JP6672069B2 - Curable resin composition - Google Patents

Description

  The present invention relates to a curable resin composition, and more particularly, to a curable resin composition capable of suppressing warpage of a semiconductor wafer or a semiconductor package, and in particular, a fan-out in which an arrangement region of an external connection electrode is larger than a plane size of a semiconductor. The present invention relates to a curable resin composition for forming a warp correction layer provided on a surface of a (Fan-out) type wafer level package opposite to a rewiring layer.

  2. Description of the Related Art In recent years, demands for miniaturization in the field of semiconductor circuits and the like have increased, and in order to meet the demands, semiconductor circuits are sometimes mounted in a package (Chip Size Package) close to the chip size. As one of means for realizing a chip size package, a packaging method called a wafer level package (hereinafter, sometimes abbreviated as WLP) for bonding and fragmenting at a wafer level has been proposed. WLP has attracted attention because it can contribute to cost reduction and miniaturization. The WLP is mounted face down on a circuit board on which electrodes are formed.

  By the way, the number of external connection electrodes (terminals, bumps) of the semiconductor chip tends to increase with the miniaturization and high integration of the semiconductor chip, and therefore, the pitch of the external connection electrodes of the semiconductor chip becomes small. Tend to be. However, it is not always easy to directly mount a semiconductor chip having bumps formed at a fine pitch on a circuit board.

  In order to solve the above problems, a semiconductor sealing material region is formed on the outer periphery of the semiconductor chip, and a rewiring layer connected to the electrode is also provided in the semiconductor sealing material region to reduce the bump pitch. It is proposed to make it larger. Such a WLP is called a fan-out type wafer level package (hereinafter sometimes abbreviated as FO-WLP) because the size of the area where the bumps are arranged is larger than the size of the semiconductor chip.

  In FO-WLP, a semiconductor chip is embedded with a semiconductor sealing material. The circuit surface of the semiconductor chip is exposed outward, and a boundary between the semiconductor chip and the semiconductor encapsulant is formed. A rewiring layer connected to the electrode of the semiconductor chip is also provided in the region of the semiconductor sealing material in which the semiconductor chip is embedded, and the bump is electrically connected to the electrode of the semiconductor chip via the rewiring layer. The pitch of the bumps can be set to be larger than the pitch of the electrodes of the semiconductor chip.

  Further, not only a semiconductor chip but also a plurality of electronic components may be housed in one package, or a plurality of semiconductor chips may be embedded in a semiconductor encapsulant to form one semiconductor component. In such a package, a plurality of electronic components are embedded with a semiconductor sealing material. A rewiring layer connected to an electrode of the electronic component is provided in the semiconductor encapsulant in which the plurality of electronic components are embedded, and the bump is electrically connected to the electrode of the electronic component via the rewiring layer. Also in this case, since the size of the area where the bumps are arranged is larger than the size of the semiconductor chip, it can be regarded as FO-WLP.

  In such a package, generally, a semiconductor chip or an electronic component is arranged at a fixed interval on a support, embedded using a sealing material for a semiconductor, and after the sealing material is cured by heating, the support is And a pseudo wafer is produced. Subsequently, a rewiring layer is formed from the semiconductor chip circuit surface of the pseudo wafer to the extended semiconductor sealing material region. In this way, the pitch of the bumps can be set larger than the pitch of the electrodes of the semiconductor chip.

  In the formation of the rewiring layer, generally, a positive-type sensitive resin is applied to the semiconductor chip circuit surface of the pseudo wafer, prebaked, and activated by UV light or the like in a region to be opened through a photomask or the like. Irradiation with light, followed by development using a developer such as TMAH (tetramethylammonium hydroxide), heat curing, oxygen plasma treatment, etc., metal electrode sputtering, and further forming a photoresist layer A wiring is patterned to form a rewiring layer (for example, Patent Document 1).

  In the case of WLP or FO-WLP, when a rewiring layer is formed on the semiconductor chip circuit surface, the circuit surface (that is, the surface on which the insulating film is formed) is mainly due to shrinkage of the insulating film such as photosensitive polyimide between the wires during curing. A concave warp deformation occurs. In order to reduce this amount of warpage, a resin layer is formed on one surface of a substrate made of a wafer-shaped semiconductor, and the entire area of the resin layer is warped so as to bulge out into a spherical shape, and then the resin layer is cured. Has been proposed (for example, Patent Document 2).

JP 2013-38270 A JP 2012-178422 A

  However, as described above, even if the amount of warpage is suppressed by heating the WLP in which the rewiring layer is provided only on one side, the rewiring layer expands when heated to the WLP mounting temperature (for example, 260 ° C.). And the package warps. As a result, there is a problem that peeling occurs between layers inside the package and that some terminals are hardly connected at the time of mounting. On the other hand, if the amount of warpage is adjusted at the WLP mounting temperature to suppress the warpage of the package when mounting the WLP, the rewiring layer including the insulating film shrinks when the package is cooled to room temperature. This causes the wafer to warp. As a result, there is a problem that it becomes difficult to transfer the wafer, or the risk that the wafer is stressed and broken by a small impact is increased.

  Accordingly, an object of the present invention is to adjust the amount of warpage at a temperature at the time of mounting a semiconductor wafer or a semiconductor package, particularly, a fan-out type wafer level package (FO-WLP) or at a room temperature such as a wafer transfer, so that the wafer or the package can be manufactured. An object of the present invention is to provide a curable resin composition for forming a warp correction layer, which can reduce warpage.

  In order to solve the above problems, it can be said that it is desirable that the amount of warpage is suppressed at both the temperature at the time of mounting the semiconductor package and at room temperature such as wafer transfer. The present inventors formed a warp correction layer having a contraction force against a stress contracted by the insulating film cure or the like of the rewiring layer on the opposite surface of the wafer where the rewiring layer was formed. It turns out that the problem can be solved. Furthermore, the present inventors have found that semiconductor wafers and pseudo wafers of FO-WLP have various thicknesses and various thicknesses and patterns of rewiring layers including an insulating film, so that they can be adjusted for the respective warpage amounts. It has been found that it is effective to provide a highly versatile warp correction layer on the surface opposite to the surface on which the rewiring layer including the insulating film is formed. Further, it has been found that by forming the warp correcting layer using the following curable resin composition, the warpage of the wafer or package can be reduced while adjusting the amount of warpage of the wafer or package.

  The curable resin composition according to the present invention is a curable resin composition curable by at least two or more kinds of curing reactions, wherein the curable component (A1) whose volume is shrunk by the one curing reaction and the other curable component. And a curable component (B1) whose volume is shrunk by a curing reaction.

  In an embodiment of the present invention, the one curing reaction may be an ionic ring-opening polymerization reaction or a polyaddition polymerization reaction, and the other curing reaction may be a radical addition polymerization reaction.

  In an embodiment of the present invention, the ionic ring-opening polymerization reaction or polyaddition polymerization reaction is an ionic ring-opening polymerization reaction or polyaddition polymerization reaction by heating, and the radical addition polymerization reaction is a photoradical. It may be an addition polymerization reaction.

  In the embodiment of the present invention, when the curable component (A1) whose volume shrinks by the ionic ring-opening polymerization reaction or the polyaddition polymerization reaction is cured, the volume shrinkage A (%) is 0 <A ≦ 7. And the volume shrinkage ratio B (%) when the curable component (B1) whose volume shrinks due to the radical addition polymerization reaction is cured may be in the range of 5 ≦ B ≦ 30. .

In an embodiment of the present invention, the volume shrinkage A and the volume shrinkage B are represented by the following formula:
A <B
It is preferable to satisfy the following.

  In an aspect of the present invention, the curable resin composition is used for forming a warp correction layer provided on a surface opposite to a surface on which a rewiring layer of FO-WLP is provided. .

  According to the present invention, in particular, in the FO-WLP, the curable component (A1) whose volume is shrunk by one curing reaction and the curable component (A1) by the other curing reaction are provided on the surface opposite to the surface on which the rewiring layer is provided. By forming a warp correction layer using a curable resin composition containing a curable component (B1) whose volume shrinks, the amount of warpage can be suppressed at a temperature at the time of mounting a semiconductor package or at room temperature such as wafer transfer. The warpage of the wafer or package can be reduced while adjusting the amount of warpage of the wafer or package. As a result, a semiconductor package with high quality reliability can be obtained.

  The curable resin composition according to the present invention is a curable resin composition curable by at least two or more kinds of curing reactions, wherein the curable component (A1) whose volume is shrunk by the one curing reaction and the other curable component. A curable component (B1) whose volume shrinks due to a curing reaction. Using the curable resin composition according to the present invention, a warp correction layer is formed on the surface opposite to the surface on which the rewiring layer of FO-WLP is provided, and the same shrinkage stress as the shrinkage stress of the rewiring layer is applied. By adjusting the volume shrinkage ratio of the warp correction layer so that the function is effected, the amount of warpage can be suppressed both at the temperature at the time of mounting the semiconductor package and at room temperature such as wafer transfer. That is, at the time of manufacturing the FO-WLP, an insulating layer is provided along with the rewiring layer on the circuit formation surface of the pseudo wafer, and the amount of warpage of the pseudo wafer changes depending on the material, thickness, and pattern of the insulating film. As in the present invention, using a curable resin composition containing a curable component curable by two or more kinds of curing reactions, a warp correction layer is provided on the surface opposite to the rewiring layer forming surface side. By curing the curable resin composition while controlling the curing reaction of more than one kind to form a warp correction layer, the same shrinkage stress as the stress acting on the FO-WLP due to the volume shrinkage of the insulating layer is corrected. Can be generated by layers. Therefore, the amount of warpage can be suppressed even at the temperature at the time of mounting the semiconductor package or at room temperature such as wafer transfer, and the warpage of the wafer or package can be reduced while adjusting the amount of warpage of the wafer or package. It is thought that a package can be obtained. This is merely a guess of the present inventors, and the present invention is not limited by the logic. Hereinafter, each component constituting the curable resin composition according to the present invention will be described.

<Curable component (A1)>
As the curable component (A1) whose volume is contracted by the curing reaction, a conventionally known material can be used without particular limitation as long as it has curability whose volume is contracted by the curing reaction. It is preferably a hardening component having a ring-opening polymerization reaction or a polyaddition polymerization reaction. In the present specification, ionic ring-opening polymerization means polymerization in which a growing chain is an ion when a polymerization reaction is advanced using a monomer that is polymerized by ring opening. Further, the polyaddition reaction is a reaction in which a monomer having two or more functional groups having a cyclic structure and a monomer having a functional group capable of reacting with the functional group having the cyclic structure at both ends are formed by an addition reaction. Is repeated and the polymerization proceeds. As such an ionic ring-opening polymerization reaction or polyaddition polymerization-reactive curing component, cyclic ethers such as epoxy and oxetane are preferable, and among them, an epoxy resin is preferable. Epoxy resins include solid, semi-solid, and liquid epoxy resins depending on the shape before the reaction. These can be used alone or in combination of two or more. By containing such a cyclic ether as the curable component (A1), the adhesion to the pseudo wafer is improved when the curable component (A1) is cured as described later, and the FO-WLP is further improved. Warpage can be suppressed.

  Examples of the solid epoxy resin include HP-4700 (a naphthalene type epoxy resin) manufactured by DIC, EXA4700 (a tetrafunctional naphthalene type epoxy resin) manufactured by DIC, and NC-7000 (a polyfunctional solid epoxy resin containing a naphthalene skeleton) manufactured by Nippon Kayaku Co., Ltd. Epoxidized product of a condensate of a phenol such as Nippon Kayaku Co., Ltd. EPPN-502H (trisphenol epoxy resin) with an aromatic aldehyde having a phenolic hydroxyl group (trisphenol epoxy resin); DIC Dicyclopentadiene aralkyl type epoxy resin such as Epicron HP-7200H (dicyclopentadiene skeleton-containing multifunctional solid epoxy resin); biphenyl aralkyl such as Nippon Kayaku Corporation NC-3000H (biphenyl skeleton-containing polyfunctional solid epoxy resin). Type epoxy Resin: Biphenyl / phenol novolak type epoxy resin such as NC-3000L manufactured by Nippon Kayaku Co .; Novolak type epoxy resin such as Epicron N660, Epicron N690 manufactured by DIC, EOCN-104S manufactured by Nippon Kayaku; YX- manufactured by Mitsubishi Chemical Corporation A biphenyl-type epoxy resin such as 4000; a phosphorus-containing epoxy resin such as TX0712 manufactured by Nippon Steel & Sumikin Chemical; a tris (2,3-epoxypropyl) isocyanurate such as TEPIC manufactured by Nissan Chemical Industries.

  Examples of the semi-solid epoxy resin include DIC's Epicron 860, Epicron 900-IM, Epicron EXA-4816, Epicron EXA-4822, Araldite AER280 manufactured by Asahi Ciba, Epototo YD-134 manufactured by Toto Kasei, jER834 manufactured by Mitsubishi Chemical, jER872, a bisphenol A type epoxy resin such as ELA-134 manufactured by Sumitomo Chemical Co., Ltd .; a naphthalene type epoxy resin such as Epicron HP-4032 manufactured by DIC; a phenol novolak type epoxy resin such as Epicron N-740 manufactured by DIC. .

  As the liquid epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, phenol novolak type epoxy resin, tert-butyl-catechol type epoxy resin, glycidylamine type epoxy resin, aminophenol type epoxy resin And alicyclic epoxy resins.

  The above-mentioned curable component (A1) can be used alone or in combination of two or more.

  The curable resin composition according to the present invention preferably contains a curing agent component (A2) capable of curing the curable component (A1). As the curing agent component (A2), even a curing agent component (A2-1) that can cause ionic ring-opening polymerization or polyaddition polymerization reaction of the curable component (A1) by heat, is cured by an active energy ray. The curing agent component (A2-2) that can cause the ionic component (A1) to undergo ionic ring-opening polymerization or polyaddition polymerization reaction may be used. Which curing agent component to be used, A2-1 or A2-2, can be appropriately selected depending on a combination with a curing agent component (B2) capable of curing the curable component (B1) described later. That is, when the curable component (A1) is intended to be polymerized, a curing agent component such that the curing reaction of the curable component (B1) does not proceed with the curing reaction of the curable component (A1) should be selected. I just need. In this specification, an active energy ray means an electromagnetic wave having energy necessary for exciting a curing agent component from a ground state to a transition state, for example, an electron beam, an ultraviolet ray, a visible light ray, or the like.

  As the curing agent component (A2-1) that can cause ionic ring-opening polymerization of the curable component (A1) by heat, imidazoles, benzylsulfonium salts, Lewis acid-amine complexes, and the like can be used. Among them, it is desirable to use imidazoles from the viewpoints of adhesion to a pseudo wafer, storage stability, and moisture resistance reliability.

  Examples of imidazoles include 2MZ, C11Z, 2PZ, 2E4MZ, 2P4MZ, 1B2MZ, 1B2PZ, 2MZ-CN, 2E4MZ-CN, 2PZ-CN, C11Z-CN, 2PZ-CNS, C11Z-CNS, 2MZ-A, C11Z -A, 2E4MZ-A, 2P4MHZ, 2PHZ, 2MA-OK, 2PZ-OK (product name, manufactured by Shikoku Chemicals Co., Ltd.), and compounds obtained by adding these imidazoles to an epoxy resin. Further, those obtained by coating these curing agents with a polyurethane-based or polyester-based polymer substance and microencapsulating them are preferable because the pot life is extended. These can be used alone or in combination of two or more.

  The amount of imidazole is preferably 0.1 to 10% by mass, more preferably 0.5 to 10% by mass, and still more preferably 1 to 10% by mass, based on the curable component (A-1). %. By mixing imidazoles, which are curing agent components (A2-1) capable of ionic ring-opening polymerization, within the above range, both curability and storage stability can be achieved.

  As benzylsulfonium salts, Sanshin Kagaku San-Aid series, SI-45, SI-60, SI-80, SI-100, SI-150, SI-110, SI-360, SI-360, SI-B2A, SI-B3A, SI-B3, SI-B4, and SI-B5 can be used. These can be used alone or in combination of two or more.

  The amount of the benzylsulfonium salt is preferably 0.1 to 10% by mass, more preferably 0.5 to 10% by mass, and still more preferably 1 to 10% by mass, based on the curable component (a-1). % By mass. By blending the benzylsulfonium salt which is a curing agent component (A2-1) capable of ionic ring-opening polymerization in the above range, both curability and storage stability can be achieved.

  In addition, as the Lewis acid-amine complex, known compounds such as a BF3-triethylamine complex and a BF3-pyridine complex can be used.

  The amount of the curing agent component (A2-1) such as a Lewis acid-amine complex is preferably 0.1 to 10% by mass, more preferably 0.1 to 10% by mass, based on the curable component (a-1). It is 5 to 10% by mass, more preferably 1 to 10% by mass. By blending the Lewis acid-amine complex, which is a curing agent component (A2-1) capable of ionic ring-opening polymerization, in the above range, both curability and storage stability can be achieved.

  The curable component (A1) may be cured by a polyaddition polymerization reaction. As the curing agent component (A2-1) capable of causing the polyaddition of the curable component (A1) by heat, acid anhydrides, carboxylic acids, amines, phenols, hydrazides, polymercaptans, and the like are used. be able to. Among them, carboxylic acids, amines, and phenols are desirably used from the viewpoints of adhesion to a pseudo wafer, storage stability, and moisture resistance reliability.

  Examples of the acid anhydrides include, for example, methyl tetrahydrophthalic anhydride, methyl hexahydrophthalic anhydride, hexahydrophthalic anhydride, methyl hymic anhydride, pyromellitic dianhydride, benzophenone tetracarboxylic dianhydride. Anhydride, 3,4-dimethyl-6- (2-methyl-1-propenyl) -1,2,3,6-tetrahydrophthalic anhydride, 1-isopropyl-4-methyl-bicyclo [2.2.2] Octo-5-ene-2,3-dicarboxylic anhydride can be used. These can be used alone or in combination of two or more.

  When the curable component (A1) is an epoxy compound, for example, the compounding amount of the acid anhydride may be a ratio of the number of curable functional groups (epoxy groups) to the number of carboxylic acids generated from the acid anhydride groups (curable component ( It is preferable that the number of cured functional groups / (the number of carboxylic acids) in A1) is from 0.2 to 20, and more preferably from 0.4 to 16. By setting the compounding amount of the acid anhydride in the above range, the curing reaction can be effectively advanced. On the other hand, when the curable component (A1) is other than an epoxy group, the ratio of the number of curable functional groups involved in the curing reaction to the number of carboxylic acids generated from the acid anhydride group (the curable function of the curable component (A1)) (The number of groups / the number of carboxylic acids).

  Examples of the carboxylic acids include adipic acid, maleic acid, methyltetrahydrophthalic acid, methylhexahydrophthalic acid, hexahydrophthalic acid, methylhymic acid, pyromellitic acid, benzophenonetetracarboxylic acid, 3,4-dimethyl-6- (2 -Methyl-1-propenyl) -1,2,3,6-tetrahydrophthalic acid, 1-isopropyl-4-methyl-bicyclo [2.2.2] oct-5-ene-2,3-dicarboxylic acid, side Resins having a carboxyl group in the chain can be used.

  When the curable component (A1) is an epoxy compound, the ratio of the number of curable functional groups (epoxy groups) to the number of carboxyl groups (the number of curable functional groups of the curable component (A1) / (The number of carboxyl groups) is preferably 0.2 to 20, more preferably 0.4 to 16. By setting the amount of the carboxylic acid in the above range, the curing reaction can be effectively advanced. On the other hand, when the curable component (A1) is other than an epoxy group, the ratio of the number of curable functional groups involved in the curing reaction to the number of carboxyl groups (the number of curable functional groups of the curable component (A1) / the number of carboxyl groups) ) Can be calculated in the same manner.

  The amines are not particularly limited as long as they have at least one primary or secondary amino group in the molecule, and aromatic amines are preferable from the viewpoint of storage stability and heat resistance of the cured product. desirable. As the aromatic amines, for example, diaminodiphenylmethane, diaminodiphenylsulfone, diaminodiphenylsulfide, metaxylenediamine, 3,3′-diethyl-4,4′-diaminodiphenylmethane, 3,3 ′, 5,5′-tetraethyl -4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfide, 2,2-bis- [4- (4-aminophenoxy) phenyl] -hexafluoropropane, , 2-Bis (4-aminophenyl) -hexafluoropropane, 2,4-diaminotoluene, 1,4-diaminobenzene, 1,3-diaminobenzene, diethyltoluenediamine, dimethyltoluenediamine, anilines, alkylated aniline , N-alkylated anily S, or the like can be used. These can be used alone or in combination of two or more.

  When the curable component (A1) is an epoxy compound, the ratio of the number of curing functional groups (epoxy groups) to the number of active hydrogens (the number of epoxy groups / the number of active hydrogens) is 0.2. It is desirable to mix them so as to be -20, more preferably 0.4-16. By setting the amount of the amines in the above range, the curing reaction can be effectively advanced. On the other hand, when the curable component (A1) is other than an epoxy group, the ratio of the number of the curable functional groups involved in the curing reaction to the number of active hydrogens (the number of curable functional groups of the curable component (A1) / the number of active hydrogens) ) Can be calculated in the same manner.

  Examples of phenols include phenol novolak resins, alkylphenol volak resins, bisphenol A novolak resins, dicyclopentadiene-type phenol resins, Xylok-type phenol resins, terpene-modified phenol resins, cresol / naphthol resins, polyvinylphenols, phenol / naphthol resins, An α-naphthol skeleton-containing phenol resin, a triazine-containing cresol novolak resin, various polyfunctional phenol resins, and the like can be used. These can be used alone or as a mixture of two or more.

  When the curable component (A1) is an epoxy compound, the ratio of the number of curable functional groups (epoxy groups) to the number of phenolic hydroxyl groups (the number of epoxy groups / the number of phenolic hydroxyl groups) is as follows. It is desirable that the amount be 0.2 to 20 and more preferably 0.4 to 16. By setting the amount of the phenol compound in the above range, the curing reaction can be effectively advanced. On the other hand, when the curable component (A1) is other than an epoxy group, the ratio of the number of curable functional groups involved in the curing reaction to the number of phenolic hydroxyl groups (the number of curable functional groups of the curable component (A1) / the number of phenolic groups) (The number of hydroxyl groups).

  In addition to the above, as the curing agent component (A2-1) capable of polymerizing the curable component (A1) by a polyaddition polymerization reaction by heat, a cyanate ester resin or an active ester resin can also be used. The cyanate ester resin is a compound having two or more cyanate ester groups (—OCN) in one molecule. Any conventionally known cyanate ester resin can be used. As the cyanate ester resin, for example, phenol novolak type cyanate ester resin, alkylphenol novolak type cyanate ester resin, dicyclopentadiene type cyanate ester resin, bisphenol A type cyanate ester resin, bisphenol F type cyanate ester resin, bisphenol S type cyanate ester resin Is mentioned. Further, a prepolymer partially triazined may be used.

  The active ester resin is a resin having two or more active ester groups in one molecule. The active ester resin can be generally obtained by a condensation reaction between a carboxylic acid compound and a hydroxy compound. Among them, an active ester compound obtained by using a phenol compound or a naphthol compound as the hydroxy compound is preferable. Examples of the phenol compound or naphthol compound include hydroquinone, resorcin, bisphenol A, bisphenol F, bisphenol S, phenolphthalin, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucin, benzenetriol , Dicyclopentadienyl diphenol, phenol novolak and the like.

  Carboxylic acid, acid anhydrides, amines, phenols, cyanate ester resin, active ester resin as a curing agent component (A2-1) capable of polymerizing the curable component (A1) by polyaddition polymerization reaction by heat When used, a curing accelerator may be used in combination. As the curing accelerator, the above-mentioned imidazoles can be used. Further, guanamines such as acetoguanamine and benzoguanamine; organic acid salts of polyamines such as diaminodiphenylmethane, m-phenylenediamine, m-xylenediamine, diaminodiphenylsulfone, dicyandiamide, urea, urea derivatives, melamine, polybasic hydrazide and / or Or an epoxy adduct; an amine complex of boron trifluoride; triazine derivatives such as ethyldiamino-S-triazine, 2,4-diamino-S-triazine and 2,4-diamino-6-xylyl-S-triazine; tributylphosphine And organic phosphines such as triphenylphosphine and tris-2-cyanoethylphosphine; tri-n-butyl (2,5-dihydroxyphenyl) phosphonium bromide, hexadecyltributylphosphonium chloride and the like Phosphonium salts; benzyl trimethyl ammonium chloride, quaternary ammonium salts such as phenyl tributylammonium chloride; the polybasic acid anhydride. One of these can be used alone, or two or more can be used in combination.

The curing accelerator component is not essential, but in particular, when it is desired to accelerate the curing reaction, 100 parts by mass of the curing agent component (A2-1) capable of polymerizing the curable component (A1) by a polyaddition polymerization reaction by the above-mentioned heat. Parts by weight, preferably in the range of 0.01 to 20 parts by mass.
When a metal catalyst is used as a curing accelerator component, its content is preferably from 10 to 550 ppm, more preferably from 25 to 200 ppm, in terms of metal, based on 100 parts by mass of the curable component.

  Among the curing agent component (A2-2) capable of ion-polymerizing the curable component (A1) by active energy rays, a cationic photocuring agent is used as the curing agent component (A2-2) capable of cationic polymerization. Can be. Specific examples of the cationic photocuring agent include, for example, diphenyliodonium tetrafluoroboroate, triphenylsulfonium hexafluoroantimonate, 2,4,6-triphenylthiopyrylium hexafluorophosphate, and commercial products such as ( ADEKA's Optoma-SP-170 and SP-152, San Apro's CPI-100P, CPI-101A, CPI-200K, CPI-210S and other sulfonium salt-based cationic photopolymerization initiators, and BASF Japan's IRGACURE ( (Registered trademark) 261 and the like. Among them, SP-152, CPI-100P and CPI-200K are preferred. One kind of such a cationic photopolymerization initiator may be used alone, or two or more kinds may be used in combination.

  When a cationic photocuring agent is used as a curing agent component (A2-2) capable of cationically polymerizing the curable component (A1) by active energy rays, the amount of the cationic curing agent is based on 100 parts by mass of the thermosetting component (A1). On the other hand, it is preferably 1 to 25 parts by mass, more preferably 5 to 20 parts by mass.

  In addition, an anionic light curing agent component can be used as the light curing agent component (A2-2). Specific examples of the anionic photocuring agent component include, for example, a compound that generates an amine upon irradiation with ultraviolet light, more specifically, 1,10-diaminodecane, 4,4′-trimethylenedipiperidine, carbamates and the like. Derivatives, cobalt-amine complexes, aminooxyiminos, ammonium borates and the like can be exemplified.

  When an anionic photocuring agent component is used as the photocuring agent component (A2-2), the amount thereof is preferably 1 to 25 parts by mass, more preferably 100 parts by mass, based on 100 parts by mass of the thermosetting component (A1). Is 5 to 20 parts by mass, more preferably 10 to 20 parts by mass.

<Curable component (B1)>
The curable resin composition according to the present invention contains a curable component (B1) whose volume shrinks by a curing reaction different from that of the curable component (A1) described above. When the curable component (A1) is a material that can be cured by, for example, the above-described ionic ring-opening polymerization reaction or polyaddition polymerization reaction, the curable component (B1) includes an ionic ring-opening polymerization reaction. Alternatively, the material can be selected from known materials other than a material curable by a polyaddition polymerization reaction. For example, a curable component curable by a radical addition polymerization reaction can be preferably used. In this specification, radical addition polymerization means a reaction in which polymerization is initiated by a radical and an unsaturated compound having a double bond or triple bond is added to form a polymer. As the curable component which can be cured by such a radical addition polymerization reaction, a compound having one or more ethylenically unsaturated groups in a molecule is preferable.

  In the curable resin composition, a curable component (A1) curable by an ionic ring-opening polymerization reaction or a polyaddition polymerization reaction as described above, and a curable component curable by a radical addition polymerization reaction By containing (B1), the curable component (A1) and the curable component (B1) can be separately cured when the curable resin composition is cured. Therefore, when a warp correction layer is formed using the curable resin composition, the amount of warp of the pseudo-wafer (that is, the stress acting on the FO-WLP due to the volume shrinkage of the insulating layer) causes the individual curable components to be hardened. The curing reaction can be controlled, and the same contraction stress as the warp stress inherent in the pseudo wafer can be generated in the warp correction layer. As a result, even when FO-WLPs having different materials, thicknesses, and patterns of insulating films are manufactured, FO-WLPs with reduced warpage can be obtained. For example, the curable component (A1) curable by an ionic ring-opening polymerization reaction or a polyaddition polymerization reaction is cured by heat, and the curable component (B1) curable by a radical addition polymerization reaction is activated energy. By curing with a line, the curing reaction can be controlled separately.

  Specific examples of the radical addition polymerization reactive component having one or more ethylenically unsaturated groups in a molecule include, for example, commonly known polyester (meth) acrylate, polyether (meth) acrylate, urethane (meth) Acrylate, carbonate (meth) acrylate, epoxy (meth) acrylate and the like can be mentioned. Specifically, hydroxyalkyl acrylates such as 2-hydroxyethyl acrylate and 2-hydroxypropyl acrylate; diacrylates of glycols such as ethylene glycol, methoxytetraethylene glycol, polyethylene glycol and propylene glycol; N, N-dimethylacrylamide Acrylamides such as N, N-methylolacrylamide and N, N-dimethylaminopropylacrylamide; aminoalkyl acrylates such as N, N-dimethylaminoethyl acrylate and N, N-dimethylaminopropyl acrylate; hexanediol, trimethylolpropane, Polyhydric alcohols such as pentaerythritol, dipentaerythritol, tris-hydroxyethyl isocyanurate and the like, Polyacrylates such as amide adducts, propylene oxide adducts or ε-caprolactone adducts; polyvalent acrylates such as phenoxy acrylate, bisphenol A diacrylate, and ethylene oxide adducts or propylene oxide adducts of these phenols Polyglycols of glycidyl ethers such as glycerin diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, triglycidyl isocyanurate; polyether polyols, polycarbonate diols, hydroxyl-terminated polybutadienes, polyesters Acryle made by directly acrylated polyols such as polyols, or urethane acrylates via diisocyanates And melamine acrylates, and at least one of methacrylates corresponding to the acrylates.

In addition to the above, the following compounds (1) to (11) may be used as the curable component (B-1) that can be cured by a radical addition polymerization reaction.
(1) An unsaturated group-containing monocarboxylic acid is reacted with a reaction product obtained by reacting a compound having a plurality of phenolic hydroxyl groups in one molecule with an alkylene oxide, and a polybasic acid is added to the obtained reaction product. An unsaturated group-containing polymer obtained by reacting an anhydride,
(2) an acrylic-containing polymer obtained by reacting (meth) acrylic acid with a bifunctional or higher polyfunctional epoxy resin and adding a dibasic acid anhydride to a hydroxyl group present in a side chain;
(3) an acrylic-containing polymer obtained by reacting (meth) acrylic acid with a polyfunctional epoxy resin obtained by further epoxidizing hydroxyl groups of a bifunctional epoxy resin with epichlorohydrin, and adding a dibasic acid anhydride to the resulting hydroxyl groups;
(4) A reaction product obtained by reacting a compound having a plurality of phenolic hydroxyl groups in one molecule with a cyclic carbonate compound is reacted with an unsaturated group-containing monocarboxylic acid, and a polybasic acid is added to the obtained reaction product. An unsaturated group-containing polymer obtained by reacting an anhydride,
(5) an acryl-containing urethane resin by a polyaddition reaction of a diisocyanate with a (meth) acrylate of a bifunctional epoxy resin or a partially acid anhydride modified product thereof, a carboxyl group-containing dialcohol compound and a diol compound,
(6) an unsaturated group-containing polymer obtained by copolymerization of an unsaturated carboxylic acid and an unsaturated group-containing compound,
(7) A compound having one hydroxyl group and one or more (meth) acryloyl groups in the molecule is added during the synthesis of the resin by the polyaddition reaction of the diisocyanate with the carboxyl group-containing dialcohol compound and the diol compound. (Meth) acrylic acrylic-containing urethane resin,
(8) A compound having one isocyanate group and one or more (meth) acryloyl groups in the molecule is added during the synthesis of the resin by the polyaddition reaction between the diisocyanate, the carboxyl group-containing dialcohol compound and the diol compound, Acrylic-containing urethane resin with terminal (meth) acrylate,
(9) During the synthesis of the resin (5), a compound having one hydroxyl group and one or more (meth) acryloyl groups in a molecule is added, and a terminal (meth) acrylated acryl-containing urethane resin is added.
(10) An acrylic urethane resin obtained by adding a compound having one isocyanate group and one or more (meth) acryloyl groups in the molecule during the synthesis of the resin of the above (5) and terminating (meth) acrylate, and 11) an acryl-containing polymer obtained by adding a compound having one epoxy group and one or more (meth) acryloyl groups in one molecule to the resin of (1) to (10);
Can be used alone or in combination of two or more, or in combination with a monomer having one or more ethylenically unsaturated groups in the molecule described above.

  The curable resin composition according to the present invention preferably contains a curing agent component (B2) capable of curing the curable component (B1). The curing agent component (B2) may be a curable component (B2-1) capable of radically polymerizing the curable component (B1) by heat, or a radical of the curable component (B1) by an active energy ray. It may be a curable component (B2-1) that can be polymerized. Which curing agent component of B2-1 or B2-2 is used can be appropriately selected depending on a combination with the curing agent component (A2) capable of curing the above-mentioned curable component (A1). That is, when the curable component (B1) is intended to be polymerized, a curing agent component such that the curing reaction of the curable component (A1) does not proceed with the curing reaction of the curable component (B1) should be selected. I just need.

  Among the thermal curing agent components (B2), examples of the curing agent component (B2-1) that can radically polymerize the curable component (B1) by heat include, for example, methyl ethyl ketone peroxide, methyl isobutyl ketone peroxide, and acetylacetone peroxide. , Cyclohexanone peroxide and ketone peroxides such as methylcyclohexanone peroxide; 1,1,3,3-tetramethylbutyl hydroperoxide, hydroperoxides such as cumene hydroperoxide and t-butyl hydroperoxide; diisobu Diacids such as tyryl peroxide, bis-3,5,5-trimethylhexanoyl peroxide, lauroyl peroxide, benzoyl peroxide and m-toluylbenzoyl peroxide Peroxides: dicumyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, 1,3-bis (t-butylperoxyisopropyl) hexane, t-butylcumyl peroxide, Dialkyl peroxides such as -t-butyl peroxide and 2,5-dimethyl-2,5-di (t-butylperoxy) hexene; 1,1-di (t-butylperoxy-3,5,5-trimethyl ) Peroxyketals such as cyclohexane, 1,1-di-t-butylperoxycyclohexane and 2,2-di (t-butylperoxy) butane; t-hexylperoxypivalate, t-butylperoxypivalate, 1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, t-amylper Xy-2-ethylhexanoate, t-butylperoxy-2-ethylhexanoate, t-butylperoxyisobutyrate, di-t-butylperoxyhexahydroterephthalate, 1,1,3,3-tetramethylbutyl Peroxy-3,5,5-trimethylhexanoate, t-amylperoxy-3,5,5-trimethylhexanoate, t-butylperoxy-3,5,5-trimethylhexanoate, t-butylperoxyacetate, alkyl peresters such as t-butylperoxybenzoate and dibutylperoxytrimethyladipate; 1,1,3,3-tetramethylbutylperoxyneodicarbonate, α-cumylperoxyneodicarbonate, t-butylperoxyneodicarbonate, di-3 -Methoxy Tilperoxydicarbonate, di-2-ethylhexylperoxydicarbonate, bis (1,1-butylcyclohexaoxydicarbonate), diisopropyloxydicarbonate, t-amylperoxyisopropylcarbonate, t-butylperoxyisopropylcarbonate, t-butyl Peroxycarbonates such as peroxy-2-ethylhexyl carbonate and 1,6-bis (t-butylperoxycarboxy) hexane; 1,1-bis (t-hexylperoxy) cyclohexane and (4-t-butylcyclohexyl) peroxy Dicarbonate and the like.

  Curing agent component capable of polymerizing curable component (B1) by radical addition polymerization reaction by heat The compounding amount of curing agent component (B2-1) is preferably based on 100 parts by mass of curable component (B1). The amount is 1 to 25 parts by mass, more preferably 5 to 20 parts by mass, and still more preferably 10 to 20 parts by mass.

  Examples of the curing agent component (B2-2) capable of polymerizing the curable component (B1) by a radical addition polymerization reaction using an active energy ray include bis- (2,6-dichlorobenzoyl) phenylphosphine oxide, Bis- (2,6-dichlorobenzoyl) -2,5-dimethylphenylphosphine oxide, bis- (2,6-dichlorobenzoyl) -4-propylphenylphosphine oxide, bis- (2,6-dichlorobenzoyl) -1 -Naphthylphosphine oxide, bis- (2,6-dimethoxybenzoyl) phenylphosphine oxide, bis- (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, bis- (2,6-dimethoxybenzoyl) ) -2,5-Dimethylphenylphosphine Oxide, bis- (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (IRGACURE 819 manufactured by BASF Japan), 2,6-dimethoxybenzoyldiphenylphosphine oxide, 2,6-dichlorobenzoyldiphenylphosphine oxide, 2,4 Acyl such as 2,6-trimethylbenzoylphenylphosphinic acid methyl ester, 2-methylbenzoyldiphenylphosphine oxide, pivaloylphenylphosphinic acid isopropyl ester, and 2,4,6-trimethylbenzoyldiphenylphosphine oxide (IRGACURE TPO manufactured by BASF Japan) Phosphine oxides; 1-hydroxy-cyclohexylphenyl ketone, 1- [4- (2-hydroxyethoxy) -phenyl] -2- Droxy-2-methyl-1-propan-1-one, 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] phenyl} -2-methyl-propan-1 Hydroxyacetophenones such as -one, 2-hydroxy-2-methyl-1-phenylpropan-1-one; benzoin, benzyl, benzoin methyl ether, benzoin ethyl ether, benzoin n-propyl ether, benzoin isopropyl ether, benzoin n- Benzoins such as butyl ether; benzoin alkyl ethers; benzophenones such as benzophenone, p-methylbenzophenone, Michler's ketone, methylbenzophenone, 4,4'-dichlorobenzophenone, and 4,4'-bisdiethylaminobenzophenone; Tophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1- [4- (methylthio) Phenyl] -2-morpholino-1-propanone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2- (dimethylamino) -2-[(4-methylphenyl) Methyl) -1- [4- (4-morpholinyl) phenyl] -1-butanone, acetophenones such as N, N-dimethylaminoacetophenone; thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2,4-dimethylthioxanthone , 2,4-diethylthioxanthone, 2- Thioxanthones such as lorothioxanthone and 2,4-diisopropylthioxanthone; anthraquinone, chloroanthraquinone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 1-chloroanthraquinone, 2-amylanthraquinone, 2-aminoanthraquinone Anthraquinones such as acetophenone dimethyl ketal and benzyl dimethyl ketal; benzoic acid esters such as ethyl-4-dimethylaminobenzoate, 2- (dimethylamino) ethyl benzoate and ethyl p-dimethylbenzoate; 2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)], ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H- Oxime esters such as carbazol-3-yl]-, 1- (O-acetyloxime); bis (η5-2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H -Tyranocenes such as -pyrrole-1-yl) phenyl) titanium and bis (cyclopentadienyl) -bis [2,6-difluoro-3- (2- (1-pyr-1-yl) ethyl) phenyl] titanium Phenyl disulfide 2-nitrofluorene, butyroin, anisoin ethyl ether, azobisisobutyronitrile, tetramethylthiuram disulfide and the like.

  As the curing agent component (B2-2) capable of polymerizing the curable component (B1) by a radical addition polymerization reaction with the above-described active energy ray, one type may be used alone, or two or more types may be used in combination. Is also good. Among them, oxime esters (hereinafter referred to as “oxime ester-based photopolymerization initiator”) and α-aminoacetophenones, which are one of acetophenones (hereinafter referred to as “α-aminoacetophenone-based photopolymerization initiator”). ), And one or more photopolymerization initiators selected from the group consisting of acylphosphine oxides (hereinafter, referred to as “acylphosphine oxide-based photopolymerization initiator”).

Examples of the oxime ester-based photopolymerization initiator include commercially available products such as CGI-325, IRGACURE OXE01, IRGACURE OXE02, and N-1919 from ADEKA manufactured by BASF Japan. Further, a photopolymerization initiator having two oxime ester groups in the molecule can also be suitably used, and specific examples thereof include an oxime ester compound having a carbazole structure represented by the following general formula.

  In the above formula, X represents a hydrogen atom, an alkyl group having 1 to 17 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a phenyl group, a phenyl group (an alkyl group having 1 to 17 carbon atoms, an alkoxy group having 1 to 8 carbon atoms) A group, an amino group, an alkylamino group having an alkyl group having 1 to 8 carbon atoms or a dialkylamino group, a naphthyl group (an alkyl group having 1 to 17 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, Y and Z are a hydrogen atom, an alkyl group having 1 to 17 carbon atoms, an alkyl group having 1 to 17 carbon atoms, and an alkyl group substituted with an alkylamino group having 1 to 8 carbon atoms or a dialkylamino group having 1 to 8 carbon atoms. To 8 alkoxy groups, halogen groups, phenyl groups, phenyl groups (alkyl groups having 1 to 17 carbon atoms, alkoxy groups having 1 to 8 carbon atoms, amino groups, and alkyl groups having 1 to 8 carbon atoms) An amino group or a dialkylamino group, a naphthyl group (an alkyl group having 1 to 17 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an amino group, an alkylamino group having an alkyl group having 1 to 8 carbon atoms) Or substituted with a dialkylamino group), an anthryl group, a pyridyl group, a benzofuryl group, a benzothienyl group, and Ar represents an alkylene having 1 to 10 carbon atoms, vinylene, phenylene, biphenylene, pyridylene, naphthylene, thiophene, anthrylene. , Thienylene, furylene, 2,5-pyrrole-diyl, 4,4'-stilbene-diyl, 4,2'-styrene-diyl, and n is an integer of 0 or 1.

  Particularly preferable as the oxime ester compound having a carbazole structure represented by the above general formula, wherein X and Y are each a methyl group or an ethyl group, Z is methyl or phenyl, and n is 0. , Ar is an oxime ester compound in which phenylene, naphthylene, thiophene or thienylene is used.

  The amount of the oxime ester-based photopolymerization initiator is preferably 0.01 to 5 parts by mass based on 100 parts by mass of the polyether compound containing an ethylenically unsaturated group in the molecule.

  As the α-aminoacetophenone-based photopolymerization initiator, specifically, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone-1, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone, N , N-dimethylaminoacetophenone and the like. Examples of commercially available products include IRGACURE 907, IRGACURE 369, and IRGACURE 379 manufactured by BASF Japan.

  Examples of the acylphosphine oxide-based photopolymerization initiator include the above compounds. Examples of commercially available products include IRGACURE TPO and IRGACURE 819 manufactured by BASF Japan.

  The amount of the photopolymerization initiator excluding the oxime ester-based photopolymerization initiator is 0.1 to 30 parts by mass with respect to 100 parts by mass of the polyether compound containing an ethylenically unsaturated group in the molecule. preferable. When the amount is 0.1 parts by mass or more, the photocurability of the resin composition becomes good, the coating film is hardly peeled off, and the coating film characteristics such as chemical resistance become good. On the other hand, when the amount is 30 parts by mass or less, the effect of reducing outgas is obtained, the light absorption on the surface of the solder resist coating film becomes good, and the deep part curability does not easily decrease. More preferably, it is 0.5 to 15 parts by mass.

  When an oxime ester-based photopolymerization initiator is used as a curing agent component (B2-2) capable of polymerizing the curable component (B1) by a radical addition polymerization reaction with an active energy ray, sufficient sensitivity can be obtained even in a small amount. Not only can the photopolymerization initiator volatilize during the heat curing when the thermosetting component is blended, and in the post-heating step at the time of mounting, so that contamination of equipment such as a drying furnace can be reduced. .

  In addition, when an acylphosphine oxide-based photopolymerization initiator is used, a deep curing property at the time of a photoreaction is improved, so that a favorable opening shape in resolution can be obtained.

  It is effective to use either an oxime ester-based photopolymerization initiator or an acylphosphine oxide-based photopolymerization initiator, but from the viewpoint of the resist line shape and opening balance and photocurability as described above, oxime It is more preferable to use an ester photopolymerization initiator and an acylphosphine oxide photopolymerization initiator in combination.

  A commercially available curing agent component (B2-2) capable of polymerizing the curable component (B1) by a radical addition polymerization reaction with an active energy ray may be used. For example, IRGACURE manufactured by BASF Japan Ltd. may be used. 389 and IRGACURE 784 can be suitably used.

  The amount of the curing agent component (B2-2) capable of polymerizing the curable component (B1) by a radical addition polymerization reaction with active energy rays is preferably 1 to 100 parts by mass of the curable component (B1). To 25 parts by mass, more preferably 5 to 20 parts by mass, still more preferably 10 to 20 parts by mass.

  In the present invention, when a photocuring agent component (A2-2 or B2-2) is contained as a curing agent component, a photoinitiating assistant or a sensitizer may be contained in the curable resin composition. Examples of the photoinitiator and sensitizer include benzoin compounds, acetophenone compounds, anthraquinone compounds, thioxanthone compounds, ketal compounds, benzophenone compounds, tertiary amine compounds, and xanthone compounds. The photoinitiator and the sensitizer may be used alone or as a mixture of two or more. Of the above, thioxanthone compounds and tertiary amine compounds are preferred. In particular, it is preferable to include a thioxanthone compound from the viewpoint of the deep curability of the resin composition. Among them, it is preferable to include a thioxanthone compound such as 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone and 2,4-diisopropylthioxanthone.

To illustrate a combination of the above-described curable component and curing agent component, for example,
1) The thermosetting component (A2-1) as the curable component (A2) capable of curing the curable component (A1) and the curable component (A1), and the curable component (B1) and the curable component (B1). A combination with a photo-curing agent component (B2-2) as a curing agent component (B2) capable of curing
2) The photocurable component (A2-2) as the curable component (A2) capable of curing the curable component (A1) and the curable component (A1), and the curable component (B1) and the curable component (B1). A combination with a thermosetting agent component (B2-1) as a curing agent component (B2) capable of curing
And the like.

  In the combination of the above (1), the curable component (A1) preferably has a volumetric shrinkage A (%) in the range of 0 <A ≦ 7 when cured, and the curable component (B1) Preferably, the volume shrinkage B (%) when cured is in the range of 5 ≦ B ≦ 30. A coating film of a curable resin composition containing two kinds of curable components having such a volume shrinkage rate is formed on a pseudo wafer of FO-WLP, and a curing reaction is advanced by active energy rays and heat. If the warp correction layer is formed by curing the curable resin composition, the adhesion between the pseudo wafer and the warp correction layer can be increased, and the warp of the pseudo wafer can be corrected.

In the present invention, the volume shrinkage in the curing reaction can be calculated by the following formula by measuring the density of the curable component before and after curing.
Volume shrinkage (%) = (1− (density of curable component before curing / density of curable component after curing)) × 100
For example, assuming that the density of the monomer solution before curing is 1.0 g / cm ³ and the density of the cured product (polymer) obtained by curing the monomer is 1.2 g / cm ³ , the volume shrinkage (%) is about 17%. The density when the curable component is in a liquid state can be measured, for example, by measuring a certain volume in an atmosphere at 25 ° C. and measuring the density from the mass. When the curable component is a solid or a cured curable component, the density can be measured by an underwater substitution method (Archimedes method). More specifically, for example, the density (ρ) can be determined by the following equation using a Mettler XS205 analytical balance and a density measurement kit “density measurement kit for solids and liquids” and distilled water as a replacement liquid. it can.
ρ = (α × ρ ₀ ) / (α-β)
(In the above formula, ρ represents the density of the solid, α represents the mass of the solid in the atmosphere, β represents the mass of the solid in the replacement liquid, and ρ ₀ represents the density of distilled water at the measurement temperature. )

The volume shrinkage C (%) when the entire curable resin composition containing the curable components (A1) and (B1) is cured is preferably in the range of 0 <C ≦ 20, and 0 More preferably, it is within the range of <C ≦ 17. The volume shrinkage ratio when the entire curable resin composition is cured can be calculated by the following equation, as described above.
Volume shrinkage (%) = (1− (density of entire curable resin composition before curing / density of entire curable resin composition after curing)) × 100

  In the present invention, the mixing ratio of the curable components (A1) and (B1) contained in the curable resin composition is in a range of 0.05 ≦ (A1) / (B1) ≦ 20 on a mass basis. Is more preferable, and more preferably in the range of 0.07 ≦ (A1) / (B1) ≦ 15. When the curable components (A1) and (B1) are blended in the above ratio, the curing reaction of both curable components proceeds to a certain extent, and as a result, a more excellent warp correcting effect can be obtained.

The curable resin composition according to the present invention may contain a film property-imparting polymer component (C1) that facilitates maintaining the film (or sheet) shape when processed into a film (or sheet) shape. Examples of such a film property-imparting polymer component (C1) include a thermoplastic polyhydroxypolyether resin, a phenoxy resin which is a condensate of epichlorohydrin and various bifunctional phenol compounds, or a hydroxyl group in a hydroxyether portion present in the skeleton thereof. Phenoxy resin esterified using an acid anhydride or acid chloride, polyvinyl acetal resin, polyamide resin, polyamide imide resin, block copolymer, and the like. These polymers may be used alone or in combination of two or more. In order to maintain the shape of the film (or sheet), the weight average molecular weight (Mw) of these polymers is usually 2 × 10 ⁴ or more, and preferably 2 × 10 ^{4 to} 3 × 10 ⁶ .

In the present specification, the value of the weight average molecular weight (Mw) can be measured by a gel permeation chromatography (GPC) method (polystyrene standard) using the following measuring apparatus and measuring conditions.
Measuring device: Waters "Waters 2695"
Detector: Waters "Waters2414", RI (differential refractometer)
Column: Waters “HSPgel Column, HR MB-L, 3 μm, 6 mm × 150 mm” × 2 + Waters “HSPgel Column, HR1, 3 μm, 6 mm × 150 mm” × 2
Measurement condition:
Column temperature: 40 ° C
RI detector set temperature: 35 ° C
Developing solvent: tetrahydrofuran Flow rate: 0.5 ml / min Sample volume: 10 μl
Sample concentration: 0.7wt%

  The polyvinyl acetal resin is obtained, for example, by acetalizing a polyvinyl alcohol resin with an aldehyde. The aldehyde is not particularly limited, and includes, for example, formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, and the like.

  Specific examples of the phenoxy resin include FX280 and FX293 manufactured by Toto Kasei Co., Ltd., and YX8100, YL6954, and YL6974 manufactured by Mitsubishi Chemical Corporation.

  Specific examples of the polyvinyl acetal resin include Slesk KS series manufactured by Sekisui Chemical Co., Ltd., and examples of the polyamide resin include KS5000 series manufactured by Hitachi Chemical Co., Ltd. and BP series manufactured by Nippon Kayaku Co., Ltd.

  Examples of the polyamide-imide resin include KS9000 series manufactured by Hitachi Chemical Co., Ltd.

  When the thermoplastic polyhydroxypolyether resin has a fluorene skeleton, it has a high glass transition point and is excellent in heat resistance, so it maintains a low coefficient of thermal expansion by a semi-solid or solid epoxy resin and maintains its glass transition point. The cured film obtained has a low coefficient of thermal expansion and a high glass transition point in a well-balanced manner. Moreover, since the thermoplastic polyhydroxy polyether resin has a hydroxyl group, it exhibits good adhesion to the pseudo wafer.

  The film property imparting polymer component (C1) may be a monomer obtained by block copolymerizing the monomers constituting the above components. The block copolymer is a copolymer having a molecular structure in which two or more types of polymers having different properties are connected by a covalent bond to form a long chain. As the block copolymer, an XYX type or XY-X 'type block copolymer is preferable. In the XYX-type and XYX'-type block copolymers, the center Y is a soft block, the glass transition temperature (Tg) is low, and both outer X or X 'are hard blocks. Those having a glass transition temperature (Tg) composed of a polymer unit higher than the central Y block are preferred. Glass transition temperature (Tg) is measured by differential scanning calorimetry (DSC).

  Further, among the XYX type and XYX ′ type block copolymers, X or X ′ is composed of a polymer unit having a Tg of 50 ° C. or more, and the glass transition temperature (Tg) of Y is A block copolymer comprising a polymer unit having a Tg of X or X 'or less is more preferred. Further, among XYX-type and XYX'-type block copolymers, those in which X or X 'has high compatibility with the curable component (A1) or the curable component (B1) may be used. Preferably, Y has low compatibility with the curable component (A1) or the curable component (B1). In this way, the block at both ends is compatible with the matrix (curable component) and the central block is a block copolymer incompatible with the matrix (curable component), so that the specific block in the matrix is obtained. It is thought that it becomes easy to show a simple structure.

  Among the above various polymer components (C1) for imparting film properties, a phenoxy resin, a polyvinyl acetal resin, a thermoplastic polyhydroxypolyether resin having a fluorene skeleton, and a block copolymer are preferable.

  When the film property-imparting polymer component (C1) is added to the curable resin composition of the present invention, the ratio of the film property-imparting polymer component (C1) to the total components constituting the curable resin composition is particularly limited. However, when the total of all components is 100 parts by mass, the amount is preferably 2 to 40 parts by mass, more preferably 5 to 35 parts by mass.

The curable resin composition according to the present invention may contain an inorganic filler component (D).
The inclusion of the inorganic filler component (D) facilitates the cutting of the FO-WLP by dicing, for example. In addition, by performing the laser marking on the protective film, the inorganic filler component (D) is exposed at the portion cut off by the laser light, and the reflected light is diffused, so that the color becomes almost white. Thereby, when the warpage corrector for FO-WLP contains the colorant component (E) described below, a contrast difference is obtained between the laser marking portion and the other portion, and the effect that the marking (printing) becomes clear is obtained. is there.

  As the inorganic filler component (D), conventionally known inorganic filler components can be used without limitation, for example, silica, alumina, talc, aluminum hydroxide, calcium carbonate, Neuburg silicate, glass powder, clay, magnesium carbonate, natural mica Powders such as synthetic mica, barium sulfate, barium titanate, hydrotalcite, mineral wool, aluminum silicate, calcium silicate, zinc white, titanium oxide, iron oxide, silicon carbide, boron nitride, etc .; spherical beads of these; Examples thereof include crystal fibers and glass fibers, and one type may be used alone or two or more types may be used in combination. Among these, silica, alumina, and titanium oxide are preferable for controlling the relative dielectric constant in the film.

  The inorganic filler component (D) preferably has an average particle diameter of 0.01 to 15 μm, more preferably 0.02 to 12 μm, and particularly preferably 0.03 to 10 μm. In this specification, the average particle diameter is the number average particle diameter calculated by measuring the long axis diameter of 20 inorganic fillers (C) randomly selected by an electron microscope and calculating the arithmetic average value.

  The content of the inorganic filler component (D) is determined by the curable components (A1) and (B1) of the curable resin composition, the curing agent components (A2) and (B2), and the reactive film-forming polymer component ( When the total of the film-forming polymer component (C2) reactive with C1) is 100 parts by mass, preferably 10 to 400 parts by mass, more preferably 20 to 350 parts by mass, and particularly preferably 30 to 300 parts by mass. 300 parts by mass.

  The curable resin composition according to the present invention may contain a colorant component (E). By including the colorant component (E), when the semiconductor chip on which the curable resin composition is disposed is incorporated in a device, malfunction of the semiconductor device due to infrared rays or the like generated from peripheral devices can be prevented. . In addition, when the curing agent composition is engraved by means such as laser marking, marks such as characters and symbols can be easily recognized. That is, in the semiconductor chip on which the curable resin composition is formed, the product number and the like are usually printed on the surface of the protective film by a laser marking method (a method of shaving and printing the surface of the protective film with a laser beam). When the composition contains a colorant, a sufficient contrast difference between a portion of the protective film that is cut off by the laser beam and a portion that is not cut off is obtained, and the visibility is improved.

  As the colorant component (E), organic or inorganic pigments and dyes can be used alone or in combination of two or more. Among them, black pigments are preferable from the viewpoint of electromagnetic wave and infrared ray shielding properties. Examples of the black pigment include, but are not limited to, carbon black, perylene black, iron oxide, manganese dioxide, aniline black, activated carbon and the like. From the viewpoint of preventing malfunction of the semiconductor device, carbon black is particularly preferable. Instead of carbon black, a pigment or dye such as red, blue, green, or yellow may be mixed to obtain a black color or a similar black color.

Examples of the red colorant include monoazo, disazo, azo lake, benzimidazolone, perylene, diketopyrrolopyrrole, condensed azo, anthraquinone, and quinacridone, and specific examples include the following. Can be Pigment Red 1, 2,
3, 4, 5, 6, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 112, 114, 146, 147, 151, 170, 184, 187, 188, Monoazo red colorants such as 193, 210, 245, 253, 258, 266, 267, 268, 269, disazo red colorants such as Pigment Red 37, 38, 41, Pigment Red 48: 1, 48: 2, 48: 3. 48: 4, 49: 1, 49: 2, 50: 1, 52: 1, 52: 2, 53: 1, 53: 2, 57: 1, 58: 4, 63: 1, 63: 2, 64: Pigment Red 171, Pigment Red 175, Pigment Red 176, Pigment Red 185, Pigment Red 20 such as monoazo lake-based red colorants such as 1,68. Benzimidazolone red colorant etc., SolventRed135, SolventRed179, PigmentRed123, PigmentRed149, PigmentRed166, PigmentRed178, PigmentRed179, PigmentRed190, PigmentRed194, perylene-based red coloring agents such as PigmentRed224, PigmentRed254, PigmentRed255, PigmentRed264, PigmentRed270, PigmentRed272 like di Ketopyrrolopyrrole red colorant, PigmentRed220, PigmentRed144, PigmentRed166, PigmentRed214, PigmentRed220, Pigm NtRed221, condensed azo red colorant such as PigmentRed242, PigmentRed168, PigmentRed177, PigmentRed216, SolventRed149, SolventRed150, SolventRed52, anthraquinone-based red coloring agents such as SolventRed207, PigmentRed122, PigmentRed202, PigmentRed206, PigmentRed207, quinacridone red colorant such PigmentRed209 Is mentioned.

  Examples of blue colorants include phthalocyanine-based and anthraquinone-based pigments, and pigment-based compounds are classified as Pigment, specifically: PigmentBlue 15, Pigment Blue 15: 1, Pigment Blue 15: 2, Pigment Blue 15: 3, Pig 15: 4, Pig 15: 4, and Pig 15: 4. , PigmentBlue 15: 6, PigmentBlue16, PigmentBlue60, and the like. As the dye system, SolventBlue35, SolventBlue63, SolventBlue68, SolventBlue70, SolventBlue83, SolventBlue87, SolventBlue94, SolventBlue97, SolventBlue97, SolventBlue67, SolventBlue67, SolventBlue122, SolventBlue67, SolventBlue122, SolventBlue122, SolventBlue122, SolventBlue122, SolventBlue122, SolventBlue122, and SolventBlue122, SolventBlue122, SolventBlue122, SolventBlue122, SolventBlue122, SolventBlue122, SolubleBlue122 In addition, metal-substituted or unsubstituted phthalocyanine compounds can also be used.

  Examples of the green colorant include phthalocyanine-based, anthraquinone-based, and perylene-based, and specifically, Pigment Green 7, Pigment Green 36, Solvent Green 3, Solvent Green 5, Solvent Green 20, Solvent Green 28, and the like can be used. In addition to the above, metal-substituted or unsubstituted phthalocyanine compounds can also be used.

Examples of the yellow colorant include a monoazo type, a disazo type, a condensed azo type, a benzimidazolone type, an isoindolinone type and an anthraquinone type, and specific examples thereof include the following.
SolventYellow163, PigmentYellow24, PigmentYellow108, PigmentYellow193, PigmentYellow147, PigmentYellow199, anthraquinone-based yellow colorant such as PigmentYellow202, PigmentYellow110, PigmentYellow109, PigmentYellow139, PigmentYellow179, isoindolinone-based yellow colorant such as PigmentYellow185, PigmentYellow93, PigmentYellow94, PigmentYellow95, PigmentYellow128, PigmentYellow155, Pigment Yellow 166, Pigment Yellow 120, Pigment Yellow 151, Pigment Yellow 154, Pigment Yellow 156, Pigment Yellow 175, Pigment Yellow 1, Pigment 1, Pigment Yellow 6, Pigment Yellow 1, etc. , 62, 62: 1, 65, 73, 74, 75, 97, 100, 104, 105, 111, 116, 167, 168, 169, 182, 183, etc., and Pigment Yellow 12, 13, 14, 16, 17, 55, 63, 81, 83, 87, 126, 127, 152, 170, 172, 174, 176, 188 Etc. can be used disazo-based yellow colorant such as 198.

  A colorant such as purple, orange, brown, or black may be added for the purpose of adjusting the color tone. Specifically, PigmentViolet 19, 23, 29, 32, 36, 38, 42, SolventViolet 13, 36, C.I. I. Pigment Orange 1, C.I. I. Pigment Orange 5, C.I. I. Pigment Orange 13, C.I. I. Pigment Orange 14, C.I. I. Pigment Orange 16, C.I. I. Pigment Orange 17, C.I. I. Pigment Orange 24, C.I. I. Pigment Orange 34, C.I. I. Pigment Orange 36, C.I. I. Pigment Orange 38, C.I. I. Pigment Orange 40, C.I. I. Pigment Orange 43, C.I. I. Pigment Orange 46, C.I. I. Pigment Orange 49, C.I. I. Pigment Orange 51, C.I. I. Pigment Orange 61, C.I. I. Pigment Orange 63, C.I. I. Pigment Orange 64, C.I. I. Pigment Orange 71, C.I. I. Pigment Orange 73, C.I. I. Pigment Brown 23, C.I. I. Pigment Brown 25, C.I. I. Pigment Black 1, C.I. I. Pigment Black 7 and the like.

  When a penetration electrode is formed in the fan-out area of the FO-WLP, the fan-out area and the FO-WLP warp correction layer need to be simultaneously laser-processed. It is preferable to have The colorant component (E) can be selected by appropriately considering such a case.

  The compounding amount of the colorant component (E) is excellent in light transmittance to the deep part, and from the viewpoint of obtaining a more preferable warp correction layer, the curable components (A1) and (B1) of the curable resin composition. And the curing agent components (A2) and (B2), the total amount of the reactive film-forming polymer component (C1) and the reactive film-forming polymer component (C2) were 100 parts by mass. The amount is preferably 0.1 to 35 parts by mass, more preferably 0.5 to 25 parts by mass, and particularly preferably 1 to 15 parts by mass.

  In the curable resin composition according to the present invention, at least any one of adhesion, adhesion and cohesiveness of the warp correction layer to the adherend (pseudo wafer) when the warp correction layer is provided on the FO-WLP. In order to improve one of them, a coupling agent component (F1) having a functional group that reacts with an inorganic substance and a functional group that reacts with an organic functional group may be included. In addition, when the coupling agent component (F1) is included, a coating film of the curable resin composition is formed on the FO-WLP, and the curable resin composition is cured to form a warp correction layer. The water resistance can be improved without impairing the heat resistance of the warp correction layer. Examples of such a coupling agent include titanate-based coupling agents, aluminate-based coupling agents, and silane coupling agents. Among these, a silane coupling agent is preferable.

  Examples of the organic group contained in the silane coupling agent include a vinyl group, an epoxy group, a styryl group, a methacryloxy group, an acryloxy group, an amino group, an ureido group, a chloropropyl group, a mercapto group, a polysulfide group, and an isocyanate group. No. Commercially available silane coupling agents can be used, for example, KA-1003, KBM-1003, KBE-1003, KBM-303, KBM-403, KBE-402, KBE-403, KBM-1403. , KBM-502, KBM-503, KBE-502, KBE-503, KBM-5103, KBM-602, KBM-603, KBE-603, KBM-903, KBE-903, KBE-9103, KBM-9103, KBM -573, KBM-575, KBM-6123, KBE-585, KBM-703, KBM-802, KBM-803, KBE-846, KBE-9007 (all are trade names; manufactured by Shin-Etsu Silicone Co., Ltd.). it can. These may be used alone or in combination of two or more.

  The curable resin composition according to the present invention may contain various additives, if necessary, in addition to the components described above. Various additives include leveling agents, plasticizers, antioxidants, ion scavengers, gettering agents, chain transfer agents, release agents, rust inhibitors, adhesion promoters, ultraviolet absorbers, thermal polymerization inhibitors, thickeners It may contain additives commonly known in the field of electronic materials, such as agents and defoamers.

  The curable resin composition according to the present invention may contain an organic solvent. The organic solvent is used for synthesizing a polyether compound containing an ethylenically unsaturated group in a molecule, mixing each component, and adjusting the viscosity when applying the obtained curable resin composition to a substrate or a support film. Can be used for

  Examples of the organic solvent include ketones, aromatic hydrocarbons, glycol ethers, glycol ether acetates, esters, alcohols, aliphatic hydrocarbons, and petroleum solvents.

  More specifically, methyl ethyl ketone, ketones such as cyclohexanone, aromatic hydrocarbons such as toluene, xylene, tetramethylbenzene, cellosolve, methyl cellosolve, butyl cellosolve, carbitol, methyl carbitol, butyl carbitol, propylene glycol monomethyl Glycol ethers such as ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, triethylene glycol monoethyl ether, ethyl acetate, butyl acetate, dipropylene glycol methyl ether acetate, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate , Esters such as propylene glycol butyl ether acetate, ethanol, propanol Ethylene glycol, or propylene glycol, octane, can be exemplified aliphatic hydrocarbons decane, petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, petroleum solvents such as solvent naphtha. One organic solvent may be used alone, or two or more organic solvents may be used in combination.

  The curable resin composition according to the present invention preferably has a maximum transmittance at a wavelength of 300 to 800 nm of 20% or less, which is a measure of the transmittance of at least one of visible light and ultraviolet light, and 0 to 15%. %, More preferably 0% to 10%, and particularly preferably 0.001 to 8%.

  On the other hand, when it is necessary to perform alignment when producing FO-WLP from a pseudo wafer, the curable resin composition has a transmittance at a wavelength of 800 to 1200 nm, which is a measure of infrared transmission, of 50% or more. It is preferably at least 55%, more preferably at least 55%, even more preferably at least 60%, particularly preferably at least 65%.

  By setting the transmittance of the curable resin composition at the wavelengths of 300 to 800 nm and 800 to 1200 nm within the above ranges, effects such as improved alignment of the semiconductor device and improved visibility of printing can be obtained.

  The maximum transmittance of the curable resin composition at a wavelength of 300 to 800 nm and a wavelength of 800 to 1200 nm can be adjusted by the type and content of the above-described colorant component (E). In the present specification, the maximum transmittance of the curable resin composition is determined by using a UV-vis spectrum inspection apparatus (manufactured by Shimadzu Corporation) to cure the curable resin composition after curing the curable resin composition (warpage). The total light transmittance of the correction layer (thickness: 25 μm) at 300 to 1200 nm is measured, and the highest value (maximum transmittance) of the transmittance is referred to.

  When the curable resin composition of the present invention is in the form of a film (or a sheet), its thickness is not particularly limited, but is preferably 3 to 300 μm, more preferably 5 to 250 μm, and particularly preferably 7 to 200 μm. is there.

  The curable resin composition according to the present invention contains, for example, a cyclic ether compound as the curable component (A1) and a compound having one or more ethylenically unsaturated groups in the molecule as the curable component (B1). In this case, since it has an initial adhesion, in an uncured state, it is easily adhered by pressing against a pseudo wafer, a chip or the like. Further, at the time of pressing, any of heating and pressing may be performed on the curable resin composition. Then, through a different curing reaction, a cured film (warp correction layer) having high adhesion and warp correcting power can be finally formed. The cured film (warp correcting layer) formed using the curable resin composition according to the present invention has excellent adhesive strength and can maintain a sufficient protective function even under severe high temperature and high humidity conditions. The warp correction layer obtained by curing the curable resin composition may have a single-layer structure or a multilayer structure.

  The curable resin composition of the present invention may be used in the form of a dry film or may be used in a liquid state. When used as a liquid, it may be one-pack or two-pack or more.

  When forming a dry film, the curable resin composition is diluted with an organic solvent to adjust to an appropriate viscosity, and a comma coater, a blade coater, a lip coater, a rod coater, a squeeze coater, a reverse coater, a transfer roll coater, a gravure coater, It is applied to a uniform thickness on a support film by a spray coater or the like, and is usually dried at a temperature of 50 to 130 ° C. for 1 to 30 minutes to obtain a film.

  The thickness of the applied film is not particularly limited, but is generally selected appropriately in the range of 5 to 150 μm, preferably 10 to 60 μm in terms of the thickness of the dry film after drying, in that a more preferable warp correction layer is obtained. .

  As the support film, conventionally known ones such as a separate paper, a separate film, a separate paper, a release film, and a release paper can be suitably used. In addition, the mold release paper substrate made of a polyester film such as polyethylene terephthalate (PET) or polyethylene naphthalate (PEN), a polyolefin film such as an oriented polypropylene film (OPP), or a plastic film such as a polyimide film is released on one or both sides of a release paper substrate. What formed the layer may be used. The release layer is not particularly limited as long as it has a release property, and examples thereof include a silicone resin, an organic resin-modified silicone resin, and a fluororesin.

  The thickness of the support film is not particularly limited, but is generally selected appropriately in the range of 10 to 150 μm.

  After forming the curable resin composition on the support film, a peelable cover film may be further laminated on the surface of the film for the purpose of preventing dust from adhering to the surface of the film. As the peelable cover film, for example, a polyethylene film, a polytetrafluoroethylene film, a polypropylene film, surface-treated paper, or the like can be used. In consideration of the peeling of the cover film, the adhesive strength between the membrane and the cover film is made smaller than the adhesive strength between the membrane and the support film.

  The curable resin composition of the present invention is adjusted to a viscosity suitable for a coating method using, for example, an organic solvent, and is coated on a substrate with a dip coating method, a flow coating method, a roll coating method, a bar coater method, a screen printing method, and a curtain. A film shape can be formed by applying the composition by a coating method or the like and evaporating and drying (temporarily drying) the organic solvent contained in the composition at a temperature of about 60 to 100 ° C.

  The volatile drying performed after the curable resin composition of the present invention is applied is performed by a hot air circulation drying oven, an IR oven, a hot plate, a convection oven, or the like (using a hot air in a dryer using a heat source of an air heating system using steam). (A method of bringing the support into contact with the support and a method of spraying the support from a nozzle).

<Use of curable resin composition>
In the case where the above-mentioned curable resin composition is used as a composition for forming a warp correction layer of FO-WLP, a pseudo wafer of FO-WLP provided with a warp correction layer will be described.

  First, a semiconductor wafer is prepared, and a circuit is formed on one surface. The semiconductor wafer may be a silicon wafer or a compound semiconductor wafer such as gallium arsenide (GaAs). Formation of a circuit on the wafer surface can be performed by various methods including a commonly used method such as an etching method and a lift-off method. The semiconductor wafer may be cut into individual semiconductor chips through a dicing process.

The semiconductor chip obtained as described above is placed on a flat carrier having a smooth surface via an adhesive layer. The carrier is not particularly limited, but a circular or square silicon wafer or metal plate can be used. In addition, as the adhesive layer, a material that can temporarily fix a semiconductor chip and that can be peeled off after manufacturing a pseudo wafer is used. As such an adhesive layer material, an acrylic adhesive, a rubber adhesive, a styrene / conjugated diene block copolymer, or the like can be used.
In addition, as the adhesive layer material, a carboxyl group-containing resin having an ethylenically unsaturated group and a radical polymerization initiator as described above can be contained. By containing such a resin, heating or active energy rays can be used. Irradiation can change the adhesiveness of the adhesive layer.

  When placing a semiconductor chip on the adhesive layer, a plurality of semiconductor chips are placed separately. The semiconductor chips to be mounted may be the same or different in the number of arrangements in the vertical and horizontal directions in plan view.In addition, from various viewpoints such as improving the density and securing the terminal area per unit semiconductor chip, point symmetry or They may be arranged in a grid or the like. The distance between the adjacent semiconductor chips is not particularly limited, but may be arranged so that a fan-out (FO) region necessary for forming a connection terminal of a finally obtained FO-WLP is obtained. desirable.

  Subsequently, the semiconductor chip mounted on the plate-shaped carrier via the adhesive layer is sealed with a sealing material. The semiconductor chip is mounted and the sealing material is applied or bonded onto the carrier such that the side wall surface and the upper surface of the semiconductor chip are sealed with the sealing material. At this time, the molding is performed so that the sealing material is also embedded in the space between the semiconductor chips. The sealing step using such a sealing material can be formed by compression molding using a known liquid, granule, or sheet-like resin composition for semiconductor sealing. In the known resin composition for semiconductor encapsulation, an epoxy resin, a curing agent for the epoxy resin, a curing accelerator, a spherical filler, and the like are mainly used.

  After curing the sealing material, the plate-shaped carrier is peeled off. The peeling is performed between the sealing material and the semiconductor chip and the adhesive layer. As a peeling method, a method of peeling by changing (decreasing) the adhesive force of the adhesive layer by performing a heat treatment, first performing peeling between the plate-shaped carrier and the adhesive layer, and then subjecting the adhesive layer to a heat treatment or After the irradiation treatment with an electron beam or an ultraviolet ray, a method of peeling off is given.

  The pseudo wafer thus obtained may be subjected to post cure. The post-curing is performed, for example, in a temperature range of 150 to 200 ° C. for a period of 10 minutes to 8 hours. Subsequently, the pseudo wafer can be thinned by polishing the opposite side of the surface of the obtained pseudo wafer in which the semiconductor is embedded. The method of grinding is not particularly limited, and the grinding may be performed by a known means using a grinder or the like. The thickness of the pseudo wafer after grinding is not particularly limited, but is usually about 50 to 500 μm.

  Subsequently, a redistribution layer is formed on the surface of the pseudo wafer where the semiconductor chip circuits are exposed. First, an insulating resin for rewiring is applied to the entire surface of the pseudo wafer where the semiconductor chip circuits are exposed by using a spin coating method or the like, and prebaked at about 100 ° C. to form an insulating resin layer for rewiring. I do. Next, in order to open connection pads of the semiconductor chip, a pattern is formed on the insulating resin layer for rewiring by using a photolithography method or the like, and a heat treatment (curing) is performed. The heat treatment is performed, for example, at a temperature of 150 to 250 ° C. for 10 minutes to 5 hours. The insulating resin for rewiring is not particularly limited, but a polyimide resin, a polybenzooxide resin, a benzocyclobutene resin, or the like is used from the viewpoint of heat resistance and reliability. As described above, when performing heat treatment on the insulating resin for rewiring, the pseudo wafer may be warped due to heat shrinkage of the insulating resin.

  A power supply layer is formed on the entire surface of the rewiring layer surface of the pseudo wafer by a method such as sputtering, and then a resist layer is formed on the power supply layer, exposed and developed in a predetermined pattern, and the via and copper are formed by electrolytic copper plating. A rewiring circuit is formed. After forming the rewiring circuit, the resist layer is peeled off, and the power supply layer is etched.

  Subsequently, a flux is applied to the land provided on the rewiring circuit, the solder ball is mounted thereon, and then heated and melted, so that the solder ball is attached to the land. Further, a solder resist layer may be formed so as to cover a part of the rewiring circuit and the solder ball. The flux to be applied may be a resin-based or water-based flux. As a heating and melting method, reflow, a hot plate or the like can be used. Thus, a pseudo wafer of FO-WLP is obtained.

  Then, the FO-WLP is obtained by singulating the pseudo wafer of FO-WLP by a method such as dicing.

  The curable resin composition is applied to the surface of the pseudo wafer obtained in this manner opposite to the surface on which the rewiring layer is formed to form a coating film. In addition, when using what made the curable resin composition into a dry film as mentioned above, a dry film is bonded. As a sticking method, a known method such as a hand roller, a laminator, a vacuum laminator, and compression molding can be used.

  Heating may be performed in the sticking step, but when sticking the dry film while heating, it is desirable to heat the curable resin composition within a range in which the thermosetting reaction does not proceed. As the temperature at which the thermosetting reaction starts, for example, the ONSET temperature at which the reaction heat is observed in the DSC measurement is confirmed, and the temperature can be set to be lower than that temperature. In the DSC measurement, for example, using a DSC Q100 manufactured by TA Instruments, the curable resin composition is heated to 30 to 300 ° C. at a rate of 5 ° C./min in a nitrogen atmosphere to obtain an ONSET temperature, a peak top temperature, The OFFSET temperature can be determined.

  Thereafter, the support film is peeled from the dry film to obtain a laminate of the pseudo wafer and the dry film.

  Next, the dry film is cured to form a warp correction layer. When a dry film (curable resin composition) contains a curable component that undergoes a curing reaction by an active energy ray, the active film is irradiated with the active energy ray to thereby expose the exposed portion (which is irradiated with the active energy ray). Part) can be cured. The entire surface of the dry film before the reaction may be exposed to active energy rays for exposure, or may be exposed to active energy rays by a contact or non-contact method through a patterned photomask. In addition, the exposed portion can be light-cured by pattern exposure using a laser direct exposure machine.

  In the case of exposing with a photomask on which a pattern is formed or direct pattern exposure with a laser direct exposure device, and in the case of partially exposing, the unexposed portion is diluted with a dilute alkaline aqueous solution (for example, 0.3 to 3 wt% tetramethyl hydroxide). Developing with an aqueous solution of ammonium (TMAH) or aqueous solution of 0.3 to 3 wt% sodium carbonate) to form a photosensitive pattern of the warp correction layer, or forming a photo-cured portion and an uncured portion without developing. Is also good.

  The pattern shape in the case of exposure with a photomask or direct pattern exposure with a laser direct exposure machine can be selected from, for example, a repetitive pattern such as a lattice pattern, a checkered pattern, and a polka dot pattern. It is preferable that the repeating unit of the pattern of the opening / light-shielding portion is smaller than the size of the semiconductor package finally obtained. Further, different patterns may be used in a region where the semiconductor chips are present in the FO-WLP pseudo wafer and a resin region forming the pseudo wafer.

  During exposure, by irradiating active energy rays from the central part of the wafer to the peripheral part by changing the aperture ratio or pattern calculated from the opening / light-shielding part of the photomask continuously or discontinuously, The reaction state of the warp correction layer can be changed in the plane. In the case of direct pattern exposure using a laser direct exposure machine, the entire surface may be exposed with a uniform pattern or may be exposed unevenly. Further, the pattern to be exposed may be changed continuously / discontinuously.

  As an exposure machine used for active energy ray irradiation, a device that mounts a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a metal halide lamp, a mercury short arc lamp, or the like and irradiates ultraviolet rays in a range of 350 to 450 nm may be used.

  A direct drawing apparatus (for example, a laser direct imaging apparatus that directly draws an image with a laser using CAD data from a computer) can also be used. As a laser light source of the direct drawing machine, any of a gas laser and a solid-state laser may be used as long as a laser light having a maximum wavelength in the range of 350 to 410 nm is used.

The exposure amount varies depending the thickness or the like, typically 10 to 10000 mJ / cm ^2, preferably be in the range of 20~8000mJ / cm ^2.

  As a developing method, a dipping method, a shower method, a spray method, a brush method, or the like can be used. As a developing solution, tetramethylammonium hydroxide (TMAH), potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, An alkaline aqueous solution of sodium phosphate, sodium silicate, ammonia, amines or the like can be used.

  In the present invention, the FO-WLP of the FO-WLP is obtained by appropriately adjusting the degree of curing of the warp correction layer of the pseudo wafer by selecting the irradiation amount of the active energy ray or the whole surface irradiation and the partial irradiation, and by performing the developing process in the case of the partial irradiation. The amount of correction can be easily adjusted depending on the degree of warpage.

  When the dry film (curable resin composition) contains a curable component whose curing reaction proceeds by heat, the curing reaction can be advanced by heating. Heating methods include oven heating, hot plate heating, high-temperature air heating, infrared heating, convection oven, etc. (a method in which a hot air in a dryer is brought into countercurrent contact using a device equipped with a steam-based air heating system, and a nozzle is used to support the substrate. Spraying).

  The temperature at which the dry film is cured by heat to form a warp correction layer can be set to a temperature equal to or higher than the ONSET temperature at which the reaction heat is observed by DSC measurement, for example. Further, it is desirable to set the temperature higher than the Peak Top temperature and lower than the OFFSET temperature. In the DSC measurement, for example, DSC Q100 manufactured by TA Instruments is used to raise the temperature of the FO-WLP warp straightening material to 30 to 300 ° C. at a rate of 5 ° C./min in a nitrogen atmosphere to obtain an ONSET temperature and a peak top. The temperature and the OFFSET temperature can be obtained.

  In the present invention, by adjusting the temperature and time at the time of curing by heat, or by performing a step heating of heating to a final temperature via an intermediate temperature or a method of raising the temperature in one step to a target temperature, the pseudo wafer The degree of curing of the warp correction layer is appropriately adjusted, and the correction amount can be easily adjusted by the degree of warpage of the FO-WLP. The time for curing the dry film by heating is preferably 30 seconds to 3 hours.

  If the dry film (curable resin composition) contains both components that react with active energy rays and components that react with heating, the curable resin is irradiated by both means of irradiation with active energy rays and heating. The composition can also be cured. Irradiation with active energy rays and heating may be performed simultaneously or separately. The irradiation with the active energy ray may be performed once or twice or more. Heating for thermosetting may be performed once or twice or more.

  When a dry film (curable resin composition) contains both a component that reacts with active energy rays and a component that reacts with heating, a method of simultaneously irradiating and heating with active energy rays, A method of performing heating after irradiation, a method of irradiating with active energy rays after heating, and a method of performing heating after irradiating with active energy rays and further irradiating with active energy rays are preferable from the viewpoint of the reactivity of the curing reaction.

  Even after the dry film (curable resin composition) is cured by irradiation or heating with active energy rays to form a warp correction layer, if the amount of warp correction is insufficient, additional active energy rays are used. Irradiation or heating may be performed to further promote the reaction to enhance the warp correcting power.

  Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited to these examples. Unless otherwise specified, “parts” and “%” mean parts by mass.

<Preparation of curable component (B1) 1>
In an autoclave equipped with a thermometer, a nitrogen introducing device, an alkylene oxide introducing device, and a stirring device, 119.4 parts of novolak-type cresol resin (manufactured by Showa Denko KK, Shonor CRG951, OH equivalent: 119.4), potassium hydroxide 1.19 parts and 119.4 parts of toluene were charged, the inside of the system was replaced with nitrogen while stirring, and the temperature was raised by heating. Next, 63.8 parts of propylene oxide was gradually dropped, and the mixture was reacted at 125 to 132 ° C. and 0 to 4.8 kg / cm ² for 16 hours. Thereafter, the reaction solution was cooled to room temperature, and 1.56 parts of 89% phosphoric acid was added and mixed to the reaction solution to neutralize potassium hydroxide. The nonvolatile content was 62.1%, and the hydroxyl value was 182.2 g / eq. A propylene oxide reaction solution of novolak cresol resin was obtained. This was an average of 1.08 mol of alkylene oxide added per equivalent of phenolic hydroxyl group.

  293.0 parts of an alkylene oxide reaction solution of the obtained novolak cresol resin, 43.2 parts of acrylic acid, 11.53 parts of methanesulfonic acid, 0.18 part of methylhydroquinone and 252.9 parts of toluene were stirred with a stirrer at a temperature of A reactor equipped with a meter and an air blowing tube was charged, air was blown at a rate of 10 ml / min, and the mixture was reacted at 110 ° C. for 12 hours with stirring. 12.6 parts of water was distilled off as an azeotrope with the water generated by the reaction. Thereafter, the mixture was cooled to room temperature, and the obtained reaction solution was neutralized with 35.35 parts of a 15% aqueous sodium hydroxide solution, and then washed with water. Thereafter, toluene was distilled off while replacing the toluene with 118.1 parts of diethylene glycol monoethyl ether acetate (carbitol acetate) using an evaporator to obtain a novolak type acrylate resin solution.

  Next, 332.5 parts of the obtained novolak type acrylate resin solution and 1.22 parts of triphenylphosphine were charged into a reactor equipped with a stirrer, a thermometer and an air blowing tube, and air was supplied at a rate of 10 ml / min. While blowing and stirring, 60.8 parts of tetrahydrophthalic anhydride is gradually added, and the mixture is reacted at 95 to 101 ° C. for 6 hours. After cooling, the solid substance has an acid value of 88 mg KOH / g and a solid content of 70.9%. An acryl-containing polyether compound solution, which is the sexual component (B1) 1, was obtained.

<Preparation of curable component (B1) 2>
A cresol novolak type epoxy resin (manufactured by Nippon Kayaku Co., Ltd., EOCN-104S, epoxy equivalent 220 g / eq) 220 parts (1 equivalent), 140.1 parts of carbitol acetate, and 60.3 parts of solvent naphtha were charged into a flask, and 90 The mixture was heated and stirred at ℃ to dissolve.
The resulting solution is once cooled to 60 ° C., added with 72 parts (1 mol) of acrylic acid, 0.5 part of methylhydroquinone and 2 parts of triphenylphosphine, heated to 100 ° C. and reacted for about 12 hours to obtain an acid value. Gave a reaction product of 0.2 mg KOH / g. 80.6 parts (0.53 mol) of tetrahydrophthalic anhydride was added thereto, and the mixture was heated to 90 ° C. and reacted for about 6 hours. A curable component having an acid value of 85 mgKOH / g and a solid content of 64.9% was obtained. (B1) An acryl-containing polyether compound solution as 2, was obtained.

<Synthesis of curing agent component (A2-1) 1>
A 2,000 ml flask equipped with a stirrer and a condenser was charged with 377 g of tripropylene glycol monomethyl ether, and heated to 90 ° C. under a nitrogen stream. A mixture of 104.2 g of styrene, 246.5 g of methacrylic acid, and 20.7 g of dimethyl 2,2′-azobis (2-methylpropionate) (V-601, manufactured by Wako Pure Chemical Industries, Ltd.) was mixed and dissolved for 4 hours. The mixture was dropped into the flask. Thus, a carboxyl group-containing resin solution as the curing agent component (A2-1) 1 was obtained. This carboxyl group-containing resin solution had a solid content acid value of 120 mgKOH / g, a solid content of 50%, and a weight average molecular weight of 2 × 10 ⁴ .

<Preparation of film-imparting polymer (C1)>
To 75 g of diethylene glycol monoethyl ether acetate (CA), 25 g of a Y-X-Y type block copolymer (M52N manufactured by Arkema) was added, and the mixture was stirred and dissolved by heating at 80 ° C. This was designated as film-imparting polymer C1.

<Preparation of curable resin compositions 1 to 11>
Each component was blended according to the blending shown in Table 1 below, preliminarily mixed by a stirrer, dispersed by a three-roll mill, and kneaded to prepare respective curable resin compositions. In addition, the compounding quantity in a table | surface shows a mass part. In addition, the curable component (B1), the curing agent component (A2-1), and the film property imparting polymer (C1) in the table are values as solid contents.

The details of each component in Table 1 are as follows.
N-770: phenol novolak type epoxy epiclone N-770 manufactured by DIC
EP-828: Mitsubishi Chemical basic liquid type epoxy "828"
EP1007: Mitsubishi Chemical basic solid type epoxy "1007"
1B2PZ: 1B2PZ 1-benzyl-2-phenylimidazole DICY7 manufactured by Shikoku Chemicals: DICY7 dicyandiamide SP-152 manufactured by Mitsubishi Chemical Corporation: Adekaoptomer SP-152 triarylsulfonium salt manufactured by ADEKA Corporation:
TMPTA: TMPT Trimethylolpropane triacrylate manufactured by Daicel Ornex Co., Ltd. DPHA: DPHA dipentaerythritol hexaacrylate manufactured by Daicel Ornex Co., Ltd. DCPA: Light acrylate DCPA manufactured by Kyoeisha Chemical Co., Ltd.
IRGACURE TPO: IRGACURE TPO manufactured by BASF Japan
IRGACURE 907: IRGACURE 907 manufactured by BASF Japan
IRGACURE OXE02: IRGACURE OXE02 manufactured by BASF Japan
Park Mill D: manufactured by NOF Corporation Park Mill D: dicumyl peroxide M52N: manufactured by Arkema Co., Ltd. Nano Strength M52N Y-XY type block copolymer Silica: manufactured by Admatechs Admafine SO-E2
Barium sulfate: B-30: Surface-treated barium sulfate manufactured by Sakai Chemical Industry Co., Ltd. Blue colorant: C.I. I. Pigment Blue 15: 3
Yellow colorant: C.I. I. Pigment Yellow 147
Red color former: Paliogen Red K3580 manufactured by BASF Japan
The values of the curing agent component (A2-1) 1, the curable component (B1) 1, and the curable component (B1) 2 in the table represent values in terms of solid content.

<Measurement of Volume Shrinkage of Curable Component (A1)>
The volume shrinkage when the curable component (A1) used in Table 1 was thermally cured with a thermosetting component was measured. The components of the curable component (A1) used in the curable resin composition 1 in Table 1 were mixed at a ratio described in Table 1 so that the total amount was 10.0 g, and the mixture was stirred while heating as necessary. A mixture was prepared by adding 0.2 g of 2-ethyl-4-methylimidazole as a thermosetting component.

When the prepared mixture was liquid at 25 ° C., the mixture was added to a 10 mL graduated cylinder and left in a room at 25 ° C. for 6 hours, after which the mass was measured, and the density was determined from the measured volume and the mass. When the prepared mixture is a solid at 25 ° C., the mixture is heated to obtain a mixture and then cooled to room temperature to obtain a solid, and the density of the solid is determined by METTLER TOLEDO Co., Ltd., XS-205. The density (ρ) was calculated by the following equation using an analytical balance and a density measuring kit “density measuring kit for solid and liquid”, and using distilled water as a replacement liquid.
ρ = (α × ρ ₀ ) / (α-β)
(In the above formula, ρ represents the density of the solid, α represents the mass of the solid in the atmosphere, β represents the mass of the solid in the replacement liquid, and ρ ₀ represents the density of distilled water at the measurement temperature. )

  Subsequently, 5.0 g of the prepared composition was filled in a Teflon (registered trademark) container having a diameter of 2 cm and a height of 2 mm, and the mixture was placed in an oven heated to 100 ° C for 60 minutes, and then placed in an oven heated to 150 ° C. The curable component was cured by being charged for 60 minutes to obtain a cured product A. The density of the cured product A was measured using an analytical balance in the same manner as described above.

From the density of the liquid or the solid of the mixture and the density of the cured product, the volume shrinkage of the curable component (A1) was determined by the following formula.
Volume shrinkage = (1− (density of curable component (A1) before curing / density after curing)) × 100
Further, for the curable component (A1) used in the curable resin compositions 2 to 11, the volume shrinkage was determined in the same manner as described above.
The volume shrinkage (%) of the curable component (A1) used in the curable resin compositions 1 to 11 was as shown in Table 3 below.

<Measurement of Volume Shrinkage of Curable Component (B1)>
The volume shrinkage when the curable component (B1) used in Table 1 was photo-cured with the photo-curing agent component was measured. The components of the curable component (B1) used in the curable resin composition 1 in Table 1 were mixed at a ratio shown in Table 1 so that the total amount was 10.0 g, and the mixture was stirred while heating as necessary. A mixture to which 0.2 g of IRGACURE TPO manufactured by BASF, which is a photocurable component, was added was prepared.

  When the prepared mixture was liquid at 25 ° C., the mixture was added to a 10 mL graduated cylinder and left in a room at 25 ° C. for 6 hours, after which the mass was measured, and the density was determined from the measured volume and the mass. When the prepared mixture is a solid at 25 ° C., the mixture is heated to obtain a mixture and then cooled to room temperature to obtain a solid, and the density of the solid is measured using an analytical balance in the same manner as described above. It was measured.

Subsequently, 0.15 g of the prepared composition was filled in a Teflon (registered trademark) container having a diameter of 2 cm and a height of 0.5 mm, and irradiated with active energy rays using a metal halide lamp (exposure amount: 5000 mJ / cm ² ). Thus, the curable component was cured to obtain a cured product B. The density of the cured product B was measured using an analytical balance in the same manner as described above.

From the liquid density or solid density of the mixture and the density of the cured product, the volume shrinkage of the curable component (B1) was determined by the following formula.
Volume shrinkage = (1− (density of the curable component (B1) before curing / density after curing)) × 100
Further, for the curable component (B1) used in the curable resin compositions 2 to 11, the volume shrinkage was determined in the same manner as described above.
The volume shrinkage (%) of the curable component (B1) used in the curable resin compositions 1 to 11 was as shown in Table 3 below.

<Preparation of dry film>
After appropriately diluting each of the curable resin compositions 1 to 11 with methyl ethyl ketone, using an applicator, apply to a PET film (FB-50: 16 μm, manufactured by Toray Industries, Inc.) so that the film thickness after drying becomes 40 μm. Drying was performed at 80 ° C. for 30 minutes to obtain dry films 1 to 11.

<Preparation of pseudo wafer>
A 4-inch, 150 μm-thick P-type silicon wafer having a 100 nm SiO ₂ film formed on one surface of Canopsis Co., Ltd. was diced using a dicing apparatus to obtain a 10 mm × 10 mm square semiconductor chip. A temporary fixing film was arranged on a SUS flat substrate, and the above-mentioned semiconductor chips were arranged 5 × 5 vertically and horizontally so that the SiO ₂ surface was in contact with the temporary fixing film and the distance between the semiconductor chips was 10 mm vertically and horizontally. A 100 mm × 100 mm square sheet-like sealing material for semiconductor was laminated thereon such that the center positions thereof substantially coincided with each other, and compression-molded at 150 ° C. for 1 hour using a heating press-compression bonding machine. As a semiconductor encapsulant, a kneaded material having the following composition is disposed so as to be sandwiched between two 50 μm cover films (Teijin Purex film), and the kneaded material is formed into a sheet by a flat plate pressing method. A 200 μm sheet was used.

<Preparation of encapsulant composition for semiconductor>
The following components were blended, and the mixture was heated by a roll kneader at 70 ° C. for 4 minutes, then at 120 ° C. for 6 minutes, and melt-kneaded for 10 minutes in total under reduced pressure (0.01 kg / cm ² ) to produce a kneaded product.
・ 30 parts of naphthalene type epoxy resin (NC-7000 manufactured by Nippon Kayaku Co., Ltd.) ・ 10 parts of bixylenol type epoxy resin (YX-4000 manufactured by Mitsubishi Chemical Corporation) ・ Phenol resin (DEN-431 manufactured by The Dow Chemical Company) 10 parts, anthraquinone 2 parts, carbon black (Mitsubishi Chemical Corporation carbon MA-100) 10 parts, spherical silica (Admatechs Admafine SO-E2) 500 parts, silane coupling agent (Shin-Etsu Chemical Co., Ltd. KBM-) 403) 2 parts 2-phenylimidazole (2PZ manufactured by Shikoku Chemicals Corporation) 2 parts

  Next, the temporary fixing film was peeled off from the obtained laminate, and the back side was polished to obtain a 100 mm × 100 mm square, 200 μm thick pseudo wafer.

  A positive-type rewiring-forming resin composition having the following composition was applied to the semiconductor circuit surface side of the obtained pseudo wafer by spin coating, and heated at 100 ° C. for 20 minutes to perform prebaking. The thickness of the photosensitive rewiring forming resin layer formed on the pseudo wafer after prebaking was 10 μm.

<Preparation of resin composition for rewiring formation>
First, 2,2-bis (3-amino-4-hydroxyphenyl) -propane is dissolved in N-methylpyrrolidone, and 0 to 5 is added while dropping N-methylpyrrolidone of 4,4′-diphenyletherdicarboxylic acid chloride. The reaction was carried out at a temperature of ° C. to synthesize a polyhydroxyamide (polybenzoxazole precursor) resin having a weight average molecular weight of 1.3 × 10 ⁴ .
Next, the following components containing a polyhydroxyamide resin were blended, and the mixed solution was subjected to pressure filtration using a 3 μm-pore Teflon (registered trademark) filter to prepare a resin composition for rewiring.
・ 100 parts of polyhydroxyamide resin (Z2) ・ 10 parts of phenol resin (DEN-431 manufactured by The Dow Chemical Company) ・ 1-naphthoquinone-2-diazide-5-sulfonic acid ester (manufactured by AZ Electronic Materials) 10 parts Y-X-Y type block copolymer (Nano Strength M52N manufactured by Arkema) 5 parts Silane coupling agent (KBM-403 manufactured by Shin-Etsu Chemical Co., Ltd.) 2 parts γ-butyrolactone 30 parts Propylene glycol monomethyl ether acetate 120 parts

Subsequently, through a photomask in which a 100 μm circular opening pattern is continuously formed vertically and horizontally at a pitch of 400 μm, a positive exposure is performed at a light exposure of 500 mJ / cm ² using a HMW680GW (metal halide lamp) manufactured by ORC. Light irradiation was performed in the form of a mold pattern, and development was performed at 25 ° C. for 2 minutes using a 2.38 wt% aqueous solution of TMAH to form a rewiring resin layer having a round opening pattern. Thereafter, a baking treatment was performed at 200 ° C. for 1 hour, and the resultant was cooled to room temperature. The pseudo wafer thus obtained had a warp such that the rewiring resin layer side was concave. The amount of warpage was such that the central portion was recessed by 6 mm with reference to the peripheral portion of 100 mm × 100 mm square.

  Each dry film obtained above was bonded to the surface of the pseudo wafer opposite to the surface on which the circuit was formed (the surface on which the rewiring resin layer was formed) using a vacuum laminator. Subsequently, the dry film was cured under a combination of exposure conditions and heating conditions shown in Table 2. In the case where the exposure step was performed before the heating step, the support film was peeled off after the exposure step, and the heating step was performed. The curing reaction was performed in the order of steps 1, 2, and 3 in Table 2.

In Table 2, the horizontal line (-) indicates that the step was not performed. UV1, UV2, UV3, UV4 and K1 respectively indicate the following curing conditions.
UV1: Under 25 ° C., the entire surface irradiated with 3000 mJ / cm ² using a metal halide lamp UV2: under 25 ° C., the entire surface irradiated with 2000 mJ / cm ² using a metal halide lamp UV3: under 25 ° C., using a metal halide lamp 1500 mJ / cm ² by irradiating the entire surface UV4: under 25 ° C., at 2000 mJ / cm ² using a metal halide lamp, irradiation only in a position which is embedded semiconductor chip through a pattern mask K1: heating 1 hour at 170 ° C.

<Measurement of warpage of pseudo wafer>
The amount of warpage of the pseudo wafer in which the dry film was cured as described above to form the warp correction layer was measured. The amount of warpage was measured at 25 ° C. by using long caliper. If the warpage at the center was ± 2 mm or less with respect to the two points at the periphery of the pseudo wafer, it was judged as good (〇). ± 2 to 3 mm was judged to be Δ, and when ± 3 mm was exceeded, it was judged to be defective (x). X: No subsequent evaluation was performed. The evaluation results were as shown in Table 3 below.

<Reliability test of pseudo wafer>
A wafer having a good result in the above-mentioned warpage evaluation is cut out into chips by dicing and solder heat resistance (10 times at 260 ° C. three times) for ten samples under one condition, 500 thermal cycles (One cycle of standing at -40 ° C. for 15 minutes and then standing at 125 ° C. for 15 minutes) was performed. Thereafter, the cross section of the pseudo wafer was observed under a microscope, and the boundary portion where the curable resin composition was in close contact was observed to confirm the presence or absence of a defective product having peeled off. The test was evaluated as pass (〇) when the peeling was zero in 10 pieces, and was rejected (x) when peeling occurred in one or more pieces. The evaluation results were as shown in Table 3 below.

  As is clear from Table 3, the curable component whose volume is contracted by a curing reaction and the curable resin compositions 1 to 8 containing the curable component whose volume is contracted by a different curing reaction are different from each other. The pseudo wafer provided with the warp correction layer formed by individually hardening by the hardening means has a high warp correction force, and good results without peeling failure even in the heat history and reliability evaluation at the time of subsequent semiconductor mounting. there were.

  On the other hand, a warp correcting layer formed by using a curable resin composition 9 to 11 containing a curable component whose volume is shrunk by a curing reaction but containing no curable component whose volume is shrunk by a different curing reaction. The pseudo-wafer provided with is insufficient in the warp correcting force, and if the reaction is further advanced to increase the warp correcting force, peeling failure occurs in the heat history and reliability evaluation during semiconductor mounting. In particular, in the pseudo wafer in which the warp correction layer was formed using the curable resin composition 11, a part of the warp correction layer was peeled off.

Claims (4)

A semiconductor chip having a circuit formed on one surface;
A sealing material sealing the semiconductor chip so that the circuit forming surface is exposed,
A redistribution layer provided on the circuit forming surface side of the sealing material,
A fan-out type wafer level package comprising: a sealing material, a warp correction layer provided on a surface opposite to a surface on which the rewiring layer is provided,
A curable resin composition in which the warp correction layer can be cured by at least two kinds of curing reactions, wherein the curable component (A1) whose volume is shrunk by the one curing reaction and the curable component (A1) whose volume is shrunk by the other curing reaction; Ri but Do a cured product of the curable resin composition containing a curable component which contracts (B1),
The one curing reaction is an ionic ring-opening polymerization reaction or a polyaddition polymerization reaction, and the other curing reaction is a radical addition polymerization reaction,
The volume shrinkage A (%) when the curable component (A1) whose volume shrinks due to the ionic ring-opening polymerization reaction or polyaddition polymerization reaction is cured is in the range of 0 <A ≦ 7, and
The radical addition-polymerizable curable components of the reaction volume by contracts (B1) volumetric shrinkage upon curing is B (%) is characterized by a range near Rukoto of 5 ≦ B ≦ 30, the fan-out Wafer level package. The ionic ring-opening polymerization reaction or polyaddition polymerization reaction is an ionic ring-opening polymerization reaction or polyaddition polymerization reaction by heating, and the radical addition polymerization reaction is a photoradical addition polymerization reaction. The fan-out type wafer level package according to claim 1 . The volume shrinkage A and the volume shrinkage B are represented by the following formula:
A <B
3. The fan-out type wafer level package according to claim 1 , wherein the wafer level package satisfies the following. A method of manufacturing a fan-out type wafer level package according to any one of claim 1 to 3
After forming the encapsulant and the rewiring layer, when the curable resin composition is cured to form a warp correction layer, the curable resin composition is determined by the degree of warpage of the fan-out type wafer level package. A method for manufacturing a fan-out type wafer level package, wherein a degree of curing of an object is adjusted to form a warp correction layer.