidyl ether, naphthalene resin glycidyl ether, trifunctional (or tetrafunctional) glycidyl ether, di Glycidyl ether of cyclopentadiene phenol resin, diallyl bisphenol A diglycidyl ether, polycondensate of allylated bisphenol A and epichlorohydrin, da Glycidyl esters of mer acid, 3 glycidylamine functional type (or tetrafunctional), and glycidyl amines of naphthalene resins.
In the present invention, a compound having an epoxy group may be contained as a cross-linking component. However, because the heat resistance can be further improved, the content of the compound having an epoxy group in 100 parts by mass of the cross-linking component is 10% by mass. % Or less, more preferably 5% by mass or less, and in particular, it may not be substantially contained. Note that substantially not containing, for example, the content of the compound having an epoxy group is preferably 1% by mass or less, more preferably 0.5% by mass or less, particularly preferably 0.1% by mass or less, and not contained. It is particularly preferred.
本発明の接着領域はさらに熱重合発生剤を含有することが好ましい。熱重合開始剤としては、公知のものを用いることができる。
好ましい熱重合開始剤としては、1分間半減期温度が130℃~300℃、好ましくは150℃~260℃の範囲の化合物を好ましく使用することができる。この態様によれば、接着領域の耐熱性をより向上できる。
熱重合開始剤の1分間半減期温度は、熱重合開始剤が分解して、1分間でその残存量(質量)が1/2となる温度である。熱重合開始剤の1分間半減期温度は、例えば、ベンゼン中に熱重合開始剤を0.1mol/lで調製し、数点の温度Ti(絶対温度)で加熱して、各温度Tiにおける半減期t1/2,T1を測定し、lnt1/2,T1を、1/Tiに対してプロットし、得られた直線から、半減期が1分となる温度を求めることで測定できる。
熱重合開始剤は、熱のエネルギーによってラジカルを発生し、マレイミド樹脂等の架橋成分の反応を開始又は促進させる化合物(熱ラジカル発生剤)であることが好ましい。
熱ラジカル発生剤としては、芳香族ケトン類、オニウム塩化合物、有機過酸化物、チオ化合物、ヘキサアリールビイミダゾール化合物、ケトオキシムエステル化合物、ボレート化合物、アジニウム化合物、メタロセン化合物、活性エステル化合物、炭素ハロゲン結合を有する化合物、アゾ系化合物等が挙げられる。中でも、有機過酸化物又はアゾ系化合物がより好ましく、有機過酸化物が特に好ましい。
熱ラジカル発生剤の具体的としては、特開2008-63554号公報の段落0074~0118に記載されている化合物が挙げられる。
また、市販品では、有機過酸化物として、日油社のパークミルD、パークミルH、パークミルND、パークミルP、パーロイルIB、パーロイルIP、パーロイルL、パーロイルNPP、パーロイルSA、パーロイルSBP、パーロイルTCP,パーロイルOPP、パーロイル355、パーブチルD、パーブチルND、パーブチルNHP、パーブチルPV、パーブチルP、パーブチルZ、パーブチルO、パーヘキシルND、パーヘキシルO、パーヘキシルPV、パーオクタND、パーオクタO、ナイパーBMT、ナイパーBW、ナイパーPMB、パーヘキサHC、パーヘキサMC、パーヘキサTMH、パーヘキサV、パーヘキサ25B、パーヘキサ25O、パーヘキシン25B、パーメタンHなどが挙げられる。アゾ系化合物として、和光製のV-601などが挙げられる。
接着領域は、熱重合開始剤を、接着領域の全固形分量(溶剤を除いた量)に対し、0.5~20質量%含有することが好ましく、1~10質量%がより好ましく、2~8質量%が特に好ましい。熱重合開始剤の含有量が上記範囲であれば、接着領域の耐熱性をより向上できる。
また、仮接着膜は、熱重合開始剤を、仮接着膜の全固形分量(溶剤を除いた量)に対し、0.5~20質量%含有することが好ましく、1~10質量%がより好ましく、2~8質量%が特に好ましい。 <<< Thermal polymerization initiator >>>
The adhesive region of the present invention preferably further contains a thermal polymerization generator. A well-known thing can be used as a thermal-polymerization initiator.
As a 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 adhesion region can be further improved.
The 1-minute half-life temperature of the thermal polymerization initiator is a temperature at which the thermal polymerization initiator decomposes and its residual amount (mass) becomes ½ in 1 minute. The one-minute half-life temperature of the thermal polymerization initiator is, for example, prepared by adding 0.1 mol / l of the thermal polymerization initiator in benzene, and heating it at several temperatures Ti (absolute temperature). The period t 1/2, T1 is measured, lnt 1/2, T1 is plotted against 1 / Ti, 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 heat energy and initiates or accelerates the reaction of a crosslinking component such as maleimide resin.
Thermal radical generators include aromatic ketones, onium salt compounds, organic peroxides, thio compounds, hexaarylbiimidazole compounds, ketoxime ester compounds, borate compounds, azinium compounds, metallocene compounds, active ester compounds, carbon halogens. Examples thereof include a compound having a bond and an azo compound. Among these, an organic peroxide or an azo compound is more preferable, and an organic peroxide is particularly preferable.
Specific examples of the thermal radical generator include compounds described in paragraphs 0074 to 0118 of JP-A-2008-63554.
In addition, in the commercial product, as an organic peroxide, NOF's Park Mill D, Park Mill H, Park Mill ND, Park Mill P, Parroyl IB, Parroyl IP, Parroyl L, Parroyl NPP, Parroyl SA, Parroyl SBP, Parroyl TCP, Parroyl OPP, perloyl 355, perbutyl D, perbutyl ND, perbutyl NHP, perbutyl PV, perbutyl P, perbutyl Z, perbutyl O, perhexyl ND, perhexyl O, perhexyl PV, perocta ND, perocta O, niper BMT, niper BW, niper PMB, Perhexa HC, perhexa MC, perhexa TMH, perhexa V, perhexa 25B, perhexa 25O, perhexine 25B, permethane H, and the like. Examples of the azo compound include V-601 manufactured by Wako.
The adhesion region preferably contains the thermal polymerization initiator in an amount of 0.5 to 20% by mass, more preferably 1 to 10% by mass, based on the total solid content of the adhesion region (excluding the solvent). 8% by mass is particularly preferred. If content of a thermal-polymerization initiator is the said range, the heat resistance of an adhesion | attachment area | region can be improved more.
Further, the temporary adhesive film preferably contains 0.5-20% by mass of the thermal polymerization initiator with respect to the total solid content of the temporary adhesive film (amount excluding the solvent), more preferably 1-10% by mass. 2 to 8% by mass is preferable.
本発明の仮接着膜における接着領域は、界面活性剤を含有してもよい。界面活性剤としては、フッ素系界面活性剤、ノニオン系界面活性剤、カチオン系界面活性剤、アニオン系界面活性剤、シリコーン系界面活性剤などの各種界面活性剤を使用でき、フッ素系界面活性剤が好ましい。
接着領域を塗布法で形成する場合において、塗布液として調製したときの液特性(特に、流動性)が向上し、塗布厚の均一性や省液性をより改善することができる。 <<< surfactant >>>
The adhesive region in the temporary adhesive film of the present invention may contain a surfactant. As the surfactant, various surfactants such as a fluorosurfactant, nonionic surfactant, cationic surfactant, anionic surfactant, and silicone surfactant can be used. Is preferred.
When the adhesion region is formed by a coating method, the liquid properties (particularly fluidity) when prepared as a coating liquid are improved, and the uniformity of coating thickness and the liquid-saving property can be further improved.
接着領域が界面活性剤を有する場合、界面活性剤の含有量は、接着領域の全固形分に対して、0.001~1質量%が好ましく、0.01~0.5質量%がより好ましく、0.05~0.1質量%が特に好ましい。
また、仮接着膜は、界面活性剤を、仮接着膜の全固形分量(溶剤を除いた量)に対し、0.001~1質量%含有することが好ましく、0.01~0.5質量%がより好ましく、0.05~0.1質量%が特に好ましい。
界面活性剤は1種類のみでもよいし、2種類以上であってもよい。界面活性剤が2種類以上の場合は、その合計が上記範囲であることが好ましい。 Examples of the silicone surfactant include “Toray Silicone DC3PA”, “Toray Silicone SH7PA”, “Tore Silicone DC11PA”, “Tore Silicone SH21PA”, “Tore Silicone SH28PA”, “Toray Silicone” manufactured by Toray Dow Corning Co., Ltd. Silicone SH29PA, Torre Silicone SH30PA, Torre Silicone SH8400, Momentive Performance Materials TSF-4440, TSF-4300, TSF-4445, TSF-4460, TSF -4552 "," KP341 "," KF6001 "," KF6002 "manufactured by Shin-Etsu Silicone Co., Ltd.," BYK307 "," BYK323 "," BYK330 "manufactured by BYK Chemie.
When the adhesion region has a surfactant, the content of the surfactant is preferably 0.001 to 1% by mass, more preferably 0.01 to 0.5% by mass, based on the total solid content of the adhesion region. 0.05 to 0.1% by mass is particularly preferable.
The temporary adhesive film preferably contains the surfactant in an amount of 0.001 to 1% by mass, based on the total solid content of the temporary adhesive film (excluding the solvent), and 0.01 to 0.5% by mass. % Is more preferable, and 0.05 to 0.1% by mass is particularly preferable.
Only one type of surfactant may be used, or two or more types may be used. When two or more surfactants are used, the total is preferably in the above range.
本発明の仮接着膜における接着領域は、加熱時の酸化による接着領域の低分子化やゲル化を防止する観点から、酸化防止剤を含有してもよい。酸化防止剤としては、フェノール系酸化防止剤、硫黄系酸化防止剤、キノン系酸化防止剤、窒素系酸化防止剤などが使用できる。
フェノール系酸化防止剤としては例えば、p-メトキシフェノール、2,6-ジ-tert-ブチル-4-メチルフェノール、BASF(株)製「Irganox1010」、「Irganox1330」、「Irganox3114」、「Irganox1035」、住友化学(株)製「Sumilizer MDP-S」、「Sumilizer GA-80」などが挙げられる。
硫黄系酸化防止剤としては例えば、3,3’-チオジプロピオネートジステアリル、住友化学(株)製「Sumilizer TPM」、「Sumilizer TPS」、「Sumilizer TP-D」などが挙げられる。
キノン系酸化防止剤としては例えば、p-ベンゾキノン、2-tert-ブチル-1,4-ベンゾキノンなどが挙げられる。
アミン系酸化防止剤としては例えば、ジメチルアニリンやフェノチアジンなどが挙げられる。
酸化防止剤は、Irganox1010、Irganox1330、3,3’-チオジプロピオネートジステアリルが好ましく、Irganox1010、Irganox1330がより好ましく、Irganox1010が特に好ましい。 <<< Antioxidant >>>
The adhesion region in the temporary adhesion film of the present invention may contain an antioxidant from the viewpoint of preventing the adhesion region from being lowered in molecular weight or gelled by oxidation during heating. As the antioxidant, a phenol-based antioxidant, a sulfur-based antioxidant, a quinone-based antioxidant, a nitrogen-based antioxidant, and the like can be used.
Examples of the phenolic antioxidant include p-methoxyphenol, 2,6-di-tert-butyl-4-methylphenol, “Irganox 1010”, “Irganox 1330”, “Irganox 3114”, “Irganox 1035” manufactured by BASF Corporation, Examples thereof include “Sumilizer MDP-S” and “Sumilizer GA-80” manufactured by Sumitomo Chemical Co., Ltd.
Examples of the sulfur-based antioxidant include 3,3′-thiodipropionate distearyl, “Sumilizer TPM”, “Sumilizer TPS”, “Sumilizer TP-D” manufactured by Sumitomo Chemical Co., Ltd., and the like.
Examples of the quinone antioxidant include p-benzoquinone and 2-tert-butyl-1,4-benzoquinone.
Examples of amine-based antioxidants include dimethylaniline and phenothiazine.
As the antioxidant, Irganox 1010, Irganox 1330, and 3,3′-thiodipropionate distearyl are preferable, Irganox 1010 and Irganox 1330 are more preferable, and Irganox 1010 is particularly preferable.
また、仮接着膜は、酸化防止剤を、仮接着膜の全固形分量(溶剤を除いた量)に対し、0.001~10質量%含有することが好ましく、0.01~5質量%がより好ましく、0.1~1質量%が特に好ましい。
酸化防止剤は1種類のみでもよいし、2種類以上であってもよい。酸化防止剤が2種類以上の場合は、その合計が上記範囲であることが好ましい。 When the adhesion region has an antioxidant, the content of the antioxidant is preferably 0.001 to 10% by mass, more preferably 0.01 to 5% by mass, based on the total solid content of the adhesion region. 1 to 1% by mass is particularly preferable.
Further, the temporary adhesive film preferably contains the antioxidant in an amount of 0.001 to 10% by mass, and 0.01 to 5% by mass relative to the total solid content (excluding the solvent) of the temporary adhesive film. More preferred is 0.1 to 1% by mass.
One type of antioxidant may be sufficient and two or more types may be sufficient. When there are two or more kinds of antioxidants, the total is preferably within the above range.
本発明の仮接着膜は、接着領域の表面に離型領域を有する。離型領域は、デバイスウエハと接着領域との接着力を調整し、仮接着膜をデバイスウエハから剥離を容易にする目的で用いる。
離型領域の平均厚みは、0.001~1μmが好ましく、0.01~0.5μmがより好ましい。上記範囲であれば、仮接着膜が適度な接着力を有し、デバイスウエハとの接着性が良好であるとともに、仮接着膜をデバイスウエハから容易に剥離することができる。
本発明の仮接着膜が、接着領域をなす層の表層に、離型領域をなす層が積層して構成された積層構造からなる場合、離型領域をなす層の平均厚みは、0.001~1μmが好ましく、0.01~0.5μmがより好ましい。
本発明の仮接着膜が、仮接着層中に離型成分が表層に偏在して離型領域を形成している態様の場合、離型領域の平均厚みは、0.001~1μmが好ましく、0.01~0.5μmがより好ましい。また、この場合おいて、接着領域の平均厚さと、離型領域の平均厚さの比率は、接着領域の平均厚さ/離型領域の平均厚み=10~1000が好ましく、50~500がより好ましい。
なお、本発明において、離型領域の平均厚みは、エリプソメトリーにより5点測定した点の平均値と定義する。 << Release area >>
The temporary adhesive film of the present invention has a release region on the surface of the adhesive region. The release region is used for the purpose of adjusting the adhesive force between the device wafer and the bonding region, and facilitating peeling of the temporary adhesive film from the device wafer.
The average thickness of the release region is preferably 0.001 to 1 μm, and more preferably 0.01 to 0.5 μm. If it is the said range, while a temporary adhesive film has moderate adhesive force and adhesiveness with a device wafer is favorable, a temporary adhesive film can be easily peeled from a device wafer.
When the temporary adhesive film of the present invention has a laminated structure in which the layer forming the release region is laminated on the surface layer of the layer forming the bonding region, the average thickness of the layer forming the release region is 0.001. ˜1 μm is preferable, and 0.01 to 0.5 μm is more preferable.
In the case where the temporary adhesive film of the present invention is an embodiment in which the release component is unevenly distributed in the surface layer in the temporary adhesive layer to form the release region, the average thickness of the release region is preferably 0.001 to 1 μm, More preferably, it is 0.01 to 0.5 μm. Further, in this case, the ratio of the average thickness of the adhesive region to the average thickness of the release region is preferably the average thickness of the adhesive region / average thickness of the release region = 10 to 1000, more preferably 50 to 500. preferable.
In the present invention, the average thickness of the release region is defined as the average value of points measured by ellipsometry at five points.
離型領域のフッ素含有率は、30~80質量%が好ましく、40~76質量%がより好ましく、60~75質量%が特に好ましい。フッ素含有率は、「{(1分子中のフッ素原子数×フッ素原子の質量)/1分子中の全原子の質量}×100」で定義される。
また、離型領域は、フッ素原子およびケイ素原子から選ばれる少なくとも一種を含有する化合物を、離型領域の全固形分に対して、10~100質量%含有することが好ましく、50~100質量%がより好ましい。
また、仮接着膜は、フッ素原子およびケイ素原子から選ばれる少なくとも一種を含有する化合物を、仮接着膜の全固形分に対して、10~100質量%が好ましく、50~100質量%がより好ましい。
本発明において、離型領域は、耐熱性の観点からフッ素原子を含有する三次元架橋物を含むことが好ましい。中でも、フッ素含有多官能モノマー・オリゴマーの三次元架橋物、またはフッ素含有シランカップリング剤の三次元架橋物が好ましく、フッ素含有シランカップリング剤の三次元架橋物が特に好ましい。フッ素含有シランカップリング剤としては、人体への危険性および金属腐食性の低い、非ハロゲン系シランカップリング剤が好ましく、特にフッ素含有アルコキシシランが好ましい。市販品としては、ダイキン工業株式会社製のオプツールDAC-HP、オプツールDSXが挙げられる。なお、ハロゲン系シランカップリング剤としては、例えばフッ化クロロシラン化合物などが挙げられる。 The release region in the temporary adhesive film of the present invention preferably contains a compound containing at least one selected from fluorine atoms and silicon atoms, and more preferably contains a fluorine-based silane coupling agent.
The fluorine content in the release region is preferably 30 to 80% by mass, more preferably 40 to 76% by mass, and particularly preferably 60 to 75% by mass. The fluorine content is defined by “{(number of fluorine atoms in one molecule × mass of fluorine atoms) / mass of all atoms in one molecule} × 100”.
Further, the release region preferably contains 10 to 100% by mass, preferably 50 to 100% by mass, of a compound containing at least one selected from fluorine atoms and silicon atoms, based on the total solid content of the release region. Is more preferable.
The temporary adhesive film is preferably 10 to 100% by mass, more preferably 50 to 100% by mass, based on the total solid content of the temporary adhesive film, of a compound containing at least one selected from fluorine atoms and silicon atoms. .
In this invention, it is preferable that a mold release area | region contains the three-dimensional crosslinked material containing a fluorine atom from a heat resistant viewpoint. Among these, a three-dimensional crosslinked product of a fluorine-containing polyfunctional monomer / oligomer or a three-dimensional crosslinked product of a fluorine-containing silane coupling agent is preferable, and a three-dimensional crosslinked product of a fluorine-containing silane coupling agent is particularly preferable. As the fluorine-containing silane coupling agent, a non-halogen silane coupling agent having a low risk to human body and low metal corrosivity is preferable, and fluorine-containing alkoxysilane is particularly preferable. Commercially available products include OPTOOL DAC-HP and OPTOOL DSX manufactured by Daikin Industries, Ltd. Examples of the halogen-based silane coupling agent include a fluorinated chlorosilane compound.
非三次元架橋構造とは、化合物中に架橋構造を含まないか、化合物中の全架橋構造に対する三次元架橋構造を形成している架橋構造の割合が、5%以下であることをいい、1%以下が好ましい。実質的に含まれていることが好ましい。
フッ素原子を有する非三次元架橋構造の高分子化合物としては、1種または2種以上の含フッ素単官能モノマーからなる重合体を好ましく使用できる。より具体的には、テトラフルオロエチレン、ヘキサフルオロプロペン、テトラフルオロエチレンオキシド、ヘキサフルオロプロペンオキシド、パーフルオロアルキルビニルエーテル、クロロトリフルオロエチレン、ビニリデンフルオライド、パーフルオロアルキル基含有(メタ)アクリル酸エステルから選ばれる1種又は2種以上の含フッ素単官能モノマーの単独重合体又はこれらモノマーの共重合体、含フッ素単官能モノマーの1種又は2種以上とエチレンとの共重合体、含フッ素単官能モノマーの1種又は2種以上とクロロトリフルオロエチレンとの共重合体から選ばれる少なくとも1種の含フッ素樹脂等を挙げることができる。 In the present invention, the release region can contain a polymer compound having a non-three-dimensional crosslinked structure having a fluorine atom.
The non-three-dimensional crosslinked structure means that the compound does not contain a crosslinked structure or the ratio of the crosslinked structure forming the three-dimensional crosslinked structure to the total crosslinked structure in the compound is 5% or less. % Or less is preferable. It is preferable that it is contained substantially.
As the polymer compound having a non-three-dimensional crosslinked structure having a fluorine atom, a polymer composed of one or more fluorine-containing monofunctional monomers can be preferably used. More specifically, it is selected from tetrafluoroethylene, hexafluoropropene, tetrafluoroethylene oxide, hexafluoropropene oxide, perfluoroalkyl vinyl ether, chlorotrifluoroethylene, vinylidene fluoride, and perfluoroalkyl group-containing (meth) acrylic acid ester. Homopolymers of one or more fluorine-containing monofunctional monomers or copolymers of these monomers, copolymers of one or more fluorine-containing monofunctional monomers with ethylene, fluorine-containing monofunctional monomers And at least one fluorine-containing resin selected from a copolymer of one or more of these and chlorotrifluoroethylene.
パーフルオロアルキル基含有(メタ)アクリル酸エステルとしては、具体的には下記式(101)で表される化合物であることが好ましい。 The polymer compound having a fluorine atom having a non-three-dimensional crosslinked structure is preferably a perfluoroalkyl group-containing (meth) acrylic resin that can be synthesized from a perfluoroalkyl group-containing (meth) acrylic ester.
Specifically, the perfluoroalkyl group-containing (meth) acrylic acid ester is preferably a compound represented by the following formula (101).
2価の芳香族基の例としては、フェニレン基、置換フェニレン基、ナフタレン基および置換ナフタレン基が挙げられ、フェニレン基が好ましい。
Y101としては、2価の直鎖状構造の脂肪族基であることが好ましい。 Y 101 represents a single bond or a divalent linking group selected from the group consisting of —CO—, —O—, —NH—, a divalent aliphatic group, a divalent aromatic group, and combinations thereof. The divalent aliphatic group is preferably a chain structure rather than a cyclic structure, and more preferably a straight chain structure than a branched chain structure. The number of carbon atoms in the divalent aliphatic group is preferably 1-20, more preferably 1-15, still more preferably 1-12, and even more preferably 1-10. It is preferably 1 to 8, more preferably 1 to 4, and particularly preferably 1 to 4.
Examples of the divalent aromatic group include a phenylene group, a substituted phenylene group, a naphthalene group, and a substituted naphthalene group, and a phenylene group is preferable.
Y 101 is preferably an aliphatic group having a divalent linear structure.
式(102)
Formula (102)
離型領域における、フッ素原子を含む三次元架橋物と、フッ素原子を有する非三次元架橋構造の高分子化合物の比(質量比)は、5:95~50:50が好ましく、10:90~40:60がより好ましく、15:85~30:70が更に好ましい。
フッ素原子を有する非三次元架橋構造の高分子化合物は、1種類のみでもよいし、2種類以上であってもよい。2種類以上の場合は、その合計が上記範囲であることが好ましい。 The content of the non-three-dimensional crosslinked polymer compound having fluorine atoms in the release region is preferably 1 to 99% by mass with respect to the total solid content of the release region, from the viewpoint of good releasability. More preferably, it is preferably -95% by mass, more preferably 5-90% by mass.
In the release region, the ratio (mass ratio) of the three-dimensional crosslinked product containing fluorine atoms to the polymer compound having a non-three-dimensional crosslinked structure having fluorine atoms is preferably 5:95 to 50:50, and 10:90 to 40:60 is more preferable, and 15:85 to 30:70 is still more preferable.
The polymer compound having a non-three-dimensional crosslinked structure having a fluorine atom may be only one kind or two or more kinds. In the case of two or more types, the total is preferably in the above range.
次に、本発明の仮接着用組成物について説明する。
本発明の仮接着用組成物は、ポリイミド樹脂、ポリアミドイミド樹脂、ポリベンズイミダゾール樹脂およびポリベンゾオキサゾール樹脂から選ばれる少なくとも1種を含む複素環含有樹脂と、マレイミド樹脂を50~100質量%含む架橋成分と、溶剤とを含有する。
本発明の仮接着用組成物を用いることで、上述した本発明の仮接着膜における接着領域を形成することができる。 <Composition for temporary adhesion>
Next, the temporary bonding composition of the present invention will be described.
The temporary bonding composition of the present invention includes a heterocyclic ring-containing resin containing at least one selected from a polyimide resin, a polyamideimide resin, a polybenzimidazole resin, and a polybenzoxazole resin, and a crosslink containing 50 to 100% by mass of a maleimide resin. Contains ingredients and solvent.
By using the temporary bonding composition of the present invention, an adhesive region in the temporary adhesive film of the present invention described above can be formed.
複素環含有樹脂は、ポリイミド樹脂、ポリアミドイミド樹脂、ポリベンズイミダゾール樹脂およびポリベンゾオキサゾール樹脂から選ばれる1種以上が用いられる。これらの具体例は、接着領域の項に記載したものが好適に用いられる。なかでも、ポリイミド樹脂が好ましい。また、ポリイミド樹脂は、γ-ブチロラクトン、シクロペンタノン、N-メチルピロリドン、シクロヘキサノン、グリコールエーテル、ジメチルスルホキシドおよびテトラメチルウレアから選ばれる1種以上溶剤に対する25℃での溶解度が10g/100gSolvent以上のポリイミド樹脂が好ましい。
複素環含有樹脂の含有量は、仮接着用組成物の全固形分量(溶剤を除いた量)に対し、1~99質量%が好ましく、10~90質量%がより好ましく、25~75質量%が特に好ましい。 << Heterocyclic ring-containing resin >>
As the heterocyclic ring-containing resin, one or more selected from polyimide resins, polyamideimide resins, polybenzimidazole resins, and polybenzoxazole resins are used. As these specific examples, those described in the section of the adhesion region are preferably used. Of these, polyimide resin is preferable. The polyimide resin is a polyimide having a solubility at 25 ° C. of 10 g / 100 g Solvent or more in one or more solvents selected from γ-butyrolactone, cyclopentanone, N-methylpyrrolidone, cyclohexanone, glycol ether, dimethyl sulfoxide and tetramethyl urea. Resins are preferred.
The content of the heterocyclic ring-containing resin is preferably 1 to 99% by mass, more preferably 10 to 90% by mass, and more preferably 25 to 75% by mass with respect to the total solid content (excluding the solvent) of the temporary bonding composition. Is particularly preferred.
架橋成分は、マレイミド樹脂を50~100質量%含むものが用いられる。
ここで、マレイミド樹脂は、ビスマレイミド樹脂が好ましい。マレイミド樹脂の具体例は、接着領域の項に記載したものが好適に用いられる。
架橋成分は、マレイミド樹脂の含有量が、全架橋成分の80~100質量%が好ましい。最も好ましくは架橋成分が実質的にマレイミド樹脂のみで構成されることである。なお、実質的にマレイミド樹脂のみで構成されるとは、マレイミド樹脂以外の架橋成分の含有量が、例えば1質量%以下が好ましく、0.5質量%以下がより好ましく、0.1質量%以下が特に好ましい。マレイミド樹脂以外の架橋成分としては、接着領域の他の架橋成分の項に記載したものが好適に用いられる。
マレイミド樹脂の含有量は、仮接着用組成物の全固形分量(溶剤を除いた量)に対し、1~99質量%が好ましく、10~90質量%がより好ましく、25~75質量%が特に好ましい。 << Crosslinking component >>
As the crosslinking component, one containing 50 to 100% by mass of maleimide resin is used.
Here, the maleimide resin is preferably a bismaleimide resin. As specific examples of the maleimide resin, those described in the section of the adhesion region are preferably used.
The crosslinking component preferably has a maleimide resin content of 80 to 100% by mass of the total crosslinking component. Most preferably, the crosslinking component is substantially composed only of maleimide resin. In addition, it is substantially comprised only with maleimide resin that content of crosslinking components other than maleimide resin is, for example, preferably 1% by mass or less, more preferably 0.5% by mass or less, and 0.1% by mass or less. Is particularly preferred. As the crosslinking component other than the maleimide resin, those described in the section of other crosslinking components in the adhesion region are preferably used.
The content of the maleimide resin is preferably 1 to 99% by mass, more preferably 10 to 90% by mass, and particularly preferably 25 to 75% by mass with respect to the total solid content (excluding the solvent) of the temporary bonding composition. preferable.
溶剤は、公知のものを制限なく使用できる。例えば、酢酸エチル、酢酸-n-ブチル、酢酸イソブチル、ギ酸アミル、酢酸イソアミル、酢酸イソブチル、プロピオン酸ブチル、酪酸イソプロピル、酪酸エチル、酪酸ブチル、乳酸メチル、乳酸エチル、オキシ酢酸アルキル(例:オキシ酢酸メチル、オキシ酢酸エチル、オキシ酢酸ブチル(例えば、メトキシ酢酸メチル、メトキシ酢酸エチル、メトキシ酢酸ブチル、エトキシ酢酸メチル、エトキシ酢酸エチル等))、3-オキシプロピオン酸アルキルエステル類(例:3-オキシプロピオン酸メチル、3-オキシプロピオン酸エチル等(例えば、3-メトキシプロピオン酸メチル、3-メトキシプロピオン酸エチル、3-エトキシプロピオン酸メチル、3-エトキシプロピオン酸エチル等))、2-オキシプロピオン酸アルキルエステル類(例:2-オキシプロピオン酸メチル、2-オキシプロピオン酸エチル、2-オキシプロピオン酸プロピル等(例えば、2-メトキシプロピオン酸メチル、2-メトキシプロピオン酸エチル、2-メトキシプロピオン酸プロピル、2-エトキシプロピオン酸メチル、2-エトキシプロピオン酸エチル))、2-オキシ-2-メチルプロピオン酸メチルおよび2-オキシ-2-メチルプロピオン酸エチル(例えば、2-メトキシ-2-メチルプロピオン酸メチル、2-エトキシ-2-メチルプロピオン酸エチル等)、ピルビン酸メチル、ピルビン酸エチル、ピルビン酸プロピル、アセト酢酸メチル、アセト酢酸エチル、2-オキソブタン酸メチル、2-オキソブタン酸エチル、PGMEA(1-メトキシ-2-プロピルアセテート)等のエステル類;
ジエチレングリコールジメチルエーテル、テトラヒドロフラン、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、メチルセロソルブアセテート、エチルセロソルブアセテート、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、ジエチレングリコールモノブチルエーテル、プロピレングリコールモノメチルエーテル、プロピレングリコールモノメチルエーテルアセテート、プロピレングリコールモノエチルエーテルアセテート、プロピレングリコールモノプロピルエーテルアセテート等のエーテル類;
メチルアミルケトン、メチルエチルケトン、2-ブタノン、シクロヘキサノン、2-ヘプタノン、3-ヘプタノン、N-メチル-2-ピロリドン等のケトン類;
トルエン、キシレン、アニソール、メシチレン、リモネン等の芳香族炭化水素類;
N,N-ジメチルアセトアミド等が好適に挙げられる。
中でも、アニソール、N-メチル-2-ピロリドン、N,N-ジメチルアセトアミド、2-ブタノン、メチルアミルケトン、リモネン、メシチレン、メチルエチルケトン、PGMEA(1-メトキシ-2-プロピルアセテート)等が好ましく、N-メチル-2-ピロリドン、N,N-ジメチルアセトアミド、メチルアミルケトン、リモネンが好ましい。
これらの溶剤は、塗布面状の改良などの観点から、2種以上を混合する形態も好ましい。
溶剤の含有量は、仮接着用組成物の固形分濃度が5~60質量%になるように使用されることが好ましい。
溶剤は1種類のみでもよいし、2種類以上であってもよい。溶剤が2種類以上の場合は、その合計が上記範囲であることが好ましい。 << Solvent >>
A known solvent can be used without limitation. For example, ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, alkyl oxyacetate (eg, oxyacetic acid) Methyl, ethyl oxyacetate, butyl oxyacetate (eg, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate)), 3-oxypropionic acid alkyl esters (eg 3-oxypropion) Methyl, ethyl 3-oxypropionate (eg, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate)), alkyl 2-oxypropionate Esters Examples: methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, etc. (for example, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, 2-ethoxy Methyl propionate, ethyl 2-ethoxypropionate)), methyl 2-oxy-2-methylpropionate and ethyl 2-oxy-2-methylpropionate (for example, methyl 2-methoxy-2-methylpropionate, 2- Ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, PGMEA (1-methoxy-2 -Propyl acetate) Kind;
Diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol Ethers such as monoethyl ether acetate and propylene glycol monopropyl ether acetate;
Ketones such as methyl amyl ketone, methyl ethyl ketone, 2-butanone, cyclohexanone, 2-heptanone, 3-heptanone, N-methyl-2-pyrrolidone;
Aromatic hydrocarbons such as toluene, xylene, anisole, mesitylene, limonene;
Preferable examples include N, N-dimethylacetamide.
Of these, anisole, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, 2-butanone, methyl amyl ketone, limonene, mesitylene, methyl ethyl ketone, PGMEA (1-methoxy-2-propyl acetate) and the like are preferable. Methyl-2-pyrrolidone, N, N-dimethylacetamide, methyl amyl ketone and limonene are preferred.
These solvents are also preferably in a form of mixing two or more kinds from the viewpoint of improving the coated surface.
The solvent content is preferably used such that the solid content concentration of the temporary bonding composition is 5 to 60% by mass.
One type of solvent may be sufficient and two or more types may be sufficient. When there are two or more solvents, the total is preferably in the above range.
仮接着用組成物は、さらに、熱重合開始剤を含有することが好ましい。熱重合開始剤を含有することで、より耐熱性、耐薬性に優れた仮接着膜を形成することができる。熱重合開始剤は、接着領域の項に記載したものが好適に用いられ、好ましい範囲も同様である。
熱重合開始剤の含有量は、仮接着用組成物の全固形分量(溶剤を除いた量)に対し、0.001~1質量%が好ましく、0.01~0.5質量%がより好ましく、0.05~0.1質量%が特に好ましい。 << Thermal polymerization initiator >>
It is preferable that the temporary bonding composition further contains a thermal polymerization initiator. By containing a thermal polymerization initiator, a temporary adhesive film having more excellent heat resistance and chemical resistance can be formed. As the thermal polymerization initiator, those described in the section of the adhesion region are preferably used, and the preferred range is also the same.
The content of the thermal polymerization initiator is preferably 0.001 to 1% by weight, more preferably 0.01 to 0.5% by weight, based on the total solid content (excluding the solvent) of the temporary bonding composition. 0.05 to 0.1% by mass is particularly preferable.
仮接着用組成物は、さらに、離型成分を含有することが好ましい。離型成分を含有することで、仮接着用組成物を膜状に適用した際に、離型成分が表層に偏在して、接着領域の表層に、離型領域が偏在してなる仮接着膜を形成することができる。
離型成分は、フッ素原子およびケイ素原子から選ばれる少なくとも一種を含有する材料が好ましい。フッ素原子およびケイ素原子から選ばれる少なくとも一種を含有する材料としては、フッ素原子またはケイ素原子を有する重合性モノマーなどが挙げられる。フッ素系シランカップリング剤がより好ましい。 << Release component >>
It is preferable that the temporary bonding composition further contains a release component. By including a release component, when the temporary bonding composition is applied in the form of a film, the release component is unevenly distributed on the surface layer, and the release region is unevenly distributed on the surface layer of the bonded region Can be formed.
The release component is preferably a material containing at least one selected from fluorine atoms and silicon atoms. Examples of the material containing at least one selected from a fluorine atom and a silicon atom include polymerizable monomers having a fluorine atom or a silicon atom. A fluorine-based silane coupling agent is more preferable.
フッ素原子またはケイ素原子を有する重合性モノマーは、フッ素原子またはケイ素原子が一分子中に1個以上含まれるラジカル重合性モノマーまたはオリゴマーであることが好ましく、フッ素原子が一分子中に2個以上含まれる、一般的にパーフルオロ基と呼ばれる基を有している重合性モノマーであることが特に好ましい。 <<< Polymerizable monomer having fluorine atom or silicon atom >>>
The polymerizable monomer having a fluorine atom or a silicon atom is preferably a radical polymerizable monomer or oligomer in which one or more fluorine atoms or silicon atoms are contained in one molecule, and two or more fluorine atoms are contained in one molecule. Particularly preferred is a polymerizable monomer having a group generally called a perfluoro group.
フッ素原子を有する重合性モノマーは、公知のモノマーから選択することができ、重合性基を有するモノマーが好ましく、フッ素系シランカップリング剤がより好ましい。重合性基としては例えば、水酸基又は加水分解可能な基を有するシリル基(例えばアルコキシシリル基、アシルオキシシリル基等)、反応性不飽和二重結合を有する基((メタ)アクリロイル基、アリル基、ビニルオキシ基等)、開環重合反応性基(エポキシ基、オキセタニル基、オキサゾリル基等)、活性水素原子を有する基(たとえば水酸基、カルボキシル基、アミノ基、カルバモイル基、メルカプト基、β-ケトエステル基、ヒドロシリル基、シラノール基等)、酸無水物、求核剤によって置換され得る基(活性ハロゲン原子、スルホン酸エステル等)等が挙げられる。 <<<<< Polymerizable monomer having a fluorine atom >>>>
The polymerizable monomer having a fluorine atom can be selected from known monomers, 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, alkoxysilyl group, acyloxysilyl group, etc.), a group having a reactive unsaturated double bond ((meth) acryloyl group, allyl group, Vinyloxy groups, etc.), ring-opening polymerization reactive groups (epoxy groups, oxetanyl groups, oxazolyl groups, etc.), groups having active hydrogen atoms (for example, hydroxyl groups, carboxyl groups, amino groups, carbamoyl groups, mercapto groups, β-ketoester groups, Hydrosilyl groups, silanol groups, etc.), acid anhydrides, groups that can be substituted by nucleophiles (active halogen atoms, sulfonate esters, etc.) and the like.
一般式(I):Rf{-L-Y}n
(式中、Rfは少なくとも炭素原子及びフッ素原子を含み、酸素原子及び水素原子のうちいずれかを含んでも良い、鎖状又は環状のn価の基を表し、nは2以上の整数を表す。Lは単結合又は二価の連結基を表す。Yは重合性基を表す。) The radically polymerizable monomer having a fluorine atom is preferably a compound represented by the following general formula (1).
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 either an oxygen atom or a hydrogen atom, and n represents an integer of 2 or more. L represents a single bond or a divalent linking group, and Y represents a polymerizable group.)
Lは単結合又は二価の連結基を表す。二価の連結基としては、2価の脂肪族基、2価の芳香族基、-O-、-S-、-CO-、-N(R)-、及びこれらを2種以上組み合わせて得られる2価の連結基を表す。ただし、Rは水素原子又は炭素数1~5のアルキル基を表す。
Lがアルキレン基又はアリーレン基を有する場合、アルキレン基及びアリーレン基はハロゲン原子で置換されていることが好ましく、フッ素原子で置換されていることがより好ましい。
Rfは、少なくとも炭素原子及びフッ素原子を含み、酸素原子及び水素原子のうちいずれかを含んでも良い、鎖状又は環状のn価の基を表す。Rfは、フッ素原子を有する繰り返し単位を有する線状または分岐状の高分子構造であってもよい。 Examples of the alkyl group are preferably alkyl groups having 1 to 8 carbon atoms. For example, a methyl group, an ethyl group, a propyl group, an octyl group, an isopropyl group, a tert-butyl group, an isopentyl group, a 2-ethylhexyl group, Examples thereof include 2-methylhexyl group and cyclopentyl group. Examples of the aryl group are preferably aryl groups having 6 to 12 carbon atoms, and examples thereof include a phenyl group, a 1-naphthyl group, and a 2-naphthyl group. R 901 to R 903 are particularly preferably a hydrogen atom or a methyl group.
L represents a single bond or a divalent linking group. As the divalent linking group, a divalent aliphatic group, a divalent aromatic group, —O—, —S—, —CO—, —N (R) —, or a combination of two or more thereof can be obtained. Represents a divalent linking group. R represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.
When L has an alkylene group or an arylene group, the alkylene group and the arylene group are preferably substituted with a halogen atom, and more preferably substituted with a fluorine atom.
Rf represents a chain or cyclic n-valent group that contains at least a carbon atom and a fluorine atom, and may contain either an oxygen atom or a hydrogen atom. Rf may be a linear or branched polymer structure having a repeating unit having a fluorine atom.
(構造式(1)中、R1は、水素原子、またはメチル基を表す。R2は、-CpH2p-、-C(CpH2p+1)H-、-CH2C(CpH2p+1)H-、または-CH2CH2O-を表す。Rfは、-CnF2n+1、-(CF2)nH、-CnF2n+1-CF3、-(CF2)pOCnH2nCiF2i+1、-(CF2)pOCmH2mCiF2iH、-N(CpH2p+1)COCnF2n+1、または、-N(CpH2p+1)SO2CnF2n+1を表す。ただし、pは1~10の整数、nは1~16の整数、mは0~10の整数、iは0~16の整数をそれぞれ表す。) 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—, where R f is —C n F 2n + 1 , — (CF 2 ) n H, —C n F 2n + 1 —CF 3, - (CF 2) p OC n H 2n C i F 2i + 1, - (CF 2) p OC m H 2m C i F 2i H, -N (C p H 2p + 1) COC n F 2n + 1, or, -N (C p H 2p + 1) represents the SO 2 C n F 2n + 1 . Here, p is an integer of 1 ~ 10, n is an integer of 1 ~ 16, m is 0 to 10 integer I represents an integer of 0 to 16, respectively.)
(構造式(2)中、Rgは、炭素数1~20のフルオロアルキル基を表す。) CF 2 = CFOR g. Structural formula (2)
(In the structural formula (2), R g represents a fluoroalkyl group having 1 to 20 carbon atoms.)
(構造式(3)中、Rgは、炭素数1~20のフルオロアルキル基を表す。) CH 2 = CHR g ... Structural formula (3)
(In the structural formula (3), R g represents a fluoroalkyl group having 1 to 20 carbon atoms.)
(構造式(4)中、R3およびR4は、水素原子、またはメチル基を表す。R5およびR6は、-CqH2q-、-C(CqH2q+1)H-、-CH2C(CqH2q+1)H-または-CH2CH2O-、Rjは-CtF2tを表す。qは1~10の整数であり、tは1~16の整数である。) 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 of 1 to 10, and t is 1 to 16 Is an integer.)
(構造式(5)中、R7およびR8は、水素原子、またはメチル基を表す。Rkは-CyF2y+1である。yは1~16の整数である。) CH 2 = CHR 7 COOCH 2 (CH 2 R k ) CHOCOCR 8 = CH 2. Structural formula (5)
(In the structural formula (5), R 7 and R 8 are, .R k representing a hydrogen atom or a methyl group, is .y is -CyF 2y + 1 is an integer of 1 to 16.)
式(7)中、R5、R6、R7は、それぞれ独立して水素原子、ハロゲン原子、水酸基、又は1価の有機基を表し、Y1は、単結合、または、-CO-、-O-、-NH-、2価の脂肪族基、2価の芳香族基およびそれらの組み合わせからなる群より選ばれる2価の連結基を表す。Rfは、フッ素原子、又は、フッ素原子を有する1価の有機基を表す。
式(10)中、R8、R9、R10、R11、R12、R13は、それぞれ独立して水素原子、ハロゲン原子、水酸基、又は1価の有機基を表し、Y2およびY3は、単結合、または、-CO-、-O-、-NH-、2価の脂肪族基、2価の芳香族基およびそれらの組み合わせからなる群より選ばれる2価の連結基を表す。Rfは、フッ素原子を有する2価の有機基を表す。 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 R 1 , R 2 , R 3 , At least one of 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 represents a hydrogen atom, a halogen atom, a hydroxyl group or a monovalent organic group, and Y 1 represents a single bond, —CO—, — It represents a divalent linking group selected from the group consisting of O—, —NH—, a divalent aliphatic group, a divalent aromatic group, and combinations thereof. Rf represents a fluorine atom or a monovalent organic group having a fluorine atom.
In the 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, Y 2 and Y 3 represents a single bond or a divalent linking group selected from the group consisting of —CO—, —O—, —NH—, a divalent aliphatic group, a divalent aromatic group, and combinations thereof. . Rf represents a divalent organic group having a fluorine atom.
より具体的な例としては、下記の構造が単独又は複数組み合わさって構成される有機基を挙げることができる。
1価の有機基は、更に置換基を有してもよく、導入可能な置換基としては、例えば、ハロゲン原子、ヒドロキシ基、カルボキシ基、スルホナト基、ニトロ基、シアノ基、アミド基、アミノ基、アルキル基、アルケニル基、アルキニル基、アリール基、置換オキシ基、置換スルホニル基、置換カルボニル基、置換スルフィニル基、スルホ基、ホスホノ基、ホスホナト基、シリル基、複素環基、等が挙げられる。また有機基は、エーテル結合、エステル結合、ウレイド結合を含んでいてもよい。 The monovalent organic group in the formulas (6), (7), and (10) is preferably an organic group composed of 3 to 10 non-metallic atoms, for example, 1 to 60 carbon atoms. At least one or more selected from atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to 100 hydrogen atoms, and 0 to 20 sulfur atoms Examples include organic groups composed of elements.
More specific examples include organic groups composed of the following structures singly 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 hydroxy group, a carboxy group, a sulfonate group, a nitro group, a cyano group, an amide group, and an amino group. , Alkyl group, alkenyl group, alkynyl group, aryl group, substituted oxy group, substituted sulfonyl group, substituted carbonyl group, substituted sulfinyl group, sulfo group, phosphono group, phosphonato group, silyl group, heterocyclic group, and the like. The organic group may contain an ether bond, an ester bond, or a ureido bond.
アルキル基の例は、炭素数1~8のアルキル基であることが好ましく、例えば、メチル基、エチル基、プロピル基、オクチル基、イソプロピル基、tert-ブチル基、イソペンチル基、2-エチルヘキシル基、2-メチルヘキシル基、シクロペンチル基等が挙げられる。アリール基の例は、炭素数6~12のアリール基であることが好ましく、フェニル基、1-ナフチル基、2-ナフチル基などが挙げられる。R901~R903はとしては、なかでも、水素原子またはメチル基が好ましい。 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 in formula (10) As the monovalent organic group represented by 11 , R 12 and R 13 , an alkyl group or an aryl group is preferable.
Examples of the alkyl group are preferably alkyl groups having 1 to 8 carbon atoms. For example, a methyl group, an ethyl group, a propyl group, an octyl group, an isopropyl group, a tert-butyl group, an isopentyl group, a 2-ethylhexyl group, Examples thereof include 2-methylhexyl group and cyclopentyl group. Examples of the aryl group are preferably aryl groups having 6 to 12 carbon atoms, and examples thereof include a phenyl group, a 1-naphthyl group, and a 2-naphthyl group. R 901 to R 903 are particularly preferably a hydrogen atom or a methyl group.
L2:-CO-NH-2価の脂肪族基-O-CO-
L3:-CO-2価の脂肪族基-O-CO-
L4:-CO-O-2価の脂肪族基-O-CO-
L5:-2価の脂肪族基-O-CO-
L6:-CO-NH-2価の芳香族基-O-CO-
L7:-CO-2価の芳香族基-O-CO-
L8:-2価の芳香族基-O-CO-
L9:-CO-O-2価の脂肪族基-CO-O-2価の脂肪族基-O-CO-
L10:-CO-O-2価の脂肪族基-O-CO-2価の脂肪族基-O-CO-
L11:-CO-O-2価の芳香族基-CO-O-2価の脂肪族基-O-CO-
L12:-CO-O-2価の芳香族基-O-CO-2価の脂肪族基-O-CO-
L13:-CO-O-2価の脂肪族基-CO-O-2価の芳香族基-O-CO-
L14:-CO-O-2価の脂肪族基-O-CO-2価の芳香族基-O-CO-
L15:-CO-O-2価の芳香族基-CO-O-2価の芳香族基-O-CO-
L16:-CO-O-2価の芳香族基-O-CO-2価の芳香族基-O-CO-
L17:-CO-O-2価の芳香族基-O-CO-NH-2価の脂肪族基-O-CO-
L18:-CO-O-2価の脂肪族基-O-CO-NH-2価の脂肪族基-O-CO-
L19:-2価の芳香族基-2価の脂肪族基
L20:-2価の芳香族基-2価の脂肪族基-O-2価の脂肪族基-
L21:-2価の芳香族基-2価の脂肪族基-O-2価の脂肪族基-O-
L22:-CO-O-2価の脂肪族基-
L23:-CO-O-2価の脂肪族基-O- L1: -CO-NH-divalent aliphatic group -O-CO-NH-divalent aliphatic group -O-CO-
L2: —CO—NH-divalent aliphatic group —O—CO—
L3: —CO-2 valent aliphatic group —O—CO—
L4: —CO—O-2 valent aliphatic group —O—CO—
L5: -valent aliphatic group -O-CO-
L6: —CO—NH-divalent aromatic group —O—CO—
L7: —CO-2 valent aromatic group —O—CO—
L8: -valent aromatic group -O-CO-
L9: -CO-O-2 valent aliphatic group -CO-O-2 valent aliphatic group -O-CO-
L10: -CO-O-2 valent aliphatic group -O-CO-2 valent aliphatic group -O-CO-
L11: -CO-O-2 valent aromatic group -CO-O-2 valent aliphatic group -O-CO-
L12: -CO-O-2 valent aromatic group -O-CO-2 valent aliphatic group -O-CO-
L13: -CO-O-2 valent aliphatic group -CO-O-2 valent aromatic group -O-CO-
L14: -CO-O-2 valent aliphatic group -O-CO-2 valent aromatic group -O-CO-
L15: -CO-O-2 valent aromatic group -CO-O-2 valent aromatic group -O-CO-
L16: -CO-O-2 valent aromatic group -O-CO-2 valent aromatic group -O-CO-
L17: -CO-O-2 divalent aromatic group -O-CO-NH-2 divalent aliphatic group -O-CO-
L18: -CO-O-2 valent aliphatic group -O-CO-NH-2 valent aliphatic group -O-CO-
L19: -2-valent aromatic group -2-valent aliphatic group L20: -2-valent aromatic group -2-valent aliphatic group -O-2-valent aliphatic group-
L21: a bivalent aromatic group, a bivalent aliphatic group, an O-2 valent aliphatic group, and -O-
L22: -CO-O-2 valent aliphatic group-
L23: —CO—O-2 valent aliphatic group —O—
2価の脂肪族基は、環状構造よりも鎖状構造の方が好ましく、さらに分岐を有する鎖状構造よりも直鎖状構造の方が好ましい。2価の脂肪族基の炭素原子数は、1~20であることが好ましく、1~15であることがより好ましく、1~12であることがさらに好ましく、1~10であることがさらにまた好ましく、1~8であることがよりさらに好ましく、1~4であることが特に好ましい。
2価の脂肪族基の置換基の例としては、ハロゲン原子(F、Cl、Br、I)、ヒドロキシ基、カルボキシ基、アミノ基、シアノ基、アリール基、アルコキシ基、アリールオキシ基、アシル基、アルコキシカルボニル基、アリールオキシカルボニル基、アシルオキシ基、モノアルキルアミノ基、ジアルキルアミノ基、アリールアミノ基およびジアリールアミノ基等が挙げられる。 Here, the divalent aliphatic group means an alkylene group, a substituted alkylene group, an alkenylene group, a substituted alkenylene group, an alkynylene group, a substituted alkynylene group or a polyalkyleneoxy group. Of these, an alkylene group, a substituted alkylene group, an alkenylene group, and a substituted alkenylene group are preferable, and an alkylene group and a substituted alkylene group are more preferable.
The divalent aliphatic group preferably has a chain structure rather than a cyclic structure, and more preferably has a straight chain structure than a branched chain structure. The number of carbon atoms in the divalent aliphatic group is preferably 1-20, more preferably 1-15, still more preferably 1-12, and even more preferably 1-10. It is preferably 1 to 8, more preferably 1 to 4, and particularly preferably 1 to 4.
Examples of the substituent of the divalent aliphatic group include a halogen atom (F, Cl, Br, I), a hydroxy group, a carboxy group, an amino group, a cyano group, an aryl group, an alkoxy group, an aryloxy group, and an acyl group. , Alkoxycarbonyl group, aryloxycarbonyl group, acyloxy group, monoalkylamino group, dialkylamino group, arylamino group and diarylamino group.
Tは一般式(9)で表されるラジカル重合性官能基を表すことが好ましい。 The alkyl group as R 801 to R 803 is preferably an alkyl group having 1 to 6 carbon atoms.
T preferably represents a radical polymerizable functional group represented by the general formula (9).
L2:-CO-NH-2価の脂肪族基-O-CO-
L3:-CO-2価の脂肪族基-O-CO-
L4:-CO-O-2価の脂肪族基-O-CO-
L5:-2価の脂肪族基-O-CO-
L6:-CO-NH-2価の芳香族基-O-CO-
L7:-CO-2価の芳香族基-O-CO-
L8:-2価の芳香族基-O-CO-
L9:-CO-O-2価の脂肪族基-CO-O-2価の脂肪族基-O-CO-
L10:-CO-O-2価の脂肪族基-O-CO-2価の脂肪族基-O-CO-
L11:-CO-O-2価の芳香族基-CO-O-2価の脂肪族基-O-CO-
L12:-CO-O-2価の芳香族基-O-CO-2価の脂肪族基-O-CO-
L13:-CO-O-2価の脂肪族基-CO-O-2価の芳香族基-O-CO-
L14:-CO-O-2価の脂肪族基-O-CO-2価の芳香族基-O-CO-
L15:-CO-O-2価の芳香族基-CO-O-2価の芳香族基-O-CO-
L16:-CO-O-2価の芳香族基-O-CO-2価の芳香族基-O-CO-
L17:-CO-O-2価の芳香族基-O-CO-NH-2価の脂肪族基-O-CO-
L18:-CO-O-2価の脂肪族基-O-CO-NH-2価の脂肪族基-O-CO- L1: -CO-NH-divalent aliphatic group -O-CO-NH-divalent aliphatic group -O-CO-
L2: —CO—NH-divalent aliphatic group —O—CO—
L3: —CO-2 valent aliphatic group —O—CO—
L4: —CO—O-2 valent aliphatic group —O—CO—
L5: -valent aliphatic group -O-CO-
L6: —CO—NH-divalent aromatic group —O—CO—
L7: —CO-2 valent aromatic group —O—CO—
L8: -valent aromatic group -O-CO-
L9: -CO-O-2 valent aliphatic group -CO-O-2 valent aliphatic group -O-CO-
L10: -CO-O-2 valent aliphatic group -O-CO-2 valent aliphatic group -O-CO-
L11: -CO-O-2 valent aromatic group -CO-O-2 valent aliphatic group -O-CO-
L12: -CO-O-2 valent aromatic group -O-CO-2 valent aliphatic group -O-CO-
L13: -CO-O-2 valent aliphatic group -CO-O-2 valent aromatic group -O-CO-
L14: -CO-O-2 valent aliphatic group -O-CO-2 valent aromatic group -O-CO-
L15: -CO-O-2 valent aromatic group -CO-O-2 valent aromatic group -O-CO-
L16: -CO-O-2 valent aromatic group -O-CO-2 valent aromatic group -O-CO-
L17: -CO-O-2 divalent aromatic group -O-CO-NH-2 divalent aliphatic group -O-CO-
L18: -CO-O-2 valent aliphatic group -O-CO-NH-2 valent aliphatic group -O-CO-
2価の脂肪族基は、環状構造よりも鎖状構造の方が好ましく、さらに分岐を有する鎖状構造よりも直鎖状構造の方が好ましい。2価の脂肪族基の炭素原子数は、1~20であることが好ましく、1~15であることがより好ましく、1~12であることがさらに好ましく、1~10であることがさらにまた好ましく、1~8であることがよりさらに好ましく、1~4であることが特に好ましい。
2価の脂肪族基の置換基の例としては、ハロゲン原子(F、Cl、Br、I)、ヒドロキシ基、カルボキシ基、アミノ基、シアノ基、アリール基、アルコキシ基、アリールオキシ基、アシル基、アルコキシカルボニル基、アリールオキシカルボニル基、アシルオキシ基、モノアルキルアミノ基、ジアルキルアミノ基、アリールアミノ基およびジアリールアミノ基等が挙げられる。 Here, the divalent aliphatic group means an alkylene group, a substituted alkylene group, an alkenylene group, a substituted alkenylene group, an alkynylene group, a substituted alkynylene group or a polyalkyleneoxy group. Of these, an alkylene group, a substituted alkylene group, an alkenylene group, and a substituted alkenylene group are preferable, and an alkylene group and a substituted alkylene group are more preferable.
The divalent aliphatic group preferably has a chain structure rather than a cyclic structure, and more preferably has a straight chain structure than a branched chain structure. The number of carbon atoms in the divalent aliphatic group is preferably 1-20, more preferably 1-15, still more preferably 1-12, and even more preferably 1-10. It is preferably 1 to 8, more preferably 1 to 4, and particularly preferably 1 to 4.
Examples of the substituent of the divalent aliphatic group include a halogen atom (F, Cl, Br, I), a hydroxy group, a carboxy group, an amino group, a cyano group, an aryl group, an alkoxy group, an aryloxy group, and an acyl group. , Alkoxycarbonyl group, aryloxycarbonyl group, acyloxy group, monoalkylamino group, dialkylamino group, arylamino group and diarylamino group.
フッ素原子を有するラジカル重合性モノマーまたはオリゴマーは1種類のみでもよいし、2種類以上であってもよい。重合性モノマーが2種類以上の場合は、その合計が上記範囲であることが好ましい。 When the release region-forming composition 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 preferably a release region. The content is preferably 0.01 to 15% by mass with respect to the total solid content of the forming composition. If it is 0.01 mass% or more, sufficient peelability is obtained. If it is 15 mass% or less, sufficient adhesive force will be obtained.
There may be only one kind of radically polymerizable monomer or oligomer having a fluorine atom, or two or more kinds. When there are two or more kinds of polymerizable monomers, the total is preferably in the above range.
本ケイ素原子を有するラジカル重合性モノマーまたはオリゴマーは、シリコーンモノマーまたはシリコーンオリゴマーであることが好ましく、例えば、ポリジメチルシロキサン結合の少なくとも片末端が(メタ)アクリロイル基およびスチリル基等のエチレン性不飽和基となっている化合物が挙げられ、(メタ)アクリロイル基を有する化合物が好ましい。 <<< Radically 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. For example, at least one terminal of a polydimethylsiloxane bond is an ethylenically unsaturated group such as a (meth) acryloyl group and a styryl group. And a compound having a (meth) acryloyl group is preferable.
Y201は、酸素原子、硫黄原子、または-N(R206)-を表す。R206は、一般式(i)のR104と同義であり、好ましい例も同様である。 Examples of the substituent that can be introduced include the same substituents as those described in formula (i).
Y 201 represents an oxygen atom, a sulfur atom, or —N (R 206 ) —. R 206 has the same meaning as R 104 in formula (i), and preferred examples thereof are also the same.
ケイ素原子を有するラジカル重合性モノマー又はオリゴマーは1種類のみでもよいし、2種類以上であってもよい。ケイ素原子を有するラジカル重合性モノマー又はオリゴマーが2種類以上の場合は、その合計が上記範囲であることが好ましい。 When the release region forming composition has a radical polymerizable monomer or oligomer having a silicon atom, the content of the radical polymerizable monomer or oligomer having a silicon atom is based on the total solid content of the release region forming composition. 0.01 to 15% by mass is preferable. If it is 0.01 mass% or more, sufficient peelability is obtained. If it is 15 mass% or less, sufficient adhesive force will be obtained.
There may be only one kind of radically polymerizable monomer or oligomer having a silicon atom, or two or more kinds. When there are two or more types of radically polymerizable monomers or oligomers having a silicon atom, the total is preferably in the above range.
仮接着用組成物は、さらに、界面活性剤を含有することが好ましい。界面活性剤は、接着領域の項に記載したものが好適に用いられ、好ましい範囲も同様である。
界面活性剤の含有量は、仮接着用組成物の全固形分量(溶剤を除いた量)に対し、0.001~1質量%が好ましく、0.01~0.5質量%がより好ましく、0.05~0.1質量%が特に好ましい。
界面活性剤は1種類のみでもよいし、2種類以上であってもよい。界面活性剤が2種類以上の場合は、その合計が上記範囲であることが好ましい。 << Surfactant >>
The temporary bonding composition preferably further contains a surfactant. As the surfactant, those described in the section of the adhesion region are preferably used, and the preferable range is also the same.
The content of the surfactant is preferably 0.001 to 1% by mass, more preferably 0.01 to 0.5% by mass, based on the total solid content (excluding the solvent) of the temporary bonding composition. 0.05 to 0.1% by mass is particularly preferable.
Only one type of surfactant may be used, or two or more types may be used. When two or more surfactants are used, the total is preferably in the above range.
仮接着用組成物は、さらに、酸化防止剤を含有することが好ましい。酸化防止剤は、接着領域の項に記載したものが好適に用いられ、好ましい範囲も同様である。
酸化防止剤の含有量は、仮接着用組成物の全固形分量(溶剤を除いた量)に対し、0.001~10質量%が好ましく、0.01~5質量%がより好ましく、0.1~1質量%が特に好ましい。
酸化防止剤は1種類のみでもよいし、2種類以上であってもよい。酸化防止剤が2種類以上の場合は、その合計が上記範囲であることが好ましい。 << Antioxidant >>
The temporary bonding composition preferably further contains an antioxidant. As the antioxidant, those described in the section of the adhesion region are preferably used, and the preferred range is also the same.
The content of the antioxidant is preferably from 0.001 to 10% by mass, more preferably from 0.01 to 5% by mass, based on the total solid content (excluding the solvent) of the temporary bonding composition. 1 to 1% by mass is particularly preferred.
One type of antioxidant may be sufficient and two or more types may be sufficient. When there are two or more kinds of antioxidants, the total is preferably within the above range.
仮接着用組成物は、高温での変形性を高め接着平坦性を向上させるために、可塑剤を含むことが好ましい。
可塑剤としては、フタル酸エステル、脂肪酸エステル、芳香族多価カルボン酸エステル、ポリエステルなどが使用できる。 << Plasticizer >>
The temporary bonding composition preferably contains a plasticizer in order to enhance the deformability at high temperature and improve the adhesion flatness.
As the plasticizer, phthalic acid esters, fatty acid esters, aromatic polycarboxylic acid esters, polyesters, and the like can be used.
脂肪酸エステルとしては例えば、ブチルステアレート、ユニスターM-9676、ユニスターM-2222SL、ユニスターH-476、ユニスターH-476D、パナセート800B、パナセート875、パナセート810(以上、日油製)、DBA、DIBA、DBS、DOA、DINA、DIDA、DOS、BXA、DOZ、DESU(以上、大八化学製)などが挙げられる。
芳香族多価カルボン酸エステルとしては、TOTM(大八化学製)、モノサイザーW-705(大八化学製)、UL-80、UL-100(ADEKA製)などが挙げられる。
ポリエステルとしては、ポリサイザーTD-1720、ポリサイザーS-2002、ポリサイザーS-2010(以上、DIC製)、BAA-15(大八化学製)などが挙げられる。
上記可塑剤の中では、DIDP、DIDA、TOTM、ユニスターM-2222SL、ポリサイザーTD-1720が好ましく、DIDA、TOTMがより好ましく、TOTMが特に好ましい。
可塑剤は1種のみを用いてもよいし、2種類以上を組み合わせてもよい。 Examples of phthalic acid esters include DMP, DEP, DBP, # 10, BBP, DOP, DINP, DIDP (above, manufactured by Daihachi Chemical), PL-200, DOIP (above, made by CG Esther), Sunsizer DUP (new) Nippon Rika).
Examples of fatty acid esters include butyl stearate, Unistar M-9676, Unistar M-2222SL, Unistar H-476, Unistar H-476D, Panaceto 800B, Panaceto 875, Panaceto 810 (above, NOF Corporation), DBA, DIBA, DBS, DOA, DINA, DIDA, DOS, BXA, DOZ, DESU (manufactured by Daihachi Chemical Co., Ltd.), and the like.
Examples of the aromatic polycarboxylic acid ester include TOTM (manufactured by Daihachi Chemical), monosizer W-705 (manufactured by Daihachi Chemical), UL-80, UL-100 (manufactured by ADEKA), and the like.
Examples of the polyester include Polycizer TD-1720, Polycizer S-2002, Polycizer S-2010 (above, manufactured by DIC), BAA-15 (produced by Daihachi Chemical).
Among the plasticizers, DIDP, DIDA, TOTM, Unistar M-2222SL and Polycizer TD-1720 are preferable, DIDA and TOTM are more preferable, and TOTM is particularly preferable.
Only one type of plasticizer may be used, or two or more types may be combined.
可塑剤は1種類のみでもよいし、2種類以上であってもよい。可塑剤が2種類以上の場合は、その合計が上記範囲であることが好ましい。 The content of the plasticizer is preferably 1 to 50.0% by mass and more preferably 5 to 20.0% by mass with respect to the total mass of the temporary bonding composition.
Only one type of plasticizer may be used, or two or more types may be used. When two or more plasticizers are used, the total is preferably within the above range.
本発明における仮接着用組成物は、本発明の効果を損なわない範囲で、必要に応じて、各種添加物、例えば、硬化剤、硬化触媒、充填剤、紫外線吸収剤、凝集防止剤等を配合することができる。これらの添加剤を配合する場合、その合計配合量は仮接着用組成物の固形分の3質量%以下とすることが好ましい。 << Other additives >>
The composition for temporary bonding in the present invention is blended with various additives such as a curing agent, a curing catalyst, a filler, an ultraviolet absorber, an anti-aggregation agent, etc. can do. When mix | blending these additives, it is preferable that the total compounding quantity shall be 3 mass% or less of solid content of the composition for temporary adhesion | attachment.
次に離型領域形成用組成物について説明する。
離型領域形成用組成物は、離型成分と溶剤とを含むことが好ましい。 <Composition for mold release region formation>
Next, the release region forming composition will be described.
The composition for forming a release region preferably contains a release component and a solvent.
離型成分は、フッ素原子およびケイ素原子から選ばれる少なくとも一種を含有する材料が好ましい。フッ素原子およびケイ素原子から選ばれる少なくとも一種を含有する材料としては、フッ素原子またはケイ素原子を有する重合性モノマーなどが挙げられる。フッ素系シランカップリング剤がより好ましい。フッ素系シランカップリング剤により、接着領域の表面に、離型領域の層を強固に形成できる。このため、接着領域の層と、離型領域の層との界面に溶剤が染み込みにくくなり、耐薬性に優れた仮接着膜を形成することができる。離型成分の詳細については、上述した仮接着用組成物の離型成分の項で説明したものと同様であり、好ましい範囲も同様である。
離型成分の含有量は、良好な剥離性の観点から、離型領域形成用組成物の全固形分に対して、5~100質量%が好ましく、50~100質量%がより好ましく、90~100質量%がさらに好ましい。 << Release component >>
The release component is preferably a material containing at least one selected from fluorine atoms and silicon atoms. Examples of the material containing at least one selected from a fluorine atom and a silicon atom include polymerizable monomers having a fluorine atom or a silicon atom. A fluorine-based silane coupling agent is more preferable. With the fluorine-based silane coupling agent, the release region layer can be firmly formed on the surface of the adhesion region. For this reason, it becomes difficult for a solvent to permeate into the interface between the layer in the adhesion region and the layer in the release region, and a temporary adhesive film having excellent chemical resistance can be formed. About the detail of a mold release component, it is the same as that of what was demonstrated by the term of the mold release component of the composition for temporary bonding mentioned above, and its preferable range is also the same.
The content of the mold release component is preferably 5 to 100% by mass, more preferably 50 to 100% by mass, more preferably 90 to 90% by mass with respect to the total solid content of the mold release region forming composition, from the viewpoint of good releasability. 100 mass% is more preferable.
溶剤は、離型領域を形成できれば、公知のものを制限なく使用でき、上述した仮接着用組成物における溶剤と同様のものを使用することができる。また、パーフルオロアルカンを使用することができる。中でも、N-メチル-2-ピロリドン、2-ブタノン、メチルアミルケトン、リモネン、1-メトキシ-2-プロピルアセテート、パーフルオロアルカン、メチルエチルケトンが好ましく、N-メチル-2-ピロリドン、2-ブタノン、メチルアミルケトン、リモネン、1-メトキシ-2-プロピルアセテートがより好ましい。
これらの溶剤は、塗布面状の改良などの観点から、2種以上を混合する形態も好ましい。 << Solvent >>
As long as the release region can be formed, 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. Perfluoroalkanes can also be used. Among them, N-methyl-2-pyrrolidone, 2-butanone, methyl amyl ketone, limonene, 1-methoxy-2-propyl acetate, perfluoroalkane, and methyl ethyl ketone are preferable. N-methyl-2-pyrrolidone, 2-butanone, methyl More preferred are amyl ketone, limonene and 1-methoxy-2-propyl acetate.
These solvents are also preferably in a form of mixing two or more kinds from the viewpoint of improving the coated surface.
離型領域形成用組成物は、上記の成分に加えて、さらに本発明の効果を損なわない範囲において、目的に応じて種々の化合物を含むことができる。例えば、熱重合開始剤、増感色素、連鎖移動剤、酸化防止剤、界面活性剤を好ましく使用することができる。これらは、上述したものを仮接着用組成物で説明したものを用いることができる。 << Other ingredients >>
In addition to the above components, the release region-forming composition can contain various compounds depending on the purpose within a range that does not impair the effects of the present invention. For example, a thermal polymerization initiator, a sensitizing dye, a chain transfer agent, an antioxidant, and a surfactant can be preferably used. As these, those described above with reference to the temporary bonding composition can be used.
次に、本発明の仮接着膜を形成するためのキットについて説明する。
本発明のキットは、上述した仮接着用組成物と、離型成分および溶剤を含む上述した離型領域形成用組成物とを含む。
支持基板上に、仮接着用組成物と、離型領域形成用組成物とを順次塗布することで、本発明の仮接着膜を作製することができる。
また、デバイスウエハに、離型領域形成用組成物と、仮接着用組成物とを順次塗布することでも、本発明の仮接着膜を作製することができる。
仮接着用組成物および離型領域形成用組成物のそれぞれの組成、好ましい範囲などは、前述したものと同様である。 <Kit>
Next, a kit for forming the temporary adhesive film of the present invention will be described.
The kit of this invention contains the composition for temporary adhesion mentioned above, and the composition for mold release area | region formation containing the mold release component and the solvent mentioned above.
The temporary adhesive film of the present invention can be produced by sequentially applying the temporary bonding composition and the release region forming composition onto the support substrate.
The temporary adhesive film of the present invention can also be produced by sequentially applying a release region forming composition and a temporary bonding composition to a device wafer.
The respective compositions and preferred ranges of the temporary bonding composition and the release region forming composition are the same as those described above.
次に、本発明の積層体について説明する。
本発明の積層体は、上述した本発明の仮接着膜の離型領域の表面に、デバイスウエハが積層されてなるものである。 <Laminate>
Next, the laminated body of this invention is demonstrated.
The laminate of the present invention is obtained by laminating a device wafer on the surface of the release region of the temporary adhesive film of the present invention described above.
デバイスウエハの表面には、機械構造や回路が形成されていてもよい。機械構造や回路が形成されたデバイスウエハとしては、例えば、MEMS(Micro Electro Mechanical Systems)、パワーデバイス、イメージセンサー、マイクロセンサー、LED、光学デバイス、インターポーザー、埋め込み型デバイス、マイクロデバイスなどが挙げられる。
デバイスウエハは、金属バンク等の構造を有していることが好ましい。本発明の仮接着膜は表面に構造を有しているデバイスウエハに対しても、安定して仮接着できるとともに、デバイスウエハに対する仮接着を容易に解除できる。構造の高さは、特に限定はないが、例えば、5~100μmが好ましい。
機械的または化学的な処理を施す前のデバイスウエハの膜厚は、500μm以上が好ましく、600μm以上がより好ましく、700μm以上が更に好ましい。
機械的または化学的な処理を施して薄膜化した後のデバイスウエハの膜厚は、例えば、500μm未満が好ましく、400μm以下がより好ましく、300μm以下が更に好ましい。 A known device wafer can be used without limitation, and examples thereof include a silicon substrate and a compound semiconductor substrate. Specific examples of the compound semiconductor substrate include a SiC substrate, a SiGe substrate, a ZnS substrate, a ZnSe substrate, a GaAs substrate, an InP substrate, and a GaN substrate.
A mechanical structure or a circuit may be formed on the surface of the device wafer. Examples of device wafers on which mechanical structures and circuits are formed include MEMS (Micro Electro Mechanical Systems), power devices, image sensors, micro sensors, LEDs, optical devices, interposers, embedded devices, and micro devices. .
The device wafer preferably has a structure such as a metal bank. The temporary adhesive film of the present invention can be stably temporarily bonded even to a device wafer having a structure on the surface, and can be easily released from temporary bonding to the device wafer. The height of the structure is not particularly limited, but is preferably 5 to 100 μm, for example.
The film thickness of the device wafer before the mechanical or chemical treatment is preferably 500 μm or more, more preferably 600 μm or more, and still more preferably 700 μm or more.
For example, the film thickness of the device wafer after thinning by mechanical or chemical treatment is preferably less than 500 μm, more preferably 400 μm or less, and even more preferably 300 μm or less.
支持基板の素材は特に限定されないが、例えば、シリコン基板、ガラス基板、金属基板、化合物半導体基板などが挙げられる。なかでも、半導体デバイスの基板として代表的に用いられるシリコン基板を汚染しにくい点や、半導体デバイスの製造工程において汎用されている静電チャックを使用できる点などを鑑みると、シリコン基板であることが好ましい。
支持基板の厚みは、特に限定されるものではないが、例えば、300μm~5mmが好ましい。 In the laminated body of the present invention, it is preferable that a support substrate is disposed on the surface of the temporary adhesive film on the side opposite to the laminated surface of the device wafer.
The material of the support substrate is not particularly limited, and examples thereof include a silicon substrate, a glass substrate, a metal substrate, and a compound semiconductor substrate. In particular, in view of the point that it is difficult to contaminate a silicon substrate that is typically used as a substrate for a semiconductor device, and that an electrostatic chuck that is widely used in the manufacturing process of a semiconductor device can be used, it may be a silicon substrate. preferable.
The thickness of the support substrate is not particularly limited, but is preferably 300 μm to 5 mm, for example.
次に、本発明のデバイスの製造方法について説明する。
本発明のデバイスの製造方法は、上述した本発明の仮接着用組成物を塗布する工程を含む。以下、本発明のデバイスの製造方法について、更に詳しく説明する。 <Device manufacturing method>
Next, the device manufacturing method of the present invention will be described.
The method for producing a device of the present invention includes a step of applying the above-described temporary bonding composition of the present invention. Hereinafter, the device manufacturing method of the present invention will be described in more detail.
支持基板-仮接着膜-デバイスウエハ積層体(以下、積層体ともいう)は、以下の(1)~(4)に示すいずれかの方法により製造できる。
(1)支持基板に、本発明の仮接着用組成物を塗布し、加熱(ベーク)して接着領域の層を形成する。仮接着用組成物の塗布方法は、スピンコート法、スプレー法、ローラーコート法、フローコート法、ドクターコート法、浸漬法など従来公知の方法が挙げられる。
次いで、接着領域の層上に、上述した離型領域形成用組成物を塗布し、加熱(ベーク)して離型領域の層を形成して本発明の仮接着膜を形成する。離型領域形成用組成物の塗布方法は、スピンコート法、スプレー法、ローラーコート法、フローコート法、ドクターコート法、浸漬法など従来公知の方法が挙げられる。
次いで、仮接着膜の支持基板が配置された面の反対側の面(すなわち、仮接着膜の離型領域側の面)を、デバイスウエハを加圧接着して、積層体を製造する。加圧接着条件は、例えば、温度100~200℃、圧力0.01~1MPa、時間1~15分が好ましい。
(2)デバイスウエハに、上述した離型領域形成用組成物を塗布し、加熱(ベーク)して離型領域の層を形成する。
次いで、離型領域の層上に、本発明の仮接着用組成物を塗布し、加熱(ベーク)して接着領域の層を形成し、本発明の仮接着膜を形成する。
次いで、仮接着膜のデバイスウエハが配置された面の反対側の面(すなわち、仮接着膜の接着領域側の面)を、支持基板を加圧接着して、積層体を製造する。加圧接着条件は、上述した条件が好ましい。
(3)支持基板およびデバイスウエハのいずれか一方の表面に、離型成分を含む本発明の仮接着用組成物を塗布し、加熱(ベーク)して、接着領域の表層に離型領域が偏在してなる仮接着膜を形成する。
次いで、仮接着膜の表面に、支持基板またはデバイスウエハを加圧接着して、積層体を製造する。加圧接着条件は、上述した条件が好ましい。
(4)デバイスウエハに、上述した離型領域形成用組成物を塗布し、加熱(ベーク)してデバイスウエハ上に離型領域の層を形成する。
次いで、支持基板に、上述した本発明の仮接着用組成物を塗布し、加熱(ベーク)して、支持基板上に接着領域の層を形成する。
次いで、デバイスウエハ上の離型領域と、支持基板上の接着領域とを加圧接着して仮接着膜を形成すると共に、積層体を製造する。加圧接着条件は、上述した条件が好ましい。 << Manufacture of Support Substrate-Temporary Adhesive Film-Device Wafer Laminate >>
A support substrate-temporary adhesive film-device wafer laminate (hereinafter also referred to as a laminate) can be produced by any of the following methods (1) to (4).
(1) The temporary adhesion composition of the present invention is applied to a support substrate and heated (baked) to form a layer of an adhesion region. Examples of the method for applying the temporary bonding composition include conventionally known methods such as spin coating, spraying, roller coating, flow coating, doctor coating, and dipping.
Next, the release region forming composition described above is applied on the layer of the adhesive region, and heated (baked) to form a layer of the release region, thereby forming the temporary adhesive film of the present invention. Examples of the application method of the release region forming composition include conventionally known methods such as spin coating, spraying, roller coating, flow coating, doctor coating, and dipping.
Next, the device wafer is pressure-bonded to the surface opposite to the surface on which the support substrate of the temporary adhesive film is disposed (that is, the surface of the temporary adhesive film on the release region side) to manufacture a laminate. The pressure bonding conditions are preferably, for example, a temperature of 100 to 200 ° C., a pressure of 0.01 to 1 MPa, and a time of 1 to 15 minutes.
(2) The above-described release region forming composition is applied to a device wafer and heated (baked) to form a release region layer.
Next, the temporary adhesion composition of the present invention is applied on the release area layer, and heated (baked) to form the adhesion area layer, thereby forming the temporary adhesion film of the present invention.
Next, the surface opposite to the surface on which the device wafer of the temporary adhesive film is disposed (that is, the surface on the adhesion region side of the temporary adhesive film) is pressure-bonded to the support substrate to produce a laminate. The pressure bonding conditions are preferably the above-described conditions.
(3) The temporary bonding composition of the present invention containing a release component is applied to the surface of either the support substrate or the device wafer, and heated (baked), so that the release area is unevenly distributed on the surface layer of the adhesive area. A temporary adhesive film is formed.
Next, a support substrate or a device wafer is pressure-bonded to the surface of the temporary adhesive film to produce a laminate. The pressure bonding conditions are preferably the above-described conditions.
(4) The mold release region forming composition described above is applied to a device wafer and heated (baked) to form a mold release layer layer on the device wafer.
Next, the above-described temporary adhesion composition of the present invention is applied to a support substrate and heated (baked) to form a layer of an adhesion region on the support substrate.
Next, the release area on the device wafer and the adhesion area on the support substrate are pressure-bonded to form a temporary adhesion film, and a laminate is manufactured. The pressure bonding conditions are preferably the above-described conditions.
デバイスウエハ60は、平均膜厚500μm以上の膜厚を有していることが好ましい。また、構造62は、デバイスチップやバンプと呼ばれるものであり、平均高さは5~100μmの範囲であることが好ましい。 As shown in FIG. 1A, the
The
また、機械的または化学的な処理として、薄膜化処理の後に、薄型デバイスウエハ60aの裏面61cからシリコン基板を貫通する貫通孔(図示せず)を形成し、この貫通孔内にシリコン貫通電極(図示せず)を形成する処理を行ってもよい。具体的には、加熱処理における最高到達温度は130℃~400℃が好ましく、180℃~350℃がより好ましい。加熱処理における最高到達温度は接着領域の軟化点よりも低い温度とされる。加熱処理は、最高到達温度での30秒~30分の加熱であることが好ましく、最高到達温度での1分~10分の加熱であることがより好ましい。 Next, the
Further, as a mechanical or chemical treatment, a through hole (not shown) penetrating the silicon substrate is formed from the
仮接着膜80の剥離は、引き剥がす等の物理的作用によって行われることが好ましい。すなわち、接着性支持体100に対して薄型デバイスウエハ60aを摺動させるか、あるいは、接着性支持体100から薄型デバイスウエハ60aを剥離することにより行うことが好ましい。上記方法により、仮接着膜80を、薄型デバイスウエハ60aの表面61aから剥離することができる。 Next, the temporary
The temporary
また、上述した実施形態において、離型層は単層構造であるが、離型層は多層構造であってもよい。
また、上述した実施形態においては、被処理部材として、シリコン基板を挙げたが、これに限定されるものではなく、デバイスの製造方法において、機械的または化学的な処理に供され得るいずれの被処理部材であっても良い。例えば、化合物半導体基板を挙げることもでき、化合物半導体基板の具体例としては、SiC基板、SiGe基板、ZnS基板、ZnSe基板、GaAs基板、InP基板、および、GaN基板などが挙げられる。
また、上述した実施形態においては、支持基板により支持されたシリコン基板に対する機械的または化学的な処理として、シリコン基板の薄膜化処理、および、シリコン貫通電極の形成処理を挙げたが、これらに限定されるものではなく、デバイスの製造方法において必要ないずれの処理も挙げられる。
その他、上述した実施形態において例示した、デバイスウエハにおけるデバイスチップの形状、寸法、数、配置箇所等は任意であり、限定されない。 The device manufacturing method of the present invention is not limited to the above-described embodiment, and appropriate modifications and improvements can be made.
In the embodiment described above, the release layer has a single layer structure, but the release layer may have a multilayer structure.
In the above-described embodiment, the silicon substrate is exemplified as the member to be processed. However, the present invention is not limited to this, and any member that can be subjected to mechanical or chemical treatment in the device manufacturing method is used. It may be a processing member. For example, a compound semiconductor substrate can also be mentioned, and specific examples of the compound semiconductor substrate include a SiC substrate, a SiGe substrate, a ZnS substrate, a ZnSe substrate, a GaAs substrate, an InP substrate, and a GaN substrate.
In the above-described embodiment, the silicon substrate thinning process and the silicon through electrode forming process are exemplified as the mechanical or chemical process for the silicon substrate supported by the support substrate. However, the present invention is not limited thereto. Any processing required in the device manufacturing method is included.
In addition, the shape, size, number, arrangement location, and the like of the device chip in the device wafer exemplified in the above-described embodiment are arbitrary and are not limited.
<接着領域の形成>
4インチSiウエハに、表1に示す組成の接着領域形成用組成物1を、スピンコーター(Mikasa製 Opticoat MS-A100、1200rpm、30秒)により塗布したのち、120℃3分、250℃3分ベークし、厚さ5μmの接着領域が設けられたウエハ1を形成した。 Example 1
<Formation of adhesion area>
After applying the adhesive region forming composition 1 having the composition shown in Table 1 to a 4-inch Si wafer with a spin coater (Optical MS-A100, 1200 rpm, 30 seconds, manufactured by Mikasa), 120 ° C. for 3 minutes, 250 ° C. for 3 minutes. Baking was performed to form a wafer 1 provided with an adhesive region having a thickness of 5 μm.
ウエハ1の接着領域に対して表2に示す組成の離型領域形成用組成物1をスピンコーター(Mikasa製 Opticoat MS-A100、1200rpm、30秒)により塗布したのち、ホットプレート上で120℃30秒、190℃3分ベークして、接着領域上に厚さ0.1μmの離形領域を形成し、仮接着膜が設けられたウエハ1を形成した。 <Formation of release area>
After applying the release region forming composition 1 having the composition shown in Table 2 to the adhesion region of the wafer 1 using a spin coater (Optical MS-A100, 1200 rpm, 30 seconds, manufactured by Mikasa) at 120 ° C. on a hot plate. Then, the wafer 1 was baked at 190 ° C. for 3 minutes to form a release region having a thickness of 0.1 μm on the adhesion region, and a wafer 1 provided with a temporary adhesion film was formed.
ウエハ1と表面に何も塗布していない4インチSiウエハ(ウエハ2)を熱圧着することで試験片を作製した。
[圧着]
ウエハ1の仮接着膜を有する面とウエハ2の何も塗布していない面とが接触するように重ね、190℃、0.20MPaで3分間加圧接着した。
[ベーク]
加圧接着後、280℃30分加熱した。 <Preparation of test piece>
A test piece was prepared by thermocompression bonding of wafer 1 and a 4-inch Si wafer (wafer 2) having nothing applied to the surface.
[Crimping]
The surface of the wafer 1 having the temporary adhesive film and the surface of the wafer 2 on which nothing was applied were overlapped and pressure-bonded at 190 ° C. and 0.20 MPa for 3 minutes.
[Bake]
After pressure bonding, it was heated at 280 ° C. for 30 minutes.
実施例1において、接着領域形成用組成物と、離型領域形成用組成物とを、それぞれ表3に示す組み合わせで接着領域と離型領域を形成し、実施例1にならって仮接着膜が設けられた試験片を作製した。 (Examples 2 to 32, 35)
In Example 1, the adhesive region forming composition and the release region forming composition were formed in the combinations shown in Table 3 to form the adhesive region and the release region, respectively. The provided test piece was produced.
接着領域形成用組成物19の99質量%と、離型領域形成用組成物1の1質量%とを混合して調製した組成物を、4インチSiウエハにスピンコーター(Mikasa製 Opticoat MS-A100、1200rpm、30秒)により塗布したのち、120℃3分、250℃3分ベークし、厚さ5μmの接着領域が設けられたウエハ1を形成し、実施例1にならって仮接着膜が設けられた試験片を作製した。 (Example 33)
A composition prepared by mixing 99% by mass of the adhesive region forming composition 19 and 1% by mass of the release region forming composition 1 was mixed with a spin coater (Opticaat MS-A100 manufactured by Mikasa) on a 4-inch Si wafer. And then baked at 120 ° C. for 3 minutes and at 250 ° C. for 3 minutes to form a wafer 1 having a 5 μm-thick adhesive region, and a temporary adhesive film is provided according to Example 1. The obtained test piece was produced.
接着領域形成用組成物19の99質量%と、離型領域形成用組成物2の1質量%とを混合して調製した組成物を、4インチSiウエハにスピンコーター(Mikasa製 Opticoat MS-A100、1200rpm、30秒)により塗布したのち、120℃3分、250℃3分ベークし、厚さ5μmの接着領域が設けられたウエハ1を形成し、実施例1にならって仮接着膜が設けられた試験片を作製した。 (Example 34)
A composition prepared by mixing 99% by mass of the adhesive region forming composition 19 and 1% by mass of the release region forming composition 2 was mixed with a spin coater (Opticaat MS-A100 made by Mikasa) on a 4-inch Si wafer. And then baked at 120 ° C. for 3 minutes and at 250 ° C. for 3 minutes to form a wafer 1 having a 5 μm-thick adhesive region, and a temporary adhesive film is provided according to Example 1. The obtained test piece was produced.
実施例1において、離型領域形成用組成物1を使用しなかった以外は、実施例1にならって、仮接着膜が設けられた試験片を作製した。 (Comparative Example 1)
In Example 1, a test piece provided with a temporary adhesive film was prepared in the same manner as in Example 1 except that the release region forming composition 1 was not used.
実施例1において、接着領域形成用組成物1を使用しなかった以外は、実施例1にならって、仮接着膜が設けられた試験片を作製した。 (Comparative Example 2)
In Example 1, a test piece provided with a temporary adhesive film was prepared in the same manner as in Example 1 except that the composition 1 for forming an adhesive region was not used.
実施例1において、接着領域形成用組成物1のかわりに、比較用組成物1~7を使用した以外は、実施例1にならって、仮接着膜が設けられた試験片を作製した。 (Comparative Examples 3 to 7)
A test piece provided with a temporary adhesive film was prepared in the same manner as in Example 1 except that Comparative Compositions 1 to 7 were used in place of the adhesive region forming composition 1.
作製された試験片のせん断接着力を、引っ張り試験機(IMADA製)を用いて、50mm/minの条件で仮接着膜の面に沿った方向に引っ張り測定し、以下の基準で評価した。以下の評価基準で、2~5が実用的であり、3~5が好ましい。
5:80N以上の接着力
4:60N以上80N未満の接着力
3:40N以上60N未満の接着力
2:20N以上40N未満の接着力
1:20N未満の接着力 <Adhesiveness>
Using the tensile tester (manufactured by IMADA), the tensile strength of the produced test piece was measured in the direction along the surface of the temporary adhesive film under the condition of 50 mm / min, and evaluated according to the following criteria. In the following evaluation criteria, 2 to 5 is practical, and 3 to 5 is preferable.
5: Adhesive force of 80N or more 4: Adhesive force of 60N or more and less than 80N 3: Adhesive force of 40N or more and less than 60N 2: Adhesive force of 20N or more and less than 40N 1: Adhesive force of less than 20N
作製された試験片を、50mm/minの条件で仮接着膜の面に垂直な方向に引っ張り測定し、以下の基準で評価した。以下の評価基準で、2~5が実用的であり、3~5が好ましい。
5:3N未満の力で剥離でき、ウエハ2の表面に目視で残渣が見られない
4:3N以上5N未満の力で剥離でき、ウエハ2の表面に目視で残渣が見られない
3:3N以上5N未満の力で剥離できるが、ウエハ2の表面に目視で残渣が見られる
2:5N以上7N以下の力で剥離できるが、ウエハ2の表面に目視で残渣が見られる
1:剥離の過程でウエハが破損する <Peelability>
The produced test piece was measured by pulling in the direction perpendicular to the surface of the temporary adhesive film under the condition of 50 mm / min, and evaluated according to the following criteria. In the following evaluation criteria, 2 to 5 is practical, and 3 to 5 is preferable.
5: Can be peeled off with a force of less than 3N, and no residue is visually observed on the surface of the wafer 2. 4: 3N or more is peeled off with a force of less than 5N, and no residue is visually found on the surface of the wafer 2: 3: 3N or more Although it can be peeled off with a force of less than 5N, a residue can be visually observed on the surface of the wafer 2. 2: It can be peeled off with a force of not less than 5N and not more than 7N, but a residue can be visually observed on the surface of the wafer 2. Damaged wafer
作製された試験片を、25℃のN-メチル-2-ピロリドンで満たしたガラス容器に入れ、超音波洗浄機を用いて15分間超音波を印加した後のサンプルを観察し、以下の基準で評価した。以下の評価基準で、2~5が実用的であり、3~5が好ましい。
5:ウエハのはがれがなく、剥離後の仮接着膜表面が溶媒により侵されていない。
4:ウエハのはがれはないが、剥離後の仮接着膜の溶媒に接触していた側面から1mm未満の範囲が溶媒により侵されている。
3:ウエハのはがれはないが、剥離後の仮接着膜の溶媒に接触していた側面から1mm以上5mm未満の範囲が溶媒により侵されている。
2:ウエハのはがれはないが、剥離後の仮接着膜の溶媒に接触していた側面から5mm以上の範囲が溶媒により侵されている。
1:ウエハがはがれた。 <Chemical resistance>
The prepared test piece is put in a glass container filled with N-methyl-2-pyrrolidone at 25 ° C., and the sample after applying ultrasonic waves for 15 minutes using an ultrasonic cleaner is observed. evaluated. In the following evaluation criteria, 2 to 5 is practical, and 3 to 5 is preferable.
5: There is no peeling of the wafer, and the surface of the temporary adhesive film after peeling is not affected by the solvent.
4: Although there is no peeling of the wafer, a range of less than 1 mm from the side surface in contact with the solvent of the temporary adhesive film after peeling is affected by the solvent.
3: Although there is no peeling of the wafer, a range of 1 mm or more and less than 5 mm from the side surface in contact with the solvent of the temporary adhesive film after peeling is affected by the solvent.
2: Although there is no peeling of the wafer, a range of 5 mm or more from the side surface in contact with the solvent of the temporary adhesive film after peeling is affected by the solvent.
1: The wafer was peeled off.
ウエハ1を形成する際に、4インチSiウエハの代わりに4インチガラスウエハを用いた以外は変更せず、実施例1~35および比較例1~9の仮接着層を形成し、4インチSiウエハと貼り合わせた。得られたサンプルを窒素雰囲気下、オーブンにて400℃3時間加熱した。その後、サンプルのガラスウエハ側から、仮接着層を目視で観察し、以下の基準で評価した。以下の評価基準で、2~5が実用的であり、3~5が好ましい。
なお、ボイドとは、仮接着層とガラスとの界面に発生した空隙である。
5:ボイドがまったく見られなかった。
4:ボイドが5個未満見られた。
3:ボイドが5個以上10個未満見られた。
2:ボイドが10個以上15個未満見られた。
1:ボイドが15個以上見られた。 <Void>
When the wafer 1 is formed, there is no change except that a 4-inch glass wafer is used instead of the 4-inch Si wafer, and the temporary adhesive layers of Examples 1 to 35 and Comparative Examples 1 to 9 are formed, and the 4-inch Si is formed. Bonded to the wafer. The obtained sample was heated in an oven at 400 ° C. for 3 hours under a nitrogen atmosphere. Thereafter, the temporary adhesive 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 is practical, and 3 to 5 is preferable.
The void is a void generated at the interface between the temporary adhesive layer and the glass.
5: Void was not seen at all.
4: Less than 5 voids were observed.
3: 5 or more and less than 10 voids were observed.
2: 10 or more and less than 15 voids were observed.
1: 15 or more voids were observed.
[樹脂成分]
B-1:Durimide(登録商標) 284
(富士フイルム製、溶剤可溶ポリイミド樹脂)
B-2:Durimide(登録商標) 10
(富士フイルム製、溶剤可溶ポリアミドイミド樹脂)
B-3:GPT-LT(群栄化学製、溶剤可溶ポリイミド樹脂)
B-4:リカコート(新日本理化製、ポリアミドイミド樹脂)
B-5:バイロマックス(登録商標) 13NX
(東洋紡製、ポリアミドイミド樹脂)
B-6:MRS0810H
(PBI製、ポリベンズイミダゾール樹脂)
B-7:CRC-8800(住友ベークライト製、ポリベンゾオキサゾール樹脂)
B-8:Ultrason E6020(BASF製、ポリエーテルスルホン樹脂)
B-9:PCZ-500(MGC製、ポリカーボネート樹脂)
[架橋成分]
C-1:BMI-1000(大和化成工業製、ビスマレイミド樹脂)
C-2:BMI-2000(大和化成工業製、ビスマレイミド樹脂)
C-3:BMI-3000(大和化成工業製、ビスマレイミド樹脂)
C-4:BMI-4000(大和化成工業製、ビスマレイミド樹脂)
C-5:BMI-5000(大和化成工業製、ビスマレイミド樹脂)
C-6:BMI-7000(大和化成工業製、ビスマレイミド樹脂)
C-7:BANI-X(新中村化学製、ビスマレイミド樹脂)
C-8:BANI-M(新中村化学製、ビスマレイミド樹脂)
C-9:A-9300(新中村化学製、アクリレート樹脂)
[熱重合開始剤]
D-1:パークミルH(日油製、有機過酸化物、1分間半減期温度254℃)
D-2:パークミルP(日油製、有機過酸化物、1分間半減期温度232.5℃)
D-3:パーブチルZ(日油製、有機過酸化物、1分間半減期温度166.8℃)
D-4:ナイパーBW(日油製、有機過酸化物、1分間半減期温度130.0℃)
D-5:V-601(和光製、アゾ開始剤、1分間半減期温度120℃) The compounds described in Table 1 are as follows.
[Resin component]
B-1: Durimide (registered trademark) 284
(Fujifilm, solvent-soluble polyimide resin)
B-2: Durimide (registered trademark) 10
(Fuji Film, solvent-soluble polyamideimide resin)
B-3: GPT-LT (manufactured by Gunei Chemical, solvent-soluble polyimide resin)
B-4: Rika Coat (manufactured by Nippon Nippon Chemical Co., Ltd., polyamideimide resin)
B-5: Viromax (registered trademark) 13NX
(Toyobo's polyamide-imide resin)
B-6: MRS0810H
(PBI, polybenzimidazole resin)
B-7: CRC-8800 (manufactured by Sumitomo Bakelite, polybenzoxazole resin)
B-8: Ultrason E6020 (manufactured by BASF, polyethersulfone resin)
B-9: PCZ-500 (manufactured by MGC, polycarbonate resin)
[Crosslinking component]
C-1: BMI-1000 (manufactured by Daiwa Kasei Kogyo, bismaleimide resin)
C-2: BMI-2000 (manufactured by Daiwa Kasei Kogyo Co., Ltd., bismaleimide resin)
C-3: BMI-3000 (manufactured by Daiwa Kasei Kogyo, bismaleimide resin)
C-4: BMI-4000 (manufactured by Daiwa Kasei Kogyo, bismaleimide resin)
C-5: BMI-5000 (manufactured by Daiwa Kasei Kogyo, bismaleimide resin)
C-6: BMI-7000 (manufactured by Daiwa Kasei Kogyo, 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 (made by Shin-Nakamura Chemical, acrylate resin)
[Thermal polymerization initiator]
D-1: Park Mill H (manufactured by NOF, organic peroxide, 1 minute half-life temperature 254 ° C.)
D-2: Park Mill P (manufactured by NOF, organic peroxide, 1 minute half-life temperature 232.5 ° C.)
D-3: Perbutyl Z (manufactured by NOF, organic peroxide, 1 minute half-life temperature 166.8 ° C)
D-4: Niper BW (manufactured by NOF, organic peroxide, 1 minute half-life temperature 130.0 ° C.)
D-5: V-601 (manufactured by Wako, azo initiator, 1 minute half-life temperature 120 ° C.)
比較用組成物1:特開2014-29999号公報の実施例1の組成物を調製した。
比較用組成物2:特開2014-29999号公報の実施例2の組成物を調製した。
比較用組成物3:特開2014-29999号公報の実施例3の組成物を調製した。
比較用組成物4:特開2014-29999号公報の実施例4の組成物を調製した。
比較用組成物5:特開2014-29999号公報の実施例5の組成物を調製した。
比較用組成物6:特開2014-29999号公報の実施例6の組成物を調製した。
比較用組成物7:仮接着用組成物1において、架橋成分C-1を含有させなかった。 Comparative compositions 1 to 8 in Table 1 were prepared by the following method.
Comparative composition 1: A composition of Example 1 of JP-A-2014-29999 was prepared.
Comparative composition 2: The composition of Example 2 of JP-A-2014-29999 was prepared.
Comparative composition 3: A composition of Example 3 of JP-A-2014-29999 was prepared.
Comparative composition 4: A composition of Example 4 of JP-A-2014-29999 was prepared.
Comparative composition 5: A composition of Example 5 of JP 2014-29999 A was prepared.
Comparative composition 6: A composition of Example 6 of JP-A-2014-29999 was prepared.
Comparative composition 7: The temporary bonding composition 1 did not contain the crosslinking component C-1.
<400℃質量減少率>
熱重量分析装置Q500(TA社製)により、2-3mgの試料をアルミパン上で60mL/minの窒素気流下、初期温度25℃から10℃/minの一定昇温条件で400℃まで昇温し、400℃に達した際の残存質量を測定した。 The 400 degreeC mass reduction | decrease rate in Table 1 was measured with the following method.
<400 ° C mass reduction rate>
Using a thermogravimetric analyzer Q500 (TA), a 2-3 mg sample was heated on an aluminum pan under a nitrogen stream of 60 mL / min to an initial temperature of 25 ° C. to 400 ° C. under a constant temperature increase condition of 10 ° C./min. The residual mass when reaching 400 ° C. was measured.
<溶解度>
N-メチル-2-ピロリドン100gに対して試料を撹拌しながら一定量添加し、溶解性を確認した。完全に溶解した場合にはさらに試料を撹拌下、一定量添加する作業を繰り返し、最終的に25℃で1時間攪拌したときに試料が溶けなくなる直前の量を溶解度とした。 The solubility in Table 1 was measured by the following method.
<Solubility>
A fixed amount of the sample was added to 100 g of N-methyl-2-pyrrolidone while stirring to confirm the solubility. When the sample was completely dissolved, the operation of adding a certain amount of the sample while stirring was repeated, and the amount immediately before the sample was not dissolved when finally stirred at 25 ° C. for 1 hour was defined as the solubility.
[離型成分]
A-1: オプツールDSX(ダイキン工業社製、フッ素系シランカップリング剤)
A-2: RS-72-K(DIC社製、フッ素系化合物)
A-3: RS-76-E(DIC社製、フッ素系化合物)
A-4: UV-3500B(BYK社製、シリコン系化合物)
A-5: (ヘプタデカフルオロ-1,1,2,2-テトラヒドロデシル)トリクロロシラン(TCI社製)
A-6: CHEMINOX FHP-2-OH(ユニマテック社製、フッ素系化合物)
A-7: TEFLON(登録商標) AF(三井デュポンフロロケミカル社製、フッ素系化合物)
A-8: CYTOP(旭硝子社製、フッ素系化合物)
A-9: KP541(信越化学社製、シリコン系化合物)
A-10: ダイオニンTHV(3M社製、フッ素系化合物)
上記のうち、離型層が三次元架橋体を構成しているのは、A-1~A-4である。
[溶剤]
S-1: パーフルオロヘキサン:(和光純薬社製)
S-2: 1-メトキシ-2-プロピルアセテート
S-3: CT-Solv180(AGC製)
S-4: メチルエチルケトン The compounds described in Table 2 are as follows.
[Release component]
A-1: OPTOOL DSX (Daikin Kogyo Co., Ltd., fluorine-based silane coupling agent)
A-2: RS-72-K (DIC Corporation, fluorine compound)
A-3: RS-76-E (DIC Corporation, fluorine 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-based compound)
A-7: TEFLON (registered trademark) AF (made by Mitsui DuPont Fluorochemical Co., Ltd., fluorine-based compound)
A-8: CYTOP (Asahi Glass Co., Ltd., fluorine compound)
A-9: KP541 (Shin-Etsu Chemical Co., Ltd., silicon compound)
A-10: Dionin THV (manufactured by 3M, fluorine compound)
Among the above, it is A-1 to A-4 that the release layer constitutes the three-dimensional crosslinked body.
[solvent]
S-1: Perfluorohexane: (Wako Pure Chemical Industries, Ltd.)
S-2: 1-methoxy-2-propyl acetate S-3: CT-Solv180 (manufactured by AGC)
S-4: Methyl ethyl ketone
一方、比較例1~9は、接着性、剥離性、耐薬性の少なくとも一つ以上の項目で、実用レベル以下であった。 From the above results, the temporary adhesive films of Examples 1 to 35 were all excellent in adhesion, peelability and chemical resistance. Moreover, there were few voids.
On the other hand, in Comparative Examples 1 to 9, at least one item of adhesiveness, peelability and chemical resistance was below the practical level.
60 デバイスウエハ
60a薄型デバイスウエハ
61 シリコン基板
61a シリコン基板の表面
61b シリコン基板の裏面
61c 薄型デバイスウエハの裏面
62 デバイスチップ
63 構造
71 離型領域
80 仮接合層
100 接着性支持体 DESCRIPTION OF
Claims (22)
- 接着領域と、前記接着領域の表面上の離型領域とを有し、
前記接着領域は、25℃から10℃/分で昇温したときの400℃における質量減少率が1質量%以下であり、25℃のN-メチルピロリドンに対する溶解度が1g/100gSolvent以下である、
仮接着膜。 An adhesive region, and a release region on the surface of the adhesive region;
The adhesion region has a mass reduction rate at 400 ° C. of 1% by mass or less when heated from 25 ° C. at 10 ° C./min, and a solubility in N-methylpyrrolidone at 25 ° C. of 1 g / 100 g Solvent or less.
Temporary adhesive film. - 前記接着領域は、ポリイミド樹脂、ポリアミドイミド樹脂、ポリベンズイミダゾール樹脂およびポリベンゾオキサゾール樹脂から選ばれる少なくとも1種を含む複素環含有樹脂と、マレイミド樹脂とを含有する、請求項1に記載の仮接着膜。 The said adhesion | attachment area | region contains the heterocyclic resin containing at least 1 sort (s) chosen from a polyimide resin, a polyamidoimide resin, a polybenzimidazole resin, and a polybenzoxazole resin, and the temporary adhesion of Claim 1 containing maleimide resin. film.
- 前記複素環含有樹脂が、γ-ブチロラクトン、シクロペンタノン、N-メチルピロリドン、シクロヘキサノン、グリコールエーテル、ジメチルスルホキシドおよびテトラメチルウレアから選ばれる少なくとも1種の溶剤に対する25℃での溶解度が10g/100gSolvent以上のポリイミド樹脂である、請求項2に記載の仮接着膜。 The heterocyclic ring-containing resin has a solubility at 25 ° C. of at least 10 g / 100 g Solvent in at least one solvent selected from γ-butyrolactone, cyclopentanone, N-methylpyrrolidone, cyclohexanone, glycol ether, dimethyl sulfoxide, and tetramethylurea. The temporary adhesive film according to claim 2, which is a polyimide resin.
- 前記マレイミド樹脂が、ビスマレイミド樹脂である請求項2または3に記載の仮接着膜。 The temporary adhesive film according to claim 2 or 3, wherein the maleimide resin is a bismaleimide resin.
- 前記接着領域に含まれる架橋成分の50~100質量%が前記マレイミド樹脂である、請求項1~4のいずれか1項に記載の仮接着膜。 The temporary adhesive film according to any one of claims 1 to 4, wherein 50 to 100% by mass of the crosslinking component contained in the adhesion region is the maleimide resin.
- 前記接着領域は、更に熱重合開始剤を含有する、請求項1~5のいずれか1項に記載の仮接着膜。 The temporary adhesive film according to any one of claims 1 to 5, wherein the adhesion region further contains a thermal polymerization initiator.
- 前記熱重合開始剤は、1分間半減期温度が130~300℃である、請求項6に記載の仮接着膜。 The temporary adhesive film according to claim 6, wherein the thermal polymerization initiator has a half-life temperature of 130 to 300 ° C for 1 minute.
- 前記熱重合開始剤は、有機過酸化物である、請求項6または7に記載の仮接着膜。 The temporary adhesive film according to claim 6 or 7, wherein the thermal polymerization initiator is an organic peroxide.
- 前記離型領域は、フッ素原子およびケイ素原子から選ばれる少なくとも一種を含有する化合物を含む、請求項1~8のいずれか1項に記載の仮接着膜。 The temporary adhesive film according to any one of claims 1 to 8, wherein the release region includes a compound containing at least one selected from a fluorine atom and a silicon atom.
- 前記離型領域は、フッ素系シランカップリング剤を含有する、請求項1~9のいずれか1項に記載の仮接着膜。 The temporary adhesive film according to any one of claims 1 to 9, wherein the release region contains a fluorine-based silane coupling agent.
- 請求項1~10のいずれか1項に記載の仮接着膜の離型領域側の表面に、デバイスウエハを有する、積層体。 A laminate having a device wafer on the surface of the temporary adhesive film according to any one of claims 1 to 10 on the release region side.
- ポリイミド樹脂、ポリアミドイミド樹脂、ポリベンズイミダゾール樹脂およびポリベンゾオキサゾール樹脂から選ばれる少なくとも1種を含む複素環含有樹脂と、
架橋成分と、
溶剤とを含有し、
前記架橋成分の50~100質量%がマレイミド樹脂である、仮接着用組成物。 A heterocyclic ring-containing resin containing at least one selected from a polyimide resin, a polyamideimide resin, a polybenzimidazole resin, and a polybenzoxazole resin;
A crosslinking component;
Containing a solvent,
A composition for temporary bonding, wherein 50 to 100% by mass of the crosslinking component is a maleimide resin. - 前記複素環含有樹脂は、γ-ブチロラクトン、シクロペンタノン、N-メチルピロリドン、シクロヘキサノン、グリコールエーテル、ジメチルスルホキシドおよびテトラメチルウレアから選ばれる少なくとも1種の溶剤に対する25℃での溶解度が10g/100gSolvent以上のポリイミド樹脂である、請求項12に記載の仮接着用組成物。 The heterocyclic ring-containing resin has a solubility at 25 ° C. of 10 g / 100 g Solvent or more in at least one solvent selected from γ-butyrolactone, cyclopentanone, N-methylpyrrolidone, cyclohexanone, glycol ether, dimethyl sulfoxide, and tetramethylurea. The composition for temporary adhesion | attachment of Claim 12 which is a polyimide resin.
- 前記マレイミド樹脂が、ビスマレイミド樹脂である請求項12または13に仮接着用組成物。 The composition for temporary bonding according to claim 12 or 13, wherein the maleimide resin is a bismaleimide resin.
- 更に熱重合開始剤を含有する、請求項12~14のいずれか1項に記載の仮接着用組成物。 The composition for temporary bonding according to any one of claims 12 to 14, further comprising a thermal polymerization initiator.
- 前記熱重合開始剤は、1分間半減期温度が130~300℃である、請求項15に記載の仮接着用組成物。 The temporary adhesion composition according to claim 15, wherein the thermal polymerization initiator has a half-life temperature of 130 to 300 ° C for 1 minute.
- 前記熱重合開始剤は、有機過酸化物である、請求項16に記載の仮接着用組成物。 The composition for temporary bonding according to claim 16, wherein the thermal polymerization initiator is an organic peroxide.
- 更に、離型成分を含有する、請求項12~17のいずれか1項に記載の仮接着用組成物。 The temporary adhesive composition according to any one of claims 12 to 17, further comprising a release component.
- 前記離型成分は、フッ素原子およびケイ素原子から選ばれる少なくとも一種を含有する化合物を含む、請求項18に記載の仮接着用組成物。 The composition for temporary adhesion according to claim 18, wherein the release component includes a compound containing at least one selected from a fluorine atom and a silicon atom.
- 前記離型成分は、フッ素系シランカップリング剤である、請求項18または19に記載の仮接着用組成物。 The composition for temporary adhesion according to claim 18 or 19, wherein the release component is a fluorine-based silane coupling agent.
- 請求項12~20のいずれか1項に記載の仮接着用組成物を塗布する工程を含む、デバイスの製造方法。 A device manufacturing method including a step of applying the temporary bonding composition according to any one of claims 12 to 20.
- 請求項1~10のいずれか1項に記載の仮接着膜を形成するためのキットであって、
請求項12~20のいずれか1項に記載の仮接着用組成物と、
離型成分および溶剤を含む離型領域形成用組成物と、
を含むキット。 A kit for forming the temporary adhesive film according to any one of claims 1 to 10,
A temporary bonding composition according to any one of claims 12 to 20,
A composition for forming a release region containing a release component and a solvent;
Including kit.
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2016523446A JP6379191B2 (en) | 2014-05-30 | 2015-05-21 | Temporary adhesive film, laminate, temporary adhesive composition, device manufacturing method and kit |
KR1020167032081A KR101884256B1 (en) | 2014-05-30 | 2015-05-21 | Temporary bonding film, laminate, composition for temporary bonding, and method and kit for manufacturing device |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2014-111949 | 2014-05-30 | ||
JP2014111949 | 2014-05-30 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2015182469A1 true WO2015182469A1 (en) | 2015-12-03 |
Family
ID=54698805
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2015/064571 WO2015182469A1 (en) | 2014-05-30 | 2015-05-21 | Temporary bonding film, laminate, composition for temporary bonding, and method and kit for manufacturing device |
Country Status (4)
Country | Link |
---|---|
JP (1) | JP6379191B2 (en) |
KR (1) | KR101884256B1 (en) |
TW (1) | TWI663239B (en) |
WO (1) | WO2015182469A1 (en) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR20190033072A (en) * | 2016-07-20 | 2019-03-28 | 히타치가세이가부시끼가이샤 | A resin composition, a resin layer-attached support, a prepreg, a laminate, a multilayer printed wiring board, and a millimeter wave radar printed wiring board |
EP3772523A1 (en) * | 2019-08-08 | 2021-02-10 | Daxin Materials Corporation | Temporary bonding composition, temporary bonding film, composite film, method for temporary bonding workpiece and semiconductor wafer packaging |
CN113574083A (en) * | 2019-03-20 | 2021-10-29 | 积水化学工业株式会社 | Adhesive composition, adhesive tape, and method for processing electronic component |
WO2023170501A1 (en) * | 2022-03-09 | 2023-09-14 | 3M Innovative Properties Company | High temperature stable curable bonding compositions |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP7114214B2 (en) * | 2016-05-24 | 2022-08-08 | 味の素株式会社 | adhesive film |
TWI675899B (en) | 2018-04-25 | 2019-11-01 | 達興材料股份有限公司 | Mothed for temporary workpiece bonding and bonding agent |
US20230035382A1 (en) * | 2019-12-23 | 2023-02-02 | Shin-Etsu Polymer Co., Ltd. | Adhesive composition |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2012241134A (en) * | 2011-05-20 | 2012-12-10 | Hitachi Chemical Co Ltd | Adhesive composition, adhesive sheet and semiconductor device |
JP2014029999A (en) * | 2012-06-29 | 2014-02-13 | Hitachi Chemical Co Ltd | Tentatively fixing film, tentatively fixing film sheet and manufacturing method of semiconductor device |
WO2014103996A1 (en) * | 2012-12-27 | 2014-07-03 | 富士フイルム株式会社 | Temporary adhesive for manufacturing semiconductor devices, adhesive support using same, and method for manufacturing semiconductor devices |
-
2015
- 2015-05-21 KR KR1020167032081A patent/KR101884256B1/en active IP Right Grant
- 2015-05-21 JP JP2016523446A patent/JP6379191B2/en not_active Expired - Fee Related
- 2015-05-21 WO PCT/JP2015/064571 patent/WO2015182469A1/en active Application Filing
- 2015-05-28 TW TW104117085A patent/TWI663239B/en not_active IP Right Cessation
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2012241134A (en) * | 2011-05-20 | 2012-12-10 | Hitachi Chemical Co Ltd | Adhesive composition, adhesive sheet and semiconductor device |
JP2014029999A (en) * | 2012-06-29 | 2014-02-13 | Hitachi Chemical Co Ltd | Tentatively fixing film, tentatively fixing film sheet and manufacturing method of semiconductor device |
WO2014103996A1 (en) * | 2012-12-27 | 2014-07-03 | 富士フイルム株式会社 | Temporary adhesive for manufacturing semiconductor devices, adhesive support using same, and method for manufacturing semiconductor devices |
Cited By (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR20190033072A (en) * | 2016-07-20 | 2019-03-28 | 히타치가세이가부시끼가이샤 | A resin composition, a resin layer-attached support, a prepreg, a laminate, a multilayer printed wiring board, and a millimeter wave radar printed wiring board |
CN113337117A (en) * | 2016-07-20 | 2021-09-03 | 昭和电工材料株式会社 | Resin composition, support, prepreg, laminate, multilayer printed wiring board, and printed wiring board for millimeter wave radar |
KR102340084B1 (en) * | 2016-07-20 | 2021-12-17 | 쇼와덴코머티리얼즈가부시끼가이샤 | A resin composition, a support body with a resin layer, a prepreg, a laminated board, a multilayer printed wiring board, and a printed wiring board for millimeter wave radar |
KR20210154871A (en) * | 2016-07-20 | 2021-12-21 | 쇼와덴코머티리얼즈가부시끼가이샤 | Resin composition, resin layer-provided support, prepreg, laminate sheet, multilayer printed wiring board, and printed wiring board for millimeter-wave radar |
KR102478957B1 (en) * | 2016-07-20 | 2022-12-16 | 쇼와덴코머티리얼즈가부시끼가이샤 | Resin composition, resin layer-provided support, prepreg, laminate sheet, multilayer printed wiring board, and printed wiring board for millimeter-wave radar |
CN113337117B (en) * | 2016-07-20 | 2023-07-14 | 株式会社力森诺科 | Resin composition, support, prepreg, laminate, multilayer printed wiring board, and printed wiring board for millimeter wave radar |
CN113574083A (en) * | 2019-03-20 | 2021-10-29 | 积水化学工业株式会社 | Adhesive composition, adhesive tape, and method for processing electronic component |
EP3772523A1 (en) * | 2019-08-08 | 2021-02-10 | Daxin Materials Corporation | Temporary bonding composition, temporary bonding film, composite film, method for temporary bonding workpiece and semiconductor wafer packaging |
JP2021119233A (en) * | 2019-08-08 | 2021-08-12 | 達興材料股▲ふん▼有限公司Daxin Materials Corporation | Temporary bonding composition, temporary bonding film, composite film, and semiconductor wafer packaging |
JP7134291B2 (en) | 2019-08-08 | 2022-09-09 | 達興材料股▲ふん▼有限公司 | Temporary sticking composition, temporary sticking film, composite film, and semiconductor wafer package |
WO2023170501A1 (en) * | 2022-03-09 | 2023-09-14 | 3M Innovative Properties Company | High temperature stable curable bonding compositions |
Also Published As
Publication number | Publication date |
---|---|
JP6379191B2 (en) | 2018-08-22 |
TW201546231A (en) | 2015-12-16 |
KR101884256B1 (en) | 2018-08-01 |
TWI663239B (en) | 2019-06-21 |
JPWO2015182469A1 (en) | 2017-04-27 |
KR20160147845A (en) | 2016-12-23 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP6379191B2 (en) | Temporary adhesive film, laminate, temporary adhesive composition, device manufacturing method and kit | |
KR101823711B1 (en) | Photosensitive adhesive composition, photosensitive adhesive film, and semiconductor device using each | |
KR101463367B1 (en) | Photosensitive resin composition, photosensitive resin composition film, and semiconductor device using the photosensitive resin composition or the photosensitive resin composition film | |
CN108138013B (en) | Laminate film for temporary bonding, substrate-processed body using laminate film for temporary bonding, method for manufacturing laminated substrate-processed body, and method for manufacturing semiconductor device using same | |
CN111108144A (en) | Curable polyimide | |
TWI669372B (en) | Composition for forming a protective layer, laminate and kit | |
KR20170042609A (en) | Adhesive for temporary bonding, adhesive layer, method for manufacturing wafer work piece and semiconductor device using same, rework solvent, polyimide copolymer, polyimide mixed resin, and resin composition | |
KR20180104311A (en) | Resin composition, resin layer, permanent adhesive, temporary adhesive, laminated film, processed wafer and electronic device or method of manufacturing semiconductor device | |
JPWO2016076261A1 (en) | Temporary adhesive film manufacturing method, temporary adhesive film, laminate, laminate with device wafer, temporary adhesive composition | |
JP6182491B2 (en) | Laminate and its application | |
JP4820615B2 (en) | Dust removal substrate for substrate processing apparatus and dust removal method using the same | |
TWI596185B (en) | Adhesive sheet for semiconductor device with bump electrode and method for manufacturing semiconductor device | |
KR20140128948A (en) | Composition for forming passivation film, including resin having carbon-carbon multiple bond | |
JP2014143308A (en) | Composition for temporal fixing and method of manufacturing semiconductor device | |
JP7183840B2 (en) | Adhesive composition for temporary attachment and method for producing semiconductor electronic component using the same | |
JP6627685B2 (en) | Method for treating target object, composition for temporary fixing, and method for manufacturing semiconductor device | |
TWI634182B (en) | Adhesive composition | |
JP2005206786A (en) | Heat resistant resin composition and dust removing substrate using the same | |
TW201620955A (en) | Compound for semiconductor package, photosensitive resin composition including the same and semiconductor package structure thereof | |
JP2013100451A (en) | Thermal delamination type sheet |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 15799250 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 20167032081 Country of ref document: KR Kind code of ref document: A |
|
ENP | Entry into the national phase |
Ref document number: 2016523446 Country of ref document: JP Kind code of ref document: A |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
122 | Ep: pct application non-entry in european phase |
Ref document number: 15799250 Country of ref document: EP Kind code of ref document: A1 |