JP2020050734A - Resin composition for sacrificial layer and method for manufacturing semiconductor electronic component using the same - Google Patents

Abstract

To provide: a resin composition for a sacrificial layer which, in a step of manufacturing a semiconductor electronic component on the sacrificial layer, has heat resistance of 200 to 500°C, further enables subsequent peeling off of the semiconductor electronic component, and still further is capable of being removed under a mild condition; and a method for manufacturing the semiconductor electronic component using the same.SOLUTION: Provided are: a resin composition for a sacrificial layer, comprising at least (A) a polyimide resin containing a hydroxyl group or a carboxyl group, or both of these in an amount of 1 to 30 mass% relative to the whole resin, and (B) a solvent; and a method for manufacturing a semiconductor electronic component using the same, comprising at least (1) a step of coating one surface of a supporting substrate with the resin composition for a sacrificial layer to form a sacrificial layer, (2) a step of forming at least a semiconductor electronic component on the sacrificial layer, and (3) a step of peeling off the semiconductor electronic component from the supporting substrate, in this order.SELECTED DRAWING: None

Description

  The present invention relates to a resin composition for a sacrificial layer and a method for manufacturing a semiconductor electronic component using the same. More specifically, in a process of manufacturing a semiconductor electronic component on a sacrificial layer, the semiconductor electronic component has heat resistance of 200 to 500 ° C., after which the semiconductor electronic component can be peeled off and then removed under a mild condition. The present invention relates to a resin composition for a sacrificial layer that can be used, and a method for manufacturing a semiconductor electronic component using the same.

  2. Description of the Related Art In recent years, as semiconductor electronic components have become more sophisticated, miniaturization and higher integration of semiconductor chips have been demanded, and the number of electrodes (terminals, bumps) for external connection of semiconductor chips has tended to increase. Therefore, the pitch of the external connection electrodes of the semiconductor chip tends to be small, but it is not easy to directly mount the fine pitch bumps on the circuit board.

  In order to solve the above problem, a fan-out type wafer level package (FO-WLP) has been proposed in which a rewiring layer connected to an electrode is formed on the outer periphery of a semiconductor chip to increase the pitch of bumps. Patent Documents 1 and 2).

  Patent Literature 1 discloses a method in which a rewiring layer is formed on a support substrate, and then the semiconductor chip is connected to the rewiring layer via bumps.

  Patent Literature 2 discloses that after a plurality of semiconductor chips are temporarily fixed on a supporting substrate on which a sacrificial layer is formed, the semiconductor chips are embedded with a sealing material, and then the semiconductor chip is exposed by grinding the sealing material. This is a method for forming a rewiring layer.

  In a method of manufacturing a semiconductor electronic component on a supporting substrate, such as a fan-out type wafer level package, a step of peeling the produced semiconductor electronic component from the supporting substrate without being damaged is required. Patent Document 1 proposes a method of dissolving and removing a metal substrate used as a support substrate by wet etching. Patent Document 2 proposes a method in which a glass substrate having a sacrifice layer of an acrylic material formed thereon is used as a support substrate, and a semiconductor electronic component is separated by irradiating a laser to the sacrifice layer from the glass substrate side.

  As one of the heat-resistant resins widely used for semiconductor electronic components, a polyimide material is known. When a polyimide-based material is used as a substitute for the acrylic-based material, there is no problem that voids are generated in a heat treatment process at 200 ° C. to 500 ° C., but thereafter, it is necessary to remove with a high-temperature organic solvent or the like. There is a problem that cannot be removed (Patent Document 3).

JP 2001-94003 A (Claims) JP-A-2017-98481 (Claims) Japanese Patent Application Laid-Open No. Hei 3-22709 (Claims)

  However, the method of dissolving and removing the metal substrate by wet etching has a problem that the etching time is long and the cost is high. Further, the heat resistance of the acrylic material is about 150 ° C., and when there is a heat treatment step at 200 ° C. to 500 ° C. in the manufacturing process of the semiconductor electronic component, there is a problem that voids are generated in the sacrificial layer, Has a problem that it cannot be removed afterwards.

  In view of such a situation, an object of the present invention is to have a heat resistance of 200 to 500 ° C. in a process of manufacturing a semiconductor electronic component on a sacrificial layer, and then to peel off the semiconductor electronic component, and further thereafter, An object of the present invention is to provide a resin composition for a sacrificial layer that can be removed under mild conditions, and a method for manufacturing a semiconductor electronic component using the same.

  That is, the present invention is a resin composition for a sacrificial layer containing (A) a polyimide resin containing at least 1 to 30% by mass of a hydroxy group and / or a carboxyl group of the whole resin and (B) a solvent.

  Further, at least (1) a step of applying the resin composition for a sacrificial layer to one surface of a support substrate to form a sacrificial layer, (2) a step of forming at least a semiconductor electronic component on the sacrificial layer, and (3) And a step of separating the semiconductor electronic component from the support substrate on which the sacrificial layer is formed.

  According to the present invention, in a process of manufacturing a semiconductor electronic component on a sacrificial layer, the semiconductor electronic component has heat resistance of 200 to 500 ° C., and thereafter, the semiconductor electronic component can be peeled off, and then removed under mild conditions. And a method for manufacturing a semiconductor electronic component using the same.

  In the present invention, a sacrificial layer refers to a layer formed on the assumption that it will be removed in a later step. The present invention is a resin composition for a sacrificial layer containing (A) a polyimide resin containing a hydroxy group and / or a carboxyl group in an amount of 1 to 30% by mass of the whole resin and (B) a solvent.

  The (A) polyimide resin of the present invention contains (A) a hydroxy group and / or a carboxyl group in an amount of 1 to 30% by mass of the whole resin. (A) When the content of the hydroxy group and / or the carboxyl group is 1% by mass or more, the sacrificial layer can be removed under mild conditions. It is preferably at least 2% by mass, more preferably at least 4% by mass. On the other hand, when the content is 30% by mass or less, the structure of the polyimide resin becomes rigid, and the generation of voids can be prevented in the heat treatment step at 200 to 500 ° C. Preferably it is 20 mass% or less. From the viewpoint of solubility in an organic solvent, a hydroxy group is preferred.

  The content of the hydroxy group and the carboxyl group in the polyimide resin can be calculated from the content of the hydroxy group and the carboxyl group in all the components used for the synthesis.

The specific method is as follows.
(1) Calculate the mass of all raw materials used for the polymerization of the polyimide resin.
(2) Calculate the mass of water generated in the polymerization step and the curing step of the polyimide resin.
(3) Calculate (1)-(2) to determine the mass of the polyimide resin.
(4) Calculate the mass of the hydroxy group or carboxyl group contained in the polyimide resin.
(5) The content of a hydroxy group or a carboxyl group is calculated from the quotient of (3) and (4).

  Further, the polyimide resin (A) may be a polyimide precursor that is closed by heating to form a polyimide, a polyimide precursor that is closed by heating, or a polyimide precursor in which a part of the polyimide resin is closed by heating. Is also good.

  Further, the (A) polyimide resin preferably has a tetracarboxylic dianhydride residue containing an aromatic ring and a diamine residue containing an aromatic ring. By having a tetracarboxylic dianhydride residue containing an aromatic ring and a diamine residue, the structure of the polyimide resin becomes rigid and the heat resistance is improved. Can be prevented.

  Specific examples of the diamine containing an aromatic ring include 2,5-diaminophenol, 3,5-diaminophenol, 3,3′-dihydroxybenzidine, 4,4′-dihydroxy-3,3′-diaminophenylpropane, 4,4'-dihydroxy-3,3'-diaminophenylhexafluoropropane, 4,4'-dihydroxy-3,3'-diaminophenylsulfone, 4,4'-dihydroxy-3,3'-diaminophenylether, 3,3′-dihydroxy-4,4′-diaminophenyl ether, 4,4′-dihydroxy-3,3′-diaminophenylpropanemethane, 4,4′-dihydroxy-3,3′-diaminobenzophenone, 3-bis (4-amino-3-hydroxyphenyl) benzene, 1,3-bis (3-amino-4-hydroxyphenyl) benzene, bis (4- (4-amino-3-hydroxyphenoxy) benzene) propane, bis (4- (3-amino-4-hydroxyphenoxy) benzene) sulfone, bis (4- (3-amino-4-hydroxyphenoxy)) Biphenyl, p-phenylenediamine, m-phenylenediamine, 2,5-diaminotoluene, 2,4-diaminotoluene, 3,5-diaminobenzoic acid, 2,6-diaminobenzoic acid, 2-methoxy-1,4- Phenylenediamine, 4,4'-diaminobenzanilide, 3,4'-diaminobenzanilide, 3,3'-diaminobenzanilide, 3,3'-dimethyl-4,4'-diaminobenzanilide, 9,9- Bis (4-aminophenyl) fluorene, 9,9-bis (3-aminophenyl) fluorene, 9,9-bis (3-methyl- -Aminophenyl) fluorene, 9,9-bis (3,5-dimethyl-4-aminophenyl) fluorene, 9,9-bis (3-methoxy-4-aminophenyl) fluorene, 9,9-bis (4- (Aminophenyl) fluorene-4-carboxylic acid, 9,9-bis (4-aminophenyl) fluorene-4-methyl, 9,9-bis (4-aminophenyl) fluorene-4-methoxy, 9,9-bis ( 4-aminophenyl) fluorene-4-ethyl, 9,9-bis (4-aminophenyl) fluorene-4-sulfone, 9,9-bis (4-aminophenyl) fluorene-3-carboxylic acid, 9,9- Bis (4-aminophenyl) fluorene-3-methyl, 1,3-diaminocyclohexane, 2,2′-dimethylbenzidine, 3,3′-dimethylbenzidine, 3′-dimethoxybenzidine, 2,4-diaminopyridine, 2,6-diaminopyridine, 1,5-diaminonaphthalene, 2,7-diaminofluorene, p-aminobenzylamine, m-aminobenzylamine, 4,4 ′ -Bis (4-aminophenoxy) biphenyl, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenyl Sulfone, 3,3'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfide, 3,3'-diaminobenzophenone, 3,4'-diaminobenzophenone, 4,4'-diaminobenzophenone 3,3'-dimethyl-4,4'-diami Diphenylmethane, 1,3-bis (4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 1,4-bis (3-amino Phenoxy) benzene, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (3-aminophenoxy) phenyl] propane, bis [4- (4-aminophenoxy) Phenyl] methane, bis [4- (3-aminophenoxy) phenyl] methane, bis [4- (4-aminophenoxy) phenyl] ether, bis [4- (3-aminophenoxy) phenyl] ether, bis [4- (4-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] sulfone, 2,2-bis [4- (4- Minofenokishi) phenyl] hexafluoropropane and the like. The aromatic diamines may be used alone or in combination of two or more.

  Among these aromatic diamines, an aromatic diamine having a hydroxy group or a carboxyl group is preferable. By containing an aromatic diamine having a hydroxy group or a carboxyl group, it is possible to introduce a hydroxy group or a carboxyl group into the polyimide resin (A), so that the solubility of the sacrificial layer is improved, and the sacrificial layer is formed under mild conditions. Can be removed. More preferably, it is an aromatic diamine compound represented by the general formula (1).

(R ¹ and R ² may be the same or different and each may be an alkyl group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, a fluoroalkyl group having 1 to 30 carbon atoms, hydrogen, a halogen, a carboxyl group , A carboxylate group, a phenyl group, a sulfone group, a nitro group and a cyano group, a and b each represent an integer of 1 to 3. X represents a direct bond or the following bond structure: .)

  Further, the structure of X of the compound represented by the general formula (1) is preferably the following bonding structure from the viewpoint of the solubility of the sacrificial layer.

  Further, the polyimide resin (A) of the present invention preferably contains a residue of the compound represented by the general formula (2) as an aromatic diamine. By including the residue of the compound represented by the general formula (2), the light transmittance in the wavelength region of 320 nm to 400 nm can be reduced. Therefore, the semiconductor electronic component is separated by laser irradiation in the same wavelength region. Can be.

(R ³ and R ⁴ may be the same or different, and each may be an alkyl group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, a fluoroalkyl group having 1 to 30 carbon atoms, hydrogen, halogen, or a hydroxy group. , A carboxyl group, a carboxylic acid ester group, a sulfone group, a nitro group, and a cyano group. C and d each represent an integer of 0 to 2 and c + d = 2.)
In the present invention, the aromatic diamine represented by the general formula (2) may be used alone, and the aromatic diamine represented by the general formula (2) and the aromatic diamine represented by the general formula (1) may be used. Diamines may be used in combination.

  Specific examples of the compound represented by the general formula (2) include 2,6-diaminoanthraquinone, 1,4-diaminoanthraquinone, 1,5-diaminoanthraquinone, 1,8-diaminoanthraquinone, and 1,4-diamino- Examples thereof include 2,3-dichloroanthraquinone, 1,5-diamino-4,8-dihydroxyanthraquinone, and 1,4-diamino-2,3-hydroxyanthraquinone. These may be used alone or in combination of two or more. From the viewpoint of cost, 2,6-diaminoanthraquinone, 1,4-diaminoanthraquinone, 1,5-diaminoanthraquinone, and 1,8-diaminoanthraquinone are preferred. More preferred is 2,6-diaminoanthraquinone, which has a large decrease in light transmittance.

In the polyimide resin (A) of the present invention, the content of the residue of the compound represented by the general formula (2) as the aromatic diamine is preferably 5 mol% or more and 60 mol% or less based on all the diamine residues. When the content is 5 mol% or more, the light transmittance in the wavelength range of 320 nm to 400 nm is reduced, and the semiconductor electronic component can be peeled off by laser irradiation in the same wavelength range. It is more preferably at least 10 mol%. From the viewpoint of solubility of the polyimide resin, the content is preferably 60 mol% or less, more preferably 40 mol% or less.
In the polyimide resin (A) of the present invention, the content of the diamine residue containing an aromatic ring is preferably from 80 mol% to 100 mol% of all the diamine residues from the viewpoint of heat resistance.

  Further, (A) the polyimide resin may have a residue of an alicyclic diamine or a silicon atom-containing diamine to such an extent that the heat resistance of the polyimide resin is not impaired. Examples of these diamines are 1,4-diaminocyclohexane, 4,4'-methylenebis (cyclohexylamine), 3,3'-methylenebis (cyclohexylamine), 4,4'-diamino-3,3'-dimethyl Dicyclohexylmethane, 4,4'-diamino-3,3'-dimethyldicyclohexyl, 1,3-bis (3-aminopropyl) tetramethyldisiloxane, 1,3-bis (4-anilino) tetramethyldisiloxane, etc. Can be mentioned. These diamines may be used alone or in combination of two or more.

  On the other hand, specific examples of the tetracarboxylic dianhydride containing an aromatic ring include pyromellitic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride and 2,2′dimethyl-anhydride. 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 5,5′dimethyl-3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,3,3 ′, 4 '-Biphenyltetracarboxylic dianhydride, 2,2', 3,3'-biphenyltetracarboxylic dianhydride, 3,3 ', 4,4'-diphenylethertetracarboxylic dianhydride, 2,3, 3 ′, 4′-diphenyl ether tetracarboxylic dianhydride, 2,2 ′, 3,3′-diphenyl ether tetracarboxylic dianhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, 2,2 ', 3,3'-benzophenonetetracarboxylic acid Hydrate, 2,3,3 ', 4'-benzophenonetetracarboxylic dianhydride, 3,3', 4,4'-diphenylsulfonetetracarboxylic dianhydride, 2,3,3 ', 4'- Diphenylsulfonetetracarboxylic dianhydride, 3,3 ', 4,4'-diphenylsulfoxidetetracarboxylic dianhydride, 3,3', 4,4'-diphenylsulfidetetracarboxylic dianhydride, 3,3 ', 4,4'-diphenylmethylenetetracarboxylic dianhydride, 4,4'-isopropylidene diphthalic anhydride, 4,4'-(hexafluoroisopropylidene) diphthalic anhydride, 3,4,9 1,10-perylenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 1,2,5,6 -Naphthalenetetracarboxylic acid Hydrate, 3,3 ", 4,4" -p-terphenyltetracarboxylic dianhydride, 3,3 ", 4,4" -methterphenyltetracarboxylic dianhydride, 2,3,6,7 -Anthracenetetracarboxylic dianhydride, 1,2,7,8-phenanthrenetetracarboxylic dianhydride and the like. The tetracarboxylic dianhydride containing an aromatic ring may be used alone or in combination of two or more.

  Among these tetracarboxylic dianhydrides containing an aromatic ring, it is preferable to include pyromellitic dianhydride. By containing pyromellitic dianhydride, the polyimide resin becomes rigid and the heat resistance is improved, so that the generation of voids can be prevented in the heat treatment step at 200 to 500 ° C. In addition, since the molecular weight is the lowest among tetracarboxylic dianhydrides containing an aromatic ring, by combining with an aromatic diamine having a hydroxy group or a carboxyl group, the hydroxyl group or carboxyl group content of the polyimide resin is reduced. And the sacrificial layer can be removed under mild conditions.

  In the polyimide resin (A) of the present invention, the content of the residue of the tetracarboxylic dianhydride containing an aromatic ring is, from the viewpoint of heat resistance, 80 mol% or more of all the tetracarboxylic dianhydride residues, 100 mol% or less is preferable.

  In addition, (A) tetracarboxylic dianhydride having an aliphatic ring can be contained so as not to impair the heat resistance of the polyimide resin. Specific examples of the tetracarboxylic dianhydride having an aliphatic ring include 2,3,5-tricarboxycyclopentylacetic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2 , 3,4-Cyclopentanetetracarboxylic dianhydride, 1,2,3,5-cyclopentanetetracarboxylic dianhydride, 1,2,4,5-bicyclohexenetetracarboxylic dianhydride, 1, 2,4,5-cyclohexanetetracarboxylic dianhydride, 1,3,3a, 4,5,9b-hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2- C] furan-1,3-dione. The above tetracarboxylic dianhydrides may be used alone or in combination of two or more.

  The molecular weight of the polyimide resin (A) can be adjusted by making the tetracarboxylic acid component and the diamine component used in the synthesis equimolar, or by making one of them excessive. Either the tetracarboxylic acid component or the diamine component may be excessive, and the polymer chain terminal may be sealed with a terminal blocking agent such as an acid component or an amine component. Dicarboxylic acid or its anhydride is preferably used as a terminal blocking agent for the acid component, and monoamine is preferably used as a terminal blocking agent for the amine component. At this time, it is preferable that the acid equivalent of the tetracarboxylic acid component including the terminal blocking agent of the acid component or the amine component and the amine equivalent of the diamine component be equimolar.

  When the molar ratio is adjusted so that the tetracarboxylic acid component is excessive or the diamine component is excessive, a dicarboxylic acid such as benzoic acid, phthalic anhydride, tetrachlorophthalic anhydride, aniline or an anhydride thereof, or a monoamine is used. It may be added as a sealant.

  In the present invention, the molar ratio of the tetracarboxylic acid component / diamine component of the polyimide copolymer and the polyimide resin can be appropriately adjusted so that the viscosity of the resin composition falls within a range that is easy to use in coating or the like. Generally, the molar ratio of the tetracarboxylic acid component / diamine component is adjusted within the range of 100/100 to 100/95, or 100/100 to 95/100. When the molar balance is lost, the molecular weight of the resin decreases, the mechanical strength of the formed film decreases, and the adhesive strength tends to weaken, so it is preferable to adjust the molar ratio within a range where the adhesive strength does not weaken. .

  The method for polymerizing the polyimide resin (A) of the present invention is not particularly limited. For example, when polymerizing a polyamic acid as a polyimide precursor, a tetracarboxylic dianhydride and a diamine are stirred in an organic solvent at 0 to 100 ° C. for 1 to 100 hours to obtain a polyamic acid resin solution. When the polyimide resin becomes soluble in the organic solvent, the temperature is raised to 120 to 300 ° C., and the mixture is stirred for 1 to 100 hours after polymerization of the polyamic acid, and converted to polyimide to obtain a polyimide solution. At this time, toluene, o-xylene, m-xylene, p-xylene or the like may be added to the reaction solution, and water generated in the imidization reaction may be removed by azeotropic distillation with these solvents.

The concentration of the polyimide resin (A) contained in the resin composition for a sacrificial layer of the present invention is usually preferably from 5 to 80% by mass, more preferably from 10 to 70% by mass, from the viewpoint of applicability. The resin composition for a sacrificial layer of the present invention contains (B) a solvent.
In polymerization of a polyimide resin, N-methyl-2-pyrrolidone (NMP) is often used as a solvent from the viewpoint of solubility. However, there is a concern that NMP may affect living organisms. Furthermore, since the boiling point under atmospheric pressure is as high as 202 ° C., the solvent does not sufficiently evaporate in the curing step of the polyimide resin, and there is a problem that the heat resistance of the sacrificial layer is reduced.

  The solvent (B) of the present invention preferably has a boiling point under atmospheric pressure of 150 to 180 ° C. If the boiling point under atmospheric pressure is 180 ° C. or lower, the solvent is sufficiently volatilized in the curing step of the polyimide resin, and the heat resistance of the sacrificial layer can be improved. Further, if the boiling point under atmospheric pressure is 150 ° C. or higher, it can be suitably used as a polymerization solvent. Further, without removing the polymerization solution, the solvent (B) contained in the resin composition for a sacrificial layer can be used. You can also.

  The solvent (B) is preferably a nitrogen-containing polar solvent from the viewpoint of solubility of the polyimide resin, and further from the viewpoint of the effect on living organisms, the solvent represented by the general formula (3) or (4). It is preferable to include

(R ⁵ and R ⁶ may be the same or different and each represents an alkyl group having 1 to 30 carbon atoms or a group selected from hydrogen. R ⁷ represents hydrogen or a hydroxyl group. R ⁸ and R ⁹ each represent the same. And may be different, and represent a group selected from an alkyl group having 1 to 30 carbon atoms and an alkoxy group having 1 to 30 carbon atoms.)

(R ^{10 to} R ¹³ may be the same or different and each represents an alkyl group having 1 to 30 carbon atoms or a group selected from hydrogen.)
Specific examples of the solvent represented by the general formula (3) include N, N, 2-trimethylpropionamide, N-ethyl, N, 2-dimethylpropionamide, N, N-diethyl-2-methylpropionamide, N, N, 2-trimethyl-2-hydroxypropionamide, N-ethyl-N, 2-dimethyl-2-hydroxypropionamide, N, N-diethyl-2-hydroxy-2-methylpropionamide and the like can be mentioned. These may be used alone or in combination of two or more.

  Specific examples of the solvent represented by the general formula (4) include N, N, N ', N'-tetramethylurea and N, N, N', N'-tetraethylurea. These may be used alone or in combination of two or more.

  The solvent (B) contained in the resin composition for a sacrificial layer of the present invention is more preferably a solvent represented by the general formula (3) or (4) and having a boiling point under atmospheric pressure of 150 to 180 ° C. . Specific examples include N, N, 2-trimethylpropionamide (boiling point: 175 ° C.), N, N, N ′, N′-tetramethylurea (boiling point: 177). These may be used alone or in combination of two or more.

  Further, other solvents can be added as long as the solubility of the polyimide resin (A) is not impaired. For example, ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ale, propylene glycol monoethyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, dipropylene glycol dimethyl ether, ethylene glycol Acetates such as monoethyl ether acetate, propylene glycol monomethyl ether acetate, propyl acetate, butyl acetate, isobutyl acetate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, methyl lactate, ethyl lactate, butyl lactate and the like, acetylacetone , Methyl propyl ketone, methyl butyl ketone, Ketones such as tyl isobutyl ketone, cyclopentanone and 2-heptanone, butyl alcohol, isobutyl alcohol, pentanol, 4-methyl-2-pentanol, 3-methyl-2-butanol, 3-methyl-3-methoxybutanol And alcohols such as diacetone alcohol, aromatic hydrocarbons such as toluene and xylene, and dimethyl sulfoxide, γ-butyrolactone, and the like, but are not limited thereto. These may be used alone or in combination of two or more.

  When the crosslinking agent is contained in the resin composition for a sacrificial layer of the present invention, the content of the crosslinking agent is preferably 0.1% by mass or less based on the polyimide resin (A). When the cross-linking agent is 0.1% by mass or less, no cross-linking occurs in the polyimide resin, and the sacrificial layer can be removed under mild conditions. The content is more preferably 0.01% by mass or less, and further preferably 0.001% by mass or less. The crosslinking agent is not particularly limited as long as it crosslinks the polyimide resin (A). Specific examples include an ethynyl group, a vinyl group, a methylol group, a methoxymethylol group, an epoxy group, and an oxetane group. Is a compound having 1 to 6 groups.

  The resin composition for a sacrificial layer of the present invention may contain inorganic fine particles as long as the effects of the present invention are not impaired. By containing the inorganic fine particles, the heat resistance of the resin composition can be improved. Specific examples of the inorganic fine particles include silica, alumina, titanium oxide, quartz powder, magnesium carbonate, potassium carbonate, barium sulfate, mica, and talc.

  When the (A) polyimide resin of the present invention is a polyamide precursor, it is applied to a substrate such as a wafer or glass, dried to form a coating film, and then converted into polyimide through a curing step. After coating, the conversion of the polyimide precursor to polyimide requires a temperature of 240 ° C. or higher, but by including an imidization catalyst in the polyamic acid resin composition, lower temperature, imidization in a short time is possible. It becomes possible. Specific examples of the imidization catalyst include pyridine, trimethylpyridine, β-picoline, quinoline, isoquinoline, imidazole, 2-methylimidazole, 1,2-dimethylimidazole, 2-phenylimidazole, 2,6-lutidine, triethylamine, m -Hydroxybenzoic acid, 2,4-dihydroxybenzoic acid, p-hydroxyphenylacetic acid, 4-hydroxyphenylpropionic acid, p-phenolsulfonic acid, p-aminophenol, p-aminobenzoic acid, and the like. It is not limited.

  Other resins can be added to the sacrificial layer resin composition of the present invention as long as the effects of the present invention are not impaired. Other resins include heat-resistant polymer resins such as acrylic resins, acrylonitrile resins, butadiene resins, urethane resins, polyester resins, polyamide resins, polyamideimide resins, epoxy resins, and phenolic resins. No. Further, a surfactant, a silane coupling agent, and the like may be added for the purpose of improving properties such as adhesiveness, heat resistance, coating properties, and storage stability.

  The resin composition for a sacrificial layer of the present invention can be used for manufacturing a semiconductor electronic component. Specifically, at least (1) a step of applying the resin composition for a sacrifice layer of the present invention to one surface of a supporting substrate to form a sacrifice layer; (2) a step of forming at least a semiconductor electronic component on the sacrifice layer; (3) It can be suitably used for manufacturing a semiconductor electronic component having a step of separating the semiconductor electronic component from the support substrate on which the sacrificial layer is formed in this order.

  The method of manufacturing a semiconductor electronic component on a support substrate on which a sacrificial layer is formed requires a step of peeling the semiconductor electronic component from the support substrate on which the sacrificial layer is formed without damaging the semiconductor electronic component. By using the resin composition for a sacrifice layer of the present invention, the semiconductor electronic component can be peeled from the support substrate without being damaged, and thereafter can be removed under mild conditions.

  Further, in the case where a heat treatment step at 200 ° C. to 500 ° C. is included in the semiconductor electronic component manufacturing process, the sacrificial layer is required to have heat resistance. The resin composition for a sacrificial layer of the present invention can be removed under a mild condition without causing voids in the sacrificial layer even in a heat treatment step at 200 to 500 ° C.

(1) The step of applying the resin composition for a sacrifice layer of the present invention to one surface of a support substrate to form a sacrifice layer will be described.
Examples of a method for applying the resin composition for a sacrificial layer of the present invention to a supporting substrate include a spin coater, a roll coater, screen printing, a slit die coater, and the like. In addition, after the resin composition is dried at 100 to 150 ° C. after the application, the sacrificial layer having good heat resistance can be formed by performing a thermosetting treatment continuously or intermittently at 200 to 500 ° C. for 1 to 3 hours. Obtainable. When the temperature of the thermosetting treatment is 200 ° C. or higher, the solvent (B) can be sufficiently removed, and the heat resistance is improved. It is more preferably at least 250 ° C., even more preferably at least 300 ° C. Furthermore, when the temperature of the thermosetting treatment is 500 ° C. or less, the oxidative deterioration of the polyimide resin (A) can be prevented, and the sacrificial layer can be removed under mild conditions. The temperature is more preferably 430 ° C or lower, and further preferably 410 ° C or lower.

  Further, the heat curing treatment is preferably performed in a nitrogen atmosphere. By performing the thermosetting treatment in a nitrogen atmosphere, it is possible to prevent (A) the oxidative deterioration of the polyimide resin and to remove the sacrificial layer under mild conditions.

  The thickness of the sacrificial layer is preferably from 0.1 μm to 10 μm. When the thickness is 10 μm or less, the time of a sacrificial layer removing step described later can be shortened. More preferably, it is 3 μm or less.

  (2) A step of forming at least a semiconductor electronic component on the sacrificial layer will be described.

In the present invention, there is no limitation on the semiconductor electronic component manufactured on the supporting substrate on which the sacrificial layer is formed.
In particular, it can be suitably used in a semiconductor electronic component manufacturing process having a heat treatment process at 200 to 500 ° C.

  For example, there is a fan-out type wafer level package (FO-WLP) in which a rewiring layer is formed on a supporting substrate on which a sacrificial layer is formed, and then the semiconductor chip is connected to the rewiring layer via bumps. . The rewiring layer is generally a laminate of an interlayer insulating film such as a heat-resistant resin and a conductive metal film such as a Cu metal wiring. Examples of the heat-resistant resin include a polyimide-based heat-resistant resin (such as Photonice PW series manufactured by Toray Industries, Inc.) and a polybenzoxazole-based heat-resistant resin (such as Pymel AM-270 series manufactured by Asahi Kasei Corporation).

  As a more detailed method for forming a rewiring layer, an interlayer insulating film is formed on a supporting substrate on which a sacrificial layer is formed, a heat-resistant resin is applied, and prebaking is performed. When the heat-resistant resin is a positive photosensitive resin, a region to be opened is irradiated with an actinic ray such as a UV ray through a photomask or the like, and then developed with a developer such as TMAH (tetramethylammonium hydroxide). . Thereafter, thermal curing is performed at 200 to 500 ° C. to obtain an interlayer insulating film. Subsequently, Cu is sputtered as a conductive metal film, a photoresist layer is formed, and the wiring is patterned. By repeating the above operation and multiply laminating the interlayer insulating film and the conductive metal film, a rewiring layer can be formed. Since a heat treatment step of 200 to 500 ° C. is performed by thermal curing of the interlayer insulating film, heat resistance is required for the sacrificial layer.

  In the present invention, the heat treatment method at 200 to 500 ° C. is not limited, and may be used for a device for heating in a high-temperature atmosphere such as an oven, a heating device for contacting a hot plate with a supporting substrate such as a hot plate, or the like.

  In the present invention, if necessary, a barrier metal may be formed on the sacrificial layer, and a semiconductor electronic component may be formed thereon. By forming the barrier metal, it is possible to prevent the sacrificial layer from being deteriorated by a chemical solution used in the manufacturing process of the semiconductor electronic component. The material of the barrier metal includes, but is not limited to, Ti, Cu, or an alloy thereof. Examples of a method for forming the barrier metal include a sputtering method, but are not limited thereto.

(3) The step of separating the semiconductor electronic component from the support substrate will be described.
The method of manufacturing a semiconductor electronic component on a support substrate on which a sacrificial layer is formed requires a step of peeling the semiconductor electronic component from the support substrate on which the sacrificial layer is formed without damaging the semiconductor electronic component. In the resin composition for a sacrifice layer of the present invention, (a) a method of irradiating a laser to the sacrifice layer through the support substrate from a side of the support substrate where the sacrifice layer is not formed to peel off the semiconductor electronic component, or (b) an organic method. A method of dissolving the sacrificial layer with a solvent or an aqueous alkali solution and peeling the semiconductor electronic component can be suitably used.

  (A) A method of exposing a semiconductor electronic component by irradiating a laser to the sacrificial layer through the support substrate from the side of the support substrate where the sacrificial layer is not formed will be described.

  When the sacrifice layer is irradiated with a laser beam, heat generated by absorption of the laser beam into the sacrifice layer causes thermal decomposition of the sacrifice layer near the interface with the support substrate, thereby separating the sacrifice layer and the support substrate. be able to. Since the resin composition for a sacrificial layer of the present invention has strong absorption in the ultraviolet light range, it is preferable that the laser irradiation has any wavelength in the wavelength range of 200 to 400 nm.

  The wavelength of the laser irradiation is not particularly limited, and includes 266 nm, 308 nm, 343 nm, 351 nm, and 355 nm. The laser device is not limited as long as the sacrificial layer can be peeled off, and examples thereof include a XeCl excimer laser (308 nm), a XeF excimer laser (351 nm), and a YAG (yttrium aluminum garnet) solid laser (355 nm). From the viewpoint of cost, a solid laser is preferred.

  When the thickness of the sacrificial layer is 1 μm, it is preferable that the minimum value of the light transmittance in the wavelength region of 200 to 400 nm is 40% or less. It is more preferably at most 20%. When the minimum value of the light transmittance is 40% or less, laser light can be absorbed and peeled off easily. It is preferable to perform laser peeling at a wavelength at which the light transmittance of the sacrificial layer is 40% or less.

  When the semiconductor electronic component is peeled off by irradiating the sacrificial layer with a laser, the light transmittance of the supporting substrate at a wavelength of 308 nm is preferably 40 to 100%. It is more preferably at least 50%. When the light transmittance of the supporting substrate at a wavelength of 308 nm is 40% or more, laser light can pass through the supporting substrate and reach the sacrificial layer, so that laser separation can be performed. Examples of the support substrate having a light transmittance of 40 to 100% at a wavelength of 308 nm include, but are not limited to, a glass substrate, a quartz substrate, and a ceramic substrate.

  (B) A method of dissolving the sacrificial layer with an organic solvent or an alkaline aqueous solution to peel off the semiconductor electronic component will be described.

  The semiconductor electronic component can be peeled off by dissolving the sacrificial layer of the present invention with an organic solvent or an aqueous alkaline solution. The dissolution method is not particularly limited, and includes, for example, a dip method and a paddle method, but is not limited thereto.

  The organic solvent preferably contains an amine-based solvent. Specific examples include, but are not limited to, monomethanolamine, dimethanolamine, trimethanolamine, monoethanolamine, diethanolamine, triethanolamine, and dimethylamine. From the viewpoint of solubility, monoethanolamine is more preferred. The amine-based solvent has the effect of opening the imide group of the polyimide resin to facilitate dissolution in the organic solvent, and can shorten the dissolution time.

  Other solvents can be added as long as the effect of the solubility of the organic solvent is not impaired. For example, ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ale, propylene glycol monoethyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, dipropylene glycol dimethyl ether, ethylene glycol Acetates such as monoethyl ether acetate, propylene glycol monomethyl ether acetate, propyl acetate, butyl acetate, isobutyl acetate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, methyl lactate, ethyl lactate, butyl lactate and the like, acetylacetone , Methyl propyl ketone, methyl butyl ketone, Ketones such as tyl isobutyl ketone, cyclopentanone and 2-heptanone, butyl alcohol, isobutyl alcohol, pentanol, 4-methyl-2-pentanol, 3-methyl-2-butanol, 3-methyl-3-methoxybutanol , Alcohols such as diacetone alcohol, aromatic hydrocarbons such as toluene and xylene, N-methyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone N, N-dimethylformamide, N, N-dimethylacetamide Dimethylsulfoxide, γ-butyrolactone, N, N, 2-trimethylpropionamide, N-ethyl, N, 2-dimethylpropionamide, N, N-diethyl-2-methylpropionamide, N, N, 2-trimethyl- 2-hydroxypropionamide, N-ethyl- N, 2-dimethyl-2-hydroxypropionamide, N, N-diethyl-2-hydroxy-2-methylpropionamide N, N, N ', N'-tetraethylurea and the like. These may be used alone or in combination of two or more.

  Specific examples of the aqueous alkaline solution include aqueous solutions of sodium hydroxide, sodium hydrogen carbonate, potassium hydroxide, tetramethylammonium hydroxide and the like. These may be used alone or in combination of two or more. A mixture of an organic solvent and an aqueous alkali solution may be used.

  The temperature of the organic solvent or the aqueous alkali solution when dissolving the sacrificial layer is preferably from 20 to 70C. When at least a part of the semiconductor electronic component is the heat-resistant resin, if the temperature of the organic solvent or the aqueous alkaline solution exceeds 70 ° C., the heat-resistant resin may be damaged. The temperature is more preferably 60 ° C or lower, and further preferably 50 ° C or lower. When the temperature of the organic solvent or the aqueous alkali solution is lower than 20 ° C., a cooling device for the organic solvent or the aqueous alkali solution is required, which is not preferable from the viewpoint of cost.

  In the present invention, it is preferable that the method further includes (4) a step of removing the sacrificial layer with an organic solvent or an aqueous alkaline solution after the step of (3) separating the semiconductor electronic component from the support substrate.

The sacrificial layer of the present invention can be removed with an organic solvent or an aqueous alkaline solution.
The organic solvent preferably contains an amine-based solvent. Specific examples include, but are not limited to, monomethanolamine, dimethanolamine, trimethanolamine, monoethanolamine, diethanolamine, triethanolamine, and dimethylamine. From the viewpoint of solubility, monoethanolamine is more preferred. The amine-based solvent has an effect of opening the imide group of the polyimide resin to facilitate dissolution in the organic solvent, and can shorten the removal time.

  Other solvents can be added as long as the effect of the solubility of the organic solvent is not impaired. For example, ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ale, propylene glycol monoethyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, dipropylene glycol dimethyl ether, ethylene glycol Acetates such as monoethyl ether acetate, propylene glycol monomethyl ether acetate, propyl acetate, butyl acetate, isobutyl acetate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, methyl lactate, ethyl lactate, butyl lactate and the like, acetylacetone , Methyl propyl ketone, methyl butyl ketone, Ketones such as tyl isobutyl ketone, cyclopentanone and 2-heptanone, butyl alcohol, isobutyl alcohol, pentanol, 4-methyl-2-pentanol, 3-methyl-2-butanol, 3-methyl-3-methoxybutanol , Alcohols such as diacetone alcohol, aromatic hydrocarbons such as toluene and xylene, N-methyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone N, N-dimethylformamide, N, N-dimethylacetamide Dimethylsulfoxide, γ-butyrolactone, N, N, 2-trimethylpropionamide, N-ethyl, N, 2-dimethylpropionamide, N, N-diethyl-2-methylpropionamide, N, N, 2-trimethyl- 2-hydroxypropionamide, N-ethyl- N, 2-dimethyl-2-hydroxypropionamide, N, N-diethyl-2-hydroxy-2-methylpropionamide N, N, N ', N'-tetraethylurea and the like. These may be used alone or in combination of two or more.

  Specific examples of the aqueous alkaline solution include aqueous solutions of sodium hydroxide, sodium hydrogen carbonate, potassium hydroxide, tetramethylammonium hydroxide and the like. These may be used alone or in combination of two or more. A mixture of an organic solvent and an aqueous alkali solution may be used.

  The temperature of the organic solvent or the aqueous alkali solution when dissolving the sacrificial layer is preferably from 20 to 70C. When at least a part of the semiconductor electronic component is the heat-resistant resin, if the temperature of the organic solvent or the aqueous alkaline solution exceeds 70 ° C., the heat-resistant resin may be damaged. The temperature is more preferably 60 ° C or lower, and further preferably 50 ° C or lower. When the temperature of the organic solvent or the aqueous alkali solution is lower than 20 ° C., a cooling device for the organic solvent or the aqueous alkali solution is required, which is not preferable from the viewpoint of cost.

Hereinafter, the present invention will be described with reference to Examples, but the present invention is not limited to these Examples.
Evaluation methods of light transmittance measurement of the sacrificial layer, heat treatment evaluation of the sacrificial layer, laser peeling evaluation of the sacrificial layer, chemical solution peeling evaluation of the sacrificial layer, removal evaluation of the sacrificial layer, and evaluation of the heat-resistant resin film thickness will be described.

(1) Measurement of light transmittance of sacrificial layer Thickness of cured resin composition for sacrificial layer prepared in Synthesis Examples 1 to 17 below on a glass substrate (Eagle XG, manufactured by Corning Inc., 5 cm square) having a thickness of 500 μm. Is adjusted by a spin coater so as to adjust the rotation speed to 1 μm, heat-treated at 120 ° C. for 10 minutes, dried, and then heat-treated at 300 ° C. for 30 minutes in an N2 oven to cure, thereby obtaining a glass substrate with a sacrificial layer. Was.

  The light transmittance at wavelengths of 266 nm, 308 nm, 343 nm, 351 nm, and 355 nm when the thickness of the sacrificial layer was 1 μm was measured using an ultraviolet-visible spectrophotometer (MultiSpec-1500, manufactured by Shimadzu Corporation).

(2) Evaluation of heat treatment of sacrificial layer On the glass substrate with the sacrificial layer obtained in (1), the polyimide heat resistant resin composition prepared in Synthesis Example 18 below was spin-coated so that the thickness after curing became 5 μm. The coating was performed by adjusting the number of rotations, heat-treated at 120 ° C. for 10 minutes, dried, and then heat-treated in an N 2 oven at 300 ° C. for 60 minutes to cure, thereby obtaining a glass substrate with a heat-resistant resin. Subsequently, a 100-nm-thick Cu metal film was formed on the heat-resistant resin by using a sputtering device (SH-450, manufactured by ULVAC). This operation was repeated twice to form a laminated glass substrate of an interlayer insulating film made of a heat-resistant resin and a conductive metal film made of a Cu metal film.

  At this time, the glass substrate with the laminated body was visually observed from the glass side, and if there was no void, the heat treatment evaluation of the sacrificial layer was “A”, and if the void was confirmed, the heat treatment evaluation of the sacrificial layer was “B”.

(3) Evaluation of laser peeling of sacrificial layer A Kapton tape was attached to the laminated body side of the glass substrate with heat resistant resin obtained in (2) to reinforce the laminated body, and then an excimer laser having a wavelength of 308 nm (shape: 14 mm × (1 mm, 80% overlap ratio) was irradiated from the glass substrate side to perform a laser peeling test. The irradiation energy required for peeling the laminate was measured and evaluated according to the following criteria.
A: irradiation energy 250 mJ / cm ² or less B: irradiation energy exceeds ^{250mJ / cm 2, 350mJ / cm} 2 or less C: the irradiation energy can not be peeled off at 350 mJ / cm ^2.
Subsequently, a Kapton tape was attached to the laminate side of the glass substrate with the laminate obtained in (2) to reinforce the laminate, and then a solid laser having a wavelength of 355 nm (shape: 40 mm × 0.4 mm, overlap ratio) (75%) from the glass substrate side to perform a laser peeling test. The irradiation energy required for peeling the laminate was measured and evaluated according to the following criteria.
A: irradiation energy 250 mJ / cm ² or less B: irradiation energy exceeds ^{250mJ / cm 2, 350mJ / cm} 2 or less C: the irradiation energy can not be peeled off at 350 mJ / cm ^2.

(4) Evaluation of chemical liquid peeling of sacrificial layer The glass substrate with heat resistant resin obtained in (2) was cut into a size of 5 mm square with a dicing device (DAD3350, manufactured by DISCO). Thereafter, a Kapton tape was stuck on the laminate side to reinforce the laminate, and then immersed in a chemical solution shown in Table 4 below at a temperature of 23 ° C. to evaluate the chemical solution peeling. The evaluation criteria are as follows. In Table 4, the term "organic solvent" refers to the organic solvent produced in Production Example 1 below.
A: Peeling was possible within 20 minutes.
B: Peeling was possible within 20 minutes to 30 minutes.
C: The film could not be peeled off within 30 minutes.

(5) Removal evaluation of sacrifice layer The laminated body after laser peeling obtained in (2) was immersed in a removal solution and temperature conditions shown in Table 4 below to remove the sacrifice layer. The evaluation criteria are as follows. In Table 4, the term "organic solvent" refers to the organic solvent produced in Production Example 1 below.
A: It could be removed within 5 minutes.
B: It could be removed within 5 minutes to 10 minutes.
C: It could be removed within 10 to 20 minutes.
D: Could not be removed within 20 minutes.

(6) Evaluation of heat-resistant resin film thickness (5) The thickness of the heat-resistant resin of the laminate evaluated for removal of the sacrificial layer was measured by a cross-sectional SEM and compared with the initial film thickness of 5 μm. The evaluation criteria are as follows.
A: There is no change in the thickness of the heat-resistant protective film. B: The reduction of the heat-resistant protective film is 1 μm or less. C: The reduction of the heat-resistant protective film is 1 μm or more.

The abbreviations of the acid dianhydrides, diamines and solvents shown in the following synthesis examples and production examples are as follows.
ODPA: 3,3 ', 4,4'-diphenylethertetracarboxylic dianhydride PMDA: pyromellitic dianhydride BAHF: 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane ABPS: 4 4,4'-dihydroxy-3,3'-diaminophenylsulfone FDA: 9,9-bis (3-amino-4-hydroxyphenyl) fluorene APB: 1,3-bis (3-aminophenoxy) benzene SiDA: 1, 1,3,3-tetramethyl-1,3-bis (3-aminopropyl) disiloxane MBAA: 5,5′-methylenebis (2-aminobenzoic acid)
DMIB: N, N, 2-trimethylpropionamide NMP: N-methyl-2-pyrrolidone GBL: γ-butyrolactone DMM: Dipropylene glycol dimethyl ether Synthesis Example 1 (Polymerization of polyimide)
In a reactor equipped with a thermometer, a dry nitrogen inlet, a heating / cooling device using hot / cooling water, and a stirrer, 347.9 g (0.95 mol) of BAHF and 12.4 g (0.05 mol) of SiDA were added to DMIB. After charging and dissolving together with 1735.5 g, 218.1 g (1 mol) of PMDA was added and reacted at 50 ° C. for 4 hours to obtain a 25% by mass polyimide solution (PA1) as a sacrificial layer resin composition. Was.

  The temperature of the polyimide solution was returned to room temperature, and the presence or absence of the precipitate was confirmed by visual evaluation. The results are shown in Table 1. The hydroxyl group content in the polyimide resin was calculated as follows, and the results are summarized in Table 1. The light transmittance of the sacrificial layer was measured, and the results are shown in Table 3.

<Content of hydroxy group in polyimide resin>
1. Calculate the total amount of polyimide resin raw material.

347.9 g (BAHF) +12.4 g (SiDA) +218.1 g (PMDA) = 578.4 g
2. The amount of dehydration by the imidization reaction is subtracted from the total amount of the polyimide resin raw material, and the weight of the polyimide resin is calculated. (Assuming the amount of dehydration is 1.8 mol)
578.4 g-(18.0 g / mol x 1.8 mol) = 546.0 g (weight of polyimide resin)
3. Calculate the weight of hydroxy groups in the polyimide resin. (It has two in BAHF.)
17.0 g / mol × 0.95 mol × 2 = 32.3 g (weight of hydroxy group in polyimide resin)
4. Calculate the hydroxyl group content in the polyimide resin.

32.3 g / 546.0 g * 100 = 5.9 wt%
Synthesis Examples 2 to 16 (Polymerization of polyimide)
The same operation as in Synthesis Example 1 was performed except that the types and amounts of the acid dianhydride, the diamine, and the solvent were changed as shown in Tables 1 and 2, and a 25% by mass polyimide solution as a sacrificial layer resin composition was obtained. (PA2 to PA16) were obtained.
The temperature of the polyimide solution was returned to room temperature, and the presence or absence of the precipitate was confirmed by visual evaluation. The results are shown in Table 1. Further, the content of the hydroxy group in the polyimide resin was calculated in the same manner as in Synthesis Example 1, and the results are shown in Tables 1 and 2. The light transmittance of the sacrificial layer was measured, and the results are shown in Table 3.

Synthesis Example 17 (Polymerization of polyimide)
In a reactor equipped with a thermometer, a dry nitrogen inlet, a heating / cooling device using hot / cooling water, and a stirrer, 272.0 g (0.95 mol) of MBAA and 12.4 g (0.05 mol) of SiDA were added to DMIB. After charging and dissolving with 1507.5 g, 218.1 g (1 mol) of PMDA was added and reacted at 50 ° C. for 4 hours to obtain a 25% by mass polyimide solution (PA17) as a sacrificial layer resin composition. Was.

  The polyimide solution was returned to room temperature, and the presence or absence of a precipitate was confirmed by visual evaluation. As a result, no precipitate was confirmed. Further, the content of the carboxyl group in the polyimide resin was calculated as follows, and as a result, it was 18.2 wt%. The light transmittance of the sacrificial layer was measured, and the results are shown in Table 3.

<Content of carboxyl group in polyimide resin>
1. Calculate the total amount of polyimide resin raw material.

272.0 g (MBAA) +12.4 g (SiDA) +218.1 g (PMDA) = 502.5 g
2. The amount of dehydration by the imidization reaction is subtracted from the total amount of the polyimide resin raw material, and the weight of the polyimide resin is calculated. (Assuming the amount of dehydration is 1.8 mol)
502.5 g-(18.0 g / mol x 1.8 mol) = 470.1 g (weight of polyimide resin)
3. Calculate the carboxyl group weight in the polyimide resin. (It has two in MBAA.)
45.0 g / mol x 0.95 mol x 2 = 85.5 g (carboxyl group weight in polyimide resin)
4. Calculate the carboxyl group content in the polyimide resin.
85.5g / 470.1g * 100 = 18.2wt%

Synthesis Example 18 (Production of polyimide heat-resistant resin composition)
In a reaction vessel equipped with a thermometer, a dry nitrogen inlet, a heating / cooling device using hot / cold water, and a stirrer, 20.87 g (0.057 mol) of BAHF, 1.24 g (0.005 mol) of SiDA, and end plugs As a stopper, 8.18 g (0.075 mol) of 3-aminophenol was dissolved in 80 g of NMP. Here, 31.02 g (0.1 mol) of ODPA was added together with 20 g of NMP, reacted at 20 ° C. for 1 hour, and then reacted at 50 ° C. for 4 hours. Thereafter, 15 g of xylene was added, and the mixture was stirred at 150 ° C. for 5 hours while azeotroping water with xylene. After the stirring, the solution was poured into 3 l of water to collect a white precipitate. The precipitate was collected by filtration, washed three times with water, and then dried in a vacuum dryer at 80 ° C. for 20 hours. 10 g of the polyimide polymer powder thus obtained and 4 g of a thermal crosslinkable compound NIKALAC MW-100LM (trade name, manufactured by Sanwa Chemical Co., Ltd.) were mixed with propylene glycol monoethyl ether. After dissolving in 20 g, the solution was filtered through a PTFE filter paper having a pore size of 1 μm to obtain a polyimide heat-resistant resin composition.

Production Example 1 (Adjustment of organic solvent)
30 g of monoethanolamine, 30 g of DMM, and 30 g of N-methyl-2-pyrrolidone were charged into a reactor equipped with a stirrer, and stirred at room temperature for 1 hour to obtain an organic solvent.

Example 1
On a glass substrate (Eagle XG, manufactured by Corning, 5 cm square) having a thickness of 500 μm, the number of revolutions was adjusted with a spin coater so that the thickness after curing the sacrificial layer resin composition prepared in Synthesis Example 1 was 1 μm. Then, after heat treatment at 120 ° C. for 10 minutes and drying, heat treatment was performed in an N 2 oven at 300 ° C. for 30 minutes for curing to obtain a glass substrate with a sacrificial layer.

  Next, the polyimide heat-resistant resin composition prepared in Synthesis Example 18 was applied on a glass substrate with a sacrificial layer by adjusting the rotation speed with a spin coater so that the thickness after curing became 5 μm, and then applied at 120 ° C. After heat-treating and drying, a heat treatment was performed in an N2 oven at 300 ° C. for 60 minutes for curing to obtain a glass substrate with a heat-resistant resin. Subsequently, a 100-nm-thick Cu metal film was formed on the heat-resistant resin by using a sputtering device (SH-450, manufactured by ULVAC). This operation was repeated twice to form a laminated glass substrate of an interlayer insulating film made of a heat-resistant resin and a conductive metal film made of a Cu metal film. A heat treatment evaluation of the sacrificial layer, a laser peeling evaluation of the sacrificial layer, a chemical solution peeling evaluation of the sacrificial layer, a removal evaluation of the sacrificial layer, and a film thickness evaluation of the heat-resistant resin were performed using the obtained glass substrate with the laminated body. 4

Examples 2 to 21
A glass substrate with a laminate was obtained in the same manner as in Example 1, except that the resin composition for the sacrificial layer and the curing temperature of the sacrificial layer were changed as shown in Table 4.

  Using the obtained glass substrate with a laminate, the heat treatment evaluation of the sacrificial layer, the laser peeling evaluation of the sacrificial layer, the chemical solution peeling evaluation of the sacrificial layer, the removal evaluation of the sacrificial layer, the heat-resistant resin film under the conditions shown in Table 4 The thickness was evaluated and the results are summarized in Table 4.

Comparative Examples 1-3
A glass substrate with a laminate was obtained in the same manner as in Example 1, except that the resin composition for the sacrificial layer and the curing temperature of the sacrificial layer were changed as shown in Table 4.

  Using the obtained glass substrate with a laminate, the heat treatment evaluation of the sacrificial layer, the laser peeling evaluation of the sacrificial layer, the chemical solution peeling evaluation of the sacrificial layer, the removal evaluation of the sacrificial layer, the heat-resistant resin film under the conditions shown in Table 4 The thickness was evaluated and the results are summarized in Table 4.

Claims (14)

A resin composition for a sacrifice layer containing at least (A) a polyimide resin containing 1 to 30% by mass of a hydroxy group and / or a carboxyl group in the entire resin and (B) a solvent. The resin for a sacrifice layer according to claim 1, wherein the (A) polyimide resin containing a hydroxy group and / or a carboxyl group in an amount of 1 to 30% by mass of the entire resin contains a diamine residue represented by the general formula (1). Composition.

(R ¹ and R ² may be the same or different and each may be an alkyl group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, a fluoroalkyl group having 1 to 30 carbon atoms, hydrogen, a halogen, a carboxyl group , A carboxylate group, a phenyl group, a sulfone group, a nitro group and a cyano group, a and b each represent an integer of 1 to 3. X represents a direct bond or the following bond structure. )

3. The sacrificial layer according to claim 1, wherein the (A) polyimide resin containing a hydroxyl group and / or a carboxyl group in an amount of 1 to 30% by mass of the entire resin contains a diamine residue represented by the general formula (2). 4. Resin composition.

(R ³ and R ⁴ may be the same or different, and each may be an alkyl group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, a fluoroalkyl group having 1 to 30 carbon atoms, hydrogen, halogen, or a hydroxy group. , A carboxyl group, a carboxylic acid ester group, a sulfone group, a nitro group, and a cyano group. C and d each represent an integer of 0 to 2 and c + d = 2.) The resin composition for a sacrificial layer according to any one of claims 1 to 3, wherein the solvent (B) contains a compound represented by the general formula (3) or the general formula (4).

(R ⁵ and R ⁶ may be the same or different and each represents an alkyl group having 1 to 30 carbon atoms or a group selected from hydrogen. R ⁷ represents hydrogen or a hydroxyl group. R ⁸ and R ⁹ each represent the same. And may be different, and represent a group selected from an alkyl group having 1 to 30 carbon atoms and an alkoxy group having 1 to 30 carbon atoms.)

(R ^{10 to} R ¹³ may be the same or different and each represents an alkyl group having 1 to 30 carbon atoms or a group selected from hydrogen.) 5. A step of applying the resin composition for a sacrificial layer according to claim 1 to at least one surface of a support substrate to form a sacrificial layer, and (2) at least a semiconductor electronic component on the sacrificial layer. And (3) separating the semiconductor electronic component from the support substrate on which the sacrificial layer is formed, in this order. The method of manufacturing a semiconductor electronic component according to claim 5, wherein the step (2) of forming at least the semiconductor electronic component on the sacrificial layer includes a step of performing a heat treatment at 200 to 500C. In the step (3) of peeling the semiconductor electronic component from the support substrate on which the sacrificial layer is formed, the semiconductor electronic component is peeled off by irradiating the sacrificial layer through the support substrate from the side of the support substrate where the sacrificial layer is not formed. The method for manufacturing a semiconductor electronic component according to claim 5, which is a step. The method for manufacturing a semiconductor electronic component according to claim 7, wherein a wavelength range of the laser used for the laser irradiation is 250 to 400 nm. The method for manufacturing a semiconductor electronic component according to claim 8, wherein the wavelength of the laser used for the laser irradiation is at least one of 266 nm, 308 nm, 343 nm, 351 nm, and 355 nm. The method for manufacturing a semiconductor electronic component according to claim 5, wherein the minimum value of the light transmittance at a wavelength of 250 to 400 nm at a thickness of 1 μm of the sacrificial layer is 40% or less. The method for manufacturing a semiconductor electronic component according to claim 5, wherein the light transmittance of the support substrate at a wavelength of 308 nm is 40 to 100%. 7. The method according to claim 5, wherein the step (3) of peeling the semiconductor electronic component from the supporting substrate on which the sacrificial layer is formed is a step of dissolving the sacrificial layer with an organic solvent or an aqueous alkaline solution to peel the semiconductor electronic component. The manufacturing method of the semiconductor electronic component as described in the above. 12. The method according to claim 5, further comprising: (4) removing the sacrificial layer with an organic solvent or an alkaline aqueous solution after the (3) removing the semiconductor electronic component from the support substrate on which the sacrificial layer is formed. 13. The manufacturing method of the semiconductor electronic component as described in the above. 14. The method for manufacturing a semiconductor electronic component according to claim 12, wherein the organic solvent contains monoethanolamine.