JP5432507B2 - Method for producing fragmented or thin plate-like material using stress of adhesive resin - Google Patents

Description

  The present invention relates to a method for producing a roughly plate-like substance fragment, a method for producing a roughly plate-like substance slice, and a substantially plate-like substance to separate the separated material and the cured adhesive. The present invention relates to a method for manufacturing a cut product.

  As a method of dividing a roughly plate-like material and a method of producing a slice of a roughly plate-like material, a method of cutting and scraping with a blade, a method of cutting or scraping with a file, a method of cutting with a high energy beam. There are a method of cutting and shaving and a method of cutting and shaving with chemicals. For example, a very thin substrate is used as a substrate for semiconductor mounting, and the mounting density can be significantly improved by stacking and using extremely thin substrates (Non-patent Document 1).

The conventional method of using a blade (Patent Document 1), using a file, or using a chemical (Patent Document 2) requires a special device to achieve these, as well as shavings and waste liquid. There was a problem that exhaust gas was generated.
Shinichi Maeda, “High-density packaging technology that can be seen”, Industrial Research Institute, Inc., 2003 JP 60-2119013 JP 2005-123425 A

  Accordingly, an object of the present invention is to provide a method for dividing a roughly plate-like substance and a method for producing a slice of a roughly plate-like substance that does not require special equipment and does not generate shavings, waste liquid, or exhaust gas. It is to be.

  As a result of diligent research to solve the above problems, the present inventors have cut off the substrate with a curing stress generated when the adhesive is cured, or cleaves the substrate into pieces of any size. And a method for producing flakes, and also a method for producing flakes by expansion or contraction stress due to heat, and the elastic modulus of the substantially plate-like substance is higher than that of the roughly plate-like substance. It has been found that by adhering a close film and stretching the film, the adhesive force between the substantially plate-like substance and the adhesive layer can be reduced, and the separation between the substantially plate-like substance and the cured adhesive can be facilitated. It came to complete.

  In the present invention, an adhesive is applied to one side of a substantially plate-like substance, and then the adhesive is cured and bonded to thereby apply a curing shrinkage stress or a curing expansion stress to the substantially plate-like substance. The present invention relates to a method for producing a fragment of a substance.

  In the present invention, an adhesive is applied to one side of a substantially plate-like substance, and then the adhesive is cured and bonded, whereby a curing shrinkage stress or a curing expansion stress is applied to the substantially plate-like substance to form the plate-like substance. The present invention relates to a method for producing a flake of a plate-like substance by thinly cleaving the substance.

  In the present invention, an adhesive is applied to one side of a substantially plate-like substance, and then the adhesive is cured and bonded, and at least a rapid temperature change is applied to the cured adhesive, thereby causing thermal expansion or contraction stress. The present invention relates to a method for producing a fragmented or thin piece of a plate-like substance by applying it to the substantially plate-like substance and dividing or slicing the plate-like substance (for example, thinly cleaving).

  In addition, the present invention provides a separation and thinning (for example, cleavage) trigger (for example, notch, introduction of a modified layer by laser, etc.) on the surface and / or end surface of the substantially plate-like substance. The present invention relates to the above method that assists in thinning (for example, cleavage) easily at a desired position.

Further, a substantially plate-like substance is cured and bonded to a film whose elastic modulus is closer to that of the adhesive after curing than the roughly plate-like substance, and by dividing the substantially plate-like substance, The present invention relates to a method for producing a substantially plate-like material fragment including separation from an adhesive after curing. By stretching the film, the stress is concentrated by concentrating the stress between the roughly plate-like substance and the adhesive layer, so that it is easy to separate the roughly plate-like substance after cutting and the adhesive after curing. It is thought that it becomes. That is, a method for producing a fragment from a substantially plate-like substance adhered to a film, wherein the elastic modulus of the substantially plate-like substance, the adhesive, and the film is
The substantially plate-like substance> the film> the cured adhesive;
And the elastic modulus of the substantially plate-like substance, the adhesive, and the film is as follows:
The substantially plate-like substance-the adhesive after curing> the film-the adhesive after curing,
The substantially plate-like substance is separated by stretching the film to which the substantially plate-like substance is bonded with the adhesive, and then further stretching the film to form the substantially plate-like substance. The adhesive strength with the adhesive after curing is lower than that before further stretching the film (for example, 1/10 or less, preferably 1/100 or less, more preferably 1/1000 or less), and divided. Separating the article and the cured adhesive.

  The present invention also relates to the above method, wherein the substantially plate-like substance is a crystalline substance, and the crystalline substance is cleaved thinly along the crystal orientation.

  Further, the present invention provides a semiconductor laminate mounting method comprising dividing or cleaving a substantially plate-like substance by a stress due to thermal expansion or thermal contraction generated by applying a curing stress and / or a rapid temperature change of the resin. The present invention relates to a method of manufacturing a thin substrate.

  Since the present invention divides or cleaves a roughly plate-like substance using the curing stress or thermal expansion and contraction stress of the resin, no waste of cleaning or shavings is generated without the need for special equipment or chemicals. Therefore, the substrate can be preferably used for semiconductor stacking and the like, and a substrate having an arbitrary size and an arbitrary thickness can be manufactured by attaching an opportunity for division to an arbitrary position of a substantially plate-like substance.

  Further, the present invention can easily remove the adhesive layer from the adherend by stretching the adhesive layer and reducing the adhesive force, and can be easily combined with the above-described method of dividing or cleaving the substantially plate-like substance. A substrate having an arbitrary size and an arbitrary thickness can be obtained.

  The adhesive in the present invention can be applied to a substantially plate-like substance in a fluid state, and then solidified and bonded by a curing method according to the cured form of the selected adhesive, whereby the adhesive layer and the approximately plate-like It is an adhesive that firmly adheres to the substance.

  The adhesive in the present invention applies stress to the adherend due to shrinkage or expansion during curing, but the adhesive layer is not peeled off by the curing stress at that time, and the elastic modulus and adhesion are sufficient to break the adherend. Have power. Similarly, the adherend is ruptured even by a stress caused by thermal expansion or contraction due to a rapid thermal change. At that time, the adherend has an elastic modulus and adhesive force sufficient to break.

  In addition, the adhesive in the present invention can be used in combination of two or more kinds. After applying and curing on one side of a substantially plate-like substance, the adhesive is further applied and cured. A structure can also be formed.

  It is also possible to apply an adhesive to two or more surfaces of a substantially plate-like substance. At least one surface is bonded to another member, and one surface is stressed and divided and / or thinned (for example, , Cleavage). By using this method, it is possible to perform bonding, slicing and slicing at the same time, and then severing and slicing after bonding rather than bonding small individual pieces or thin fragile thin pieces. Can be handled easily.

  As the adhesive in the present invention, a curable organic component and an inorganic component can be appropriately used. As the curable organic component, in addition to various epoxy compounds, siloxane compounds, etc., prepolymers such as curable monomers and oligomers can be used, and these can be melted in a polymer state or dissolved in a solvent. It can also be used, or a fine powder having fluidity can be used. Among these, thermoplastic resins include vinyl acetate, vinyl alcohol, vinyl butyral, vinyl chloride, methacrylate, acrylic acid, methacrylic acid, styrene, ethylene, amide, cellulose, isobutylene, vinyl ether, polyvinylidene fluoride, polyester, and the like. A prepolymer and a polymer can be mentioned. Examples of the thermosetting resin include urea, melamine, phenol, resorcinol, epoxy, oxetane, episulfide, isocyanate, a mixture of chitosan and carboxylic acid, a prepolymer and a polymer made of imide and the like. These compounds can be used alone or in combination of two or more.

  When blending such a curable prepolymer, a curing agent and a polymerization initiator for curing the prepolymer can be blended as necessary. The kind of these hardening | curing agents and a polymerization initiator can be suitably selected according to the kind of prepolymer to mix | blend. As such a curing agent and polymerization initiator, a compound that initiates a reaction by energy rays can be preferably used. For example, a photo radical polymerization resin of an acrylic monomer / oligomer, a photo-michael addition resin of a polyene-thiol curing system, a photo cationic polymerization resin of an epoxy, oxetane, and a vinyl ether monomer / oligomer can be exemplified. Moreover, various well-known photoreaction sensitizers can also be used for these formulations. By using such a photocurable resin, the shape after formation or after printing can be quickly fixed.

  Insulating inorganic components with fluidity that can be solidified include various metal alkoxides, various metal chlorides, water glass, colloidal silica, various silicon oxides, silicon nitrides, silicon fluorides, metal oxides, metals It is possible to use solutions of nitrides, metal silicides, metal phosphates, or these fine powders that are flowable.

  Such a fluid substance containing an inorganic component can be solidified by using a sol-gel reaction, high-temperature baking, or the like, and a sol-gel reaction catalyst can be blended with the fluid substance.

  As a catalyst for the sol-gel reaction, an inorganic component is hydrolyzed and polycondensed; an acid such as hydrochloric acid; an alkali such as sodium hydroxide; an amine; or dibutyltin diacetate, dibutyltin dioctate, dibutyltin dilaurate, Organotin compounds such as dibutyltin dimaleate, dioctyltin dilaurate, dioctyltin dimaleate, tin octylate; isopropyl triisostearoyl titanate, isopropyl tris (dioctyl pyrophosphate) titanate, bis (dioctyl pyrophosphate) oxyacetate titanate, tetraalkyl titanate Organic titanate compounds such as tetrabutyl zirconate, tetrakis (acetylacetonate) zirconium, tetraisobutyl zirconate, butoxy tris (acetate) Organozirconium compounds such as ruacetonate) zirconium and zirconium naphthenate; Organoaluminum compounds such as tris (ethylacetoacetate) aluminum and tris (acetylacetonato) aluminum; Organometallic catalysts such as zinc naphthenate, cobalt naphthenate and cobalt octylate Etc. Among these, a dibutyltin compound (SCAT-24 manufactured by Sansha Machinery Chemical Co., Ltd.) can be specifically mentioned as a commercial product. These compounds can be used alone or in combination of two or more.

  These organic components and inorganic components can be used as needed alone or in combination of organic and inorganic as appropriate.

  It is also possible to add various solvents to the adhesive, such as hydrocarbon (propane, n-butane, n-pentane, isohexane, cyclohexane, n-octane, isooctane, benzene, toluene, xylene, ethylbenzene, amylbenzene, turpentine oil. , Pinene, etc.), halogenated hydrocarbons (methyl chloride, chloroform, carbon tetrachloride, ethylene chloride, methyl bromide, ethyl bromide, chlorobenzene, chlorobromomethane, bromobenzene, fluorodichloromethane, dichlorodifluoromethane, difluorochloroethane, etc.) Alcohol (methanol, ethanol, n-propanol, isopropanol, n-amyl alcohol, isoamyl alcohol, n-hexanol, n-heptanol, 2-octanol, n-dodecanol, nonanol, siku Hexanol, glycidol, etc.), ether, acetal (ethyl ether, dichloroethyl ether, isopropyl ether, n-butyl ether, diisoamyl ether, methylphenyl ether, ethylbenzyl ether, furan, furfural, 2-methylfuran, cineol, methylal), Ketone (acetone, methyl ethyl ketone, methyl-n-propyl ketone, methyl-n-amyl ketone, diisobutyl ketone, phorone, isophorone, cyclohexanone, acetophenone, etc.), ester (methyl formate, ethyl formate, propyl formate, methyl acetate, ethyl acetate, acetic acid) Propyl, acetic acid-n-amyl, methyl cyclohexyl acetate, methyl butyrate, ethyl butyrate, propyl butyrate, butyl stearate), polyhydric alcohols and their derivatives (e.g. Lenglycol, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether, methoxymethoxyethanol, ethylene glycol monoacetate, diethylene glycol, diethylene glycol monomethyl ether, propylene glycol, propylene glycol monoethyl ether, etc.), fatty acids and phenols ( Formic acid, acetic acid, acetic anhydride, propionic acid, propionic anhydride, butyric acid, isovaleric acid, phenol, cresol, o-cresol, xylenol, etc., nitrogen compounds (nitromethane, nitroethane, 1-nitropropane, nitrobenzene, monomethylamine, dimethyl) Amine, trimethylamine, monoethylamine, diamylamine, aniline, monomethylamine Niline, o-toluidine, o-chloroaniline, dichloroamine, dicyclohexylamine, monoethanolamine, formamide, N, N-dimethylformamide, acetamide, acetonitrile, pyridine, α-picoline, 2,4-lutidine, quinoline, morpholine Etc.), sulfur, phosphorus, other compounds (carbon disulfide, dimethyl sulfoxide, 4,4-diethyl-1,2-dithiolane, dimethyl sulfide, dimethyl disulfide, methanethiol, propane sultone, triethyl phosphate, tophenyl phosphate, carbonic acid Examples thereof include liquids such as diethyl, ethylene carbonate, amyl borate), inorganic solvents (liquid ammonia, silicone oil, etc.), liquid metals, and water.

  In the adhesive, a stabilizer, a coupling agent and the like can be appropriately selected and blended as necessary. Specific examples of such stabilizers include 2,6-di-tert-butyl-phenol, 2,4-di-tert-butyl-phenol, 2,6-di-tert-butyl-4-ethyl- Phenol-based antioxidants exemplified by phenol, 2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5-di-tert-butyl-anilino) -1,3,5-triazine and the like Agent, alkyldiphenylamine, N, N′-diphenyl-p-phenylenediamine, 6-ethoxy-2,2,4-trimethyl-1,2-dihydroquinoline, N-phenyl-N′-isopropyl-p-phenylenediamine, etc. Aromatic amine antioxidants, dilauryl-3,3′-thiodipropionate, ditridecyl-3,3′-thiodipropionate exemplified by A sulfide hydroperoxide decomposer exemplified by bis [2-methyl-4- {3-n-alkylthiopropionyloxy} -5-tert-butyl-phenyl] sulfide, 2-mercapto-5-methyl-benzimidazole and the like; Tris (isodecyl) phosphite, phenyl diisooctyl phosphite, diphenyl isooctyl phosphite, di (nonylphenyl) pentaerythritol diphosphite, 3,5-di-tert-butyl-4-hydroxy-benzyl phosphate diethyl ester , Phosphorus hydroperoxide decomposing agents exemplified by sodium bis (4-tert-butylphenyl) phosphate, etc., salicylates exemplified by phenyl salicylate, 4-tert-octylphenyl salicylate, etc. Benzophenone-based light stabilizers exemplified by 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid, etc., 2- (2′-hydroxy-5′-methylphenyl) Benzotriazole-based light exemplified by benzotriazole, 2,2′-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6- (2N-benzotriazol-2-yl) phenol], etc. A hindered amine light stabilizer exemplified by a stabilizer, phenyl-4-piperidinyl carbonate, bis- [2,2,6,6-tetramethyl-4-piperidinyl sebacate] and the like, [2,2′- Exemplified by thio-bis (4-t-octylphenolate)]-2-ethylhexylamine-nickel- (II) Examples thereof include Ni-based light stabilizers, cyanoacrylate-based light stabilizers, and oxalic acid anilide-based light stabilizers. As such a coupling agent, specifically, as a fluorine-based silane coupling agent, (tridecafluoro-1,1,2,2-tetrahydrooctyl) triethoxysilane, an epoxy-modified silane coupling agent Coupling agent (trade name: KBM-403) manufactured by Shin-Etsu Chemical Co., Ltd., coupling agent (trade name: TESOX) manufactured by Toagosei Co., Ltd. as an oxetane-modified silane coupling agent, or vinyltrimethoxysilane, vinyltriethoxy Silane, γ-chloropropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane, N- (β-aminoethyl) -γ-aminopropylmethyldimethoxy Silane, γ-glycidoxypropyltrimethoxysilane Silane coupling agents such as N, β-glycidoxypropylmethyldimethoxysilane, γ-methacryloxyxypropyltrimethoxysilane, γ-methacryloxyxypropylmethyldimethoxysilane, γ-mercaptopropyltrimethoxysilane, and triethanolamine Titanate, titanium acetylacetonate, titanium ethyl acetoacetate, titanium lactate, titanium lactate ammonium salt, tetrastearyl titanate, isopropyltricumylphenyl titanate, isopropyltri (N-aminoethyl-aminoethyl) titanate, dicumylphenyloxyacetate titanate, Isopropyltrioctanoyl titanate, isopropyl dimethacrylisostearoyl titanate, titanium lactate Ester, octylene glycol titanate, isopropyl triisostearoyl titanate, triisostearyl isopropyl titanate, isopropyl tridodecylbenzenesulfonyl titanate, tetra (2-ethylhexyl) titanate, butyl titanate dimer, isopropyl isostearoyl diacryl titanate, isopropyl tri (dioctyl phosphate) ) Titanate, isopropyltris (dioctylpyrophosphate) titanate, tetraisopropylbis (dioctylphosphite) titanate, tetraoctylbis (ditridecylphosphite) titanate, tetra (2,2-diallyloxymethyl-1-butyl) bis (di) -Tridecyl) phosphite titanate, bis (dioctyl pyrophosphate) Oxyacetate titanate, bis (dioctyl pyrophosphate) ethylene titanate, tetra -i- propyl titanate, tetra -n- butyl titanate, and titanium-based coupling agents such as diisostearoyl ethylene titanate. These compounds can be used alone or in combination of two or more.

  The adhesive can contain various surfactants in order to adjust the wetting. Examples of such surfactants include soaps, lauryl sulfate, polyoxyethylene alkyl ether sulfate, alkyl benzene sulfonate, polyoxyethylene alkyl ether phosphate, polyoxyethylene alkyl phenyl ether phosphate. Acid, N-acyl amino acid salt, α-olefin sulfonate, alkyl sulfate ester salt, alkyl phenyl ether sulfate ester salt, methyl taurate, and the like. Examples of amphoteric surfactants include alkyl diaminoethyl glycine hydrochloride, 2 -Alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine, lauryldimethylaminoacetic acid betaine, coconut oil fatty acid amidopropyl betaine, fatty acid alkyl betaine, sulfobetaine, amidoxide, etc. Nonionic (nonionic) surfactants include polyethylene glycol alkyl ester compounds, alkyl ether compounds such as triethylene glycol monobutyl ether, ester compounds such as polyoxysorbitan esters, alkylphenol compounds, and fluorine compounds. Examples thereof include silicone compounds and silicone type compounds. These compounds can be used alone or in combination of two or more.

  In order to improve mechanical strength and thermal characteristics, various types of fillers can be blended with the adhesive as necessary in a range that does not impair the required performance. Insulating fillers include powders of metal oxides such as alumina, silica, zirconia and titania, sols such as colloidal silica, titania sol and alumina sol, clay minerals such as talc, kaolinite and smectite, and carbides such as silicon carbide and titanium carbide. And nitrides such as silicon nitride, aluminum nitride and titanium nitride, borides such as boron nitride, titanium boride and boron oxide, complex oxides such as mullite, hydroxides such as aluminum hydroxide and magnesium hydroxide, etc. It is done.

  Furthermore, in order to impart conductivity to the adhesive, a conductive filler can be used. Examples of such conductive filler include Ag, Cu, Au, Al, Mg, Rh, W, Mo, Co, Ni, Pt, Pd, Cr, Ta, Pb, V, Zr, Ti, In, Fe, and Zn. Metal powder, flakes or colloids such as Sn—Pb, Sn—In, Sn—Bi, Sn—Ag, Sn—Zn alloy powders and flakes, acetylene black, furnace black Carbon black such as channel black, graphite, graphite fiber, graphite fibril, carbon fiber, activated carbon, charcoal, carbon nanotube, fullerene and other conductive carbon materials, metal oxide conductive fillers include zinc oxide and tin oxide , Indium oxide, titanium oxide (titanium dioxide, titanium monoxide, etc.) Ri surplus electrons filler, and the like indicating the generated conductive. Such fillers can be used alone or in combination of two or more, and it is also preferable to use a filler whose surface is treated with a coupling agent or the like.

  The conductive filler is preferably conductive particles, and the size of the particles is more preferably smaller than the size of the member to be formed. When the conductive particles are blended in a fluid conductive composition capable of solidifying, the conductive particles can be imparted by contacting each other in the fluid conductive composition capable of solidifying. As such conductive particles, powders or flakes of the above metals or alloys can be used.

The conductive particles preferably have a flat shape that can be oriented by an electric field, a magnetic field, or both. In this case, the conductive composition can be solidified in a state where the conductive particles are oriented. The solidified product of the conductive composition has anisotropy in the electrical resistance value corresponding to the direction oriented by the electric field and / or the magnetic field, and is a preferable embodiment for enhancing the electrical efficiency of the electronic device. It is.
Further, as a bonding agent, a molten metal or alloy can be cooled and solidified for bonding, and a low melting point alloy can be preferably used. When the conductive material is a metal or an alloy, electrical connection can be made with low resistance. Examples of such an alloy include Sn—Pb, Sn—In, Sn—Bi, Sn—Ag, and Sn—Zn alloys.

  The adhesive of the present invention can be obtained as a solution or a suspension by mixing and stirring the above components. Stirring can be performed by appropriately selecting various stirring devices such as a propeller mixer, a planetary mixer, a hybrid mixer, a kneader, a homogenizer for emulsification, and an ultrasonic homogenizer. Moreover, it can also stir, heating or cooling as needed.

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

  A method for producing a fragment or thin piece by dividing or thinly slicing (cleaving) a substantially plate-like substance using the adhesive of the present invention is performed by removing a substance having anisotropy in the breaking direction, It is divided by stress due to the difference in the linear thermal expansion coefficient between the adhesive layer and the roughly plate-like material due to a sudden temperature change, or cleaved thinly, and further by applying tensile stress to the adhesive layer The adhesive layer can be easily removed from the material that has been divided or cleaved by reducing the adhesive force in the direction. By using the above method, even plate-like substances that are difficult to break with adhesives with weak adhesion, etc. can be broken with an adhesive that has strong adhesive strength, and can be easily bonded by stretching the film and reducing the adhesive strength. The agent can be removed.

  As the substantially plate-like substance in the present invention, wafers and ingots of various substances can be exemplified, and those having a shape in which at least one surface is substantially flat and can form an adhesive layer can be used.

  Above all, crystalline materials such as silicon and gallium, and layered crystal materials such as mica and graphite have the property of being easily broken along the crystal lattice, so they can be cut or sliced (cleaved) along the crystal lattice. preferable. The substantially plate-like substance may be a semiconductor substrate such as a silicon wafer or a silicon chip.

  A crystalline substance, a substance having a fibrous fine structure, or the like has a property of being easily broken along the structural unit. For example, it is known that a substance having a sheet-like crystal structure such as graphite or a clay layered compound can be cleaved thinly into a sheet. Crystalline materials such as silicon and diamond are known to cleave along the crystal plane and are generally used as processing methods. Thus, cleavage means that a material breaks along a structural unit. Here, a silicon wafer or the like used for an electronic device is required to be thin in order to reduce the weight and size of the electronic device, but it is difficult to cleave the silicon wafer thinly so as not to break. Here, “thin” means, for example, a thickness of about 0.01 to 1 mm.

  Accordingly, the present inventors have found that the adhesive of the present invention is applied to the surface of a material that is easily broken along the structural unit, and can be thinly broken by the hardening stress. After the breakage, the adhesive can be removed, or the adhesive layer can be used as a protective layer so that the thinned silicon wafer does not warp, and a subsequent process can be performed. Especially in the case of a structure in which the ground is taken on the back side of the wiring surface, such as a silicon wafer, the adhesive substance applied to the back side needs to be conductive, and it is also necessary to form a fine pattern by electrolytic plating or the like. It may become. Part of the silicon that has been broken and removed the adhesive layer can be reused as a material for solar cells.

  In addition, it is possible to create a break (notch) on the end face of a plate-like substance so that it is easy to break along the structural unit, thereby giving a defect to the crystal structure along the crystal structure or scratching the surface. Thus, the guide can be formed so that the fracture proceeds along the structural unit. Such a notch can also be made with a laser, for example, a notch for thinly breaking can be formed by irradiating the end face with a laser from the direction perpendicular to the surface normal of a silicon wafer or silicon chip. .

  Hereinafter, a method for producing a fragment or a flake by dividing or cleaving a substantially plate-like substance of the present invention will be described with reference to diagrams and tables such as schematic diagrams, but the present invention is limited to the following examples. It is not a thing.

  In the first embodiment of the conductive composition of the present invention, by applying stress at the time of curing of the adhesive, thermal expansion or thermal contraction stress to the substantially plate-like substance as the adherend, the substantially plate-like material is formed. It is a manufacturing method of the fragmented material of a plate-shaped substance including dividing or flaking a substance.

  By applying the stress derived from the adhesive to the substantially plate-like substance by the above method, the roughly plate-like substance can be divided or sliced as shown in the schematic diagrams of FIGS.

  Here, FIG. 1 shows an example of a substantially plate-like substance 3 in which an adhesive layer 1 and a severance trigger 2 are formed and in close contact with the adhesive layer. (A) is before the adhesive is cured, (b) Indicates after curing of the adhesive.

  As shown in FIGS. 1A to 1B, an adhesive 1 is applied to one side of a substantially plate-like substance 1 on which a trigger 2 is formed (a), and the approximate plate is formed by the shrinkage stress of the adhesive 1 at the time of curing. The material 3 is warped and the chip is divided along the trigger 2 (b).

  Next, FIG. 2 shows an example of a substantially plate-like substance 6 in which an adhesive layer 4 and a separation trigger 5 are formed. (A) is before the adhesive is cured, and (b) is after the adhesive is cured. Show.

  As shown in FIGS. 2A to 2B, the adhesive 4 is applied to the substantially plate-like substance 6 on which the trigger 5 is formed (a), and the substantially plate-like material is formed by the shrinkage stress of the adhesive 4 at the time of curing. The material 6 warps and the flakes 7 are cleaved.

  FIG. 3 shows an example of a substantially plate-like substance 11 in which a film 8 and an adhesive 9 and a hook 10 are formed. (A) shows after the adhesive is cured, and (b) shows after the film is stretched. Here, the elastic modulus of the film is closer to the elastic modulus of the adhesive after curing than the elastic modulus of the substantially plate-like substance. The film is selected according to the type of the substantially plate-like substance and the adhesive, and can be selected from, for example, a simple substance such as nylon, vinylon, polyvinyl alcohol, polyester, silicone resin, polycarbonate, polyimide, or a composite film.

  As shown in FIGS. 3A to 3B, a substantially plate-like substance 11 on which a film 8 and a hook 10 are formed is cured and bonded with an adhesive 9 (a), and the film is sufficiently stretched to adhere. Since stress can be concentrated on the interface between the adhesive and the adhesive strength can be reduced to, for example, 1/10 or less, the divided substantially plate-like substance and the adhesive after curing can be separated.

  As described above, by using the method of producing a fragment or flake by dividing or cleaving the roughly plate-like substance using the stress at the time of curing and the stress at the time of the present invention, the roughly plate-like substance can be easily obtained. Can be divided or sliced. Furthermore, a film having a modulus of elasticity close to that of the adhesive and a substantially plate-like substance are cured and bonded, and then a tensile stress is applied to the film to apply stress to the interface between the adhesive and the substantially plate-like substance, thereby reducing the adhesiveness. The substantially plate-like substance can be easily removed from the adhesive interface from the film.

  Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto. The amount added is in parts by weight unless otherwise noted.

(Method of dividing by hardening stress)
In Example 1, the silicon wafer was divided using the stress at the time of curing of the thermosetting adhesive.

(Manufacture of heat curable adhesive)
100 parts of bisphenol F type epoxy resin (product name: Epicron 830S) manufactured by Dainippon Ink & Chemicals, Inc., 30 parts of amine adduct-based latent thermosetting agent (product name: Amicure MY-H) manufactured by Ajinomoto Fine Techno Co., Ltd. 5 parts of epoxy-modified silane coupling agent (product name: KBM-403) manufactured by Shin-Etsu Chemical Co., Ltd. and 20 parts of fine talc (product name: MICRO ACEP-3) manufactured by Nippon Talc Co., Ltd. in a planetary mixer with a cooling jacket The mixture was stirred until a uniform liquid was obtained to obtain an adhesive. At this time, stirring was performed while cooling the solution so as not to exceed 25 ° C. so that the coating solution did not react with heat generated during stirring.

(Manufacture of roughly plate-like substances with triggers)
The surface of a silicon chip (100 × 100 × 0.3 mm) was scribed so as to intersect at intervals of 10 mm using glass cutting.

(Applying adhesive)
The adhesive was applied to the entire back surface of the silicon chip with a thickness of 100 μm.

(Partition test)
When the above-mentioned adhesive-coated test piece was heated and cured at 150 ° C. for 10 minutes and then returned to room temperature, the silicon chip warped due to the curing shrinkage of the adhesive, and the chip could be divided along the trigger.

(Method for producing flakes by thermal expansion and contraction)
In Example 2, a silicon flake was manufactured using a thermosetting resin.

(Manufacture of photocurable adhesive)
50 parts of a naphthalene type epoxy resin (product name: Epicron HP4032D) manufactured by Dainippon Ink & Chemicals, Inc., 10 parts of an alicyclic epoxy resin (product name: Celoxide 2021P) manufactured by Daicel Chemical Industries, Ltd., manufactured by Sanshin Chemical Industry Co., Ltd. Put 5 parts of thermal cation initiator (product name: Sun-Aid SI-100L) and 5 parts of epoxy-modified silane coupling agent (product name: KBM-403) manufactured by Shin-Etsu Chemical Co., Ltd. into a planetary mixer with cooling jacket. The resulting mixture was stirred until it became a liquid. At this time, stirring was performed while cooling the liquid temperature in a range not exceeding 25 ° C. so that the coating liquid did not react with heat generated during stirring.

(Manufacture of roughly plate-like substances with triggers)
A cue using a femtosecond laser was applied to a portion 0.1 mm from the cylindrical end surface of the outer periphery of a silicon cylindrical ingot (diameter 50 mm, length 100 mm, crystal orientation 100 plane) (the positional relationship is the same as in FIG. 2).

(Applying adhesive)
The adhesive was applied to the entire bottom surface of the silicon cylinder ingot with a thickness of 5 mm (the positional relationship is the same as in FIG. 2).

(Partition test)
The above-mentioned adhesive-coated test piece was heated and cured at 150 ° C. for 10 minutes, then returned to room temperature, and further subjected to a heat cycle of −40 to 120 ° C. 30 times, whereby the chip could be divided along the trigger.

(Method of easily peeling off the adhesive force due to tensile stress)
In Example 3, the adhesive layer and the silicon chip were easily peeled by applying a tensile stress to the film adhered to the silicon chip.

(Manufacture of photocurable adhesive)
100 parts urethane acrylate oligomer manufactured by Negami Kogyo Co., Ltd. (product name: Art Resin UN-9200A), 25 parts hydroxy acrylic monomer (product name: light ester HOB) manufactured by Kyoeisha Chemical Co., Ltd., acrylic monomer manufactured by Rohm and Haas Co., Ltd. Product name: QM657) 25 parts, Ciba Specialty Chemicals photo radical initiator (product name: Irgacure 184) 5 parts, Shin-Etsu Chemical Co., Ltd. acrylic modified silane coupling agent (product name: KBE-1003) 5 parts Was put into a planetary mixer with a cooling jacket and stirred until a uniform liquid was obtained, to obtain an adhesive (elastic modulus after UV curing = 1.5 GPa). At this time, stirring was performed while cooling the solution so as not to exceed 25 ° C. so that the coating solution did not react with heat generated during stirring.

(Adhesion test piece preparation)
The same method as in Example 1 was applied to a biaxially stretched nylon film (product name: Santonyl SNR 25 μm, elastic modulus = 2.5 GPa) made by Mitsubishi Plastics Co., Ltd. adhered to the expanded frame with a thickness of 50 μm. The surface of the silicon wafer (elastic modulus = 105 GPa) having a trigger prepared in (1) without any trigger was adhered. Then, UV6000mJ / cm < ² > (365nm) was irradiated, the adhesive was photocured, and the test piece for a tension test was produced.

(Tensile test)
The above-mentioned test piece was pulled up 10 mm using an expander manufactured by Technovision Co., Ltd. (product name: TEX-21BG), and a tensile stress in the outer peripheral direction was applied. As a result, the silicon was divided along the opportunity to cut the glass. At this time, the adhesive force between the film and the silicon split solid side was 50 kgf in the vertical direction. Furthermore, when a tensile stress was applied by pulling up 20 mm, the interface between the chip and the adhesive layer began to peel off. At this time, the adhesive force between the film and the silicon split solid side was 0.03 kgf in the vertical direction. In this state, it was possible to remove the chips that were easily separated from the film with tweezers.

Comparative Example 1
(Method of cutting using an adhesive film)
In the comparative example 1, the parting test of the parting silicon chip was done using the film with the adhesive.

(Adhesion test piece preparation)
A silicon wafer used in Example 3 was attached to a dicing tape (product name: ELEP Holder UE-110BJ) manufactured by Nitto Denko Corporation to prepare an adhesion test piece.

(Tensile test)
A tensile stress was applied to the above-described test piece in the same manner as in Example 3. Although it was stretched until the adhesive film was broken, the silicon wafer could not be divided. Moreover, since the adhesive layer continued to grow, the silicon wafer could not be easily removed from the adhesive layer.

(A) is a figure which shows the state by which the adhesive agent is apply | coated to the back surface of the substantially plate-shaped substance with which the opportunity was formed in the surface. (B) is a figure which shows the state by which the substantially plate-shaped substance was parted along the trigger with the hardening stress and / or thermal stress of the adhesive agent. (A) is a figure which shows the state by which the adhesive agent is apply | coated to the end surface of the substantially plate-shaped substance with which the opportunity was formed in the outer periphery. (B) is a figure which shows the state by which the substantially plate-shaped substance was thinned along the trigger by the hardening stress and / or thermal stress of the adhesive agent. (A) is a figure which shows the state which affixed the back surface of the substantially plate-shaped substance by which the trigger was formed in the film on the surface. (B) shows that a substantially plate-like substance is divided along the trigger by applying a tensile stress in the outer peripheral direction of the film, and a substantially plate-like substance having a large elastic modulus difference by applying a tensile stress to the adhesive layer. It is a figure which shows a mode that stress concentrates between and the adhesive force falls.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Adhesive 2 Trigger attached to the surface 3 Approximate plate-shaped substance formed with a trigger on the surface 4 Adhesive 5 Trigger attached to the outer periphery 6 Approximate plate-shaped substance formed with a trigger on the outer periphery 7 Thin piece 8 Film 9 Adhesion Agent 10 Trigger attached to the surface 11 Approximate plate-like substance with a trigger formed on the surface

Claims (5)

A method of manufacturing a flake from a substantially plate-like substance, wherein an adhesive is applied to one side of the roughly plate-like substance, and then the adhesive is cured and bonded to thereby obtain a curing shrinkage stress or a curing expansion stress. Applying to a sheet material to cleave the sheet material substantially to produce a flake of the sheet material . A method for producing flakes from a substantially plate-like substance, wherein an adhesive is applied to one side of a substantially plate-like substance, then the adhesive is cured and bonded, and at least a rapid temperature change is applied to the cured adhesive. Applying a thermal expansion or contraction stress to the substantially plate-like substance by applying to cleave the substantially plate-like substance into a thin piece of the substantially plate-like substance . The method according to claim 1 or 2 , wherein the thinning is applied to an end face of the substantially plate-like substance . Characterized in that said outline-shaped material is crystalline material, any one method according to claim 1-3. Flakes is a semiconductor, any one method according to claim 1-4.