Classifications

• • H10W74/47—
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F2/00—Processes of polymerisation
  • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F2/00—Processes of polymerisation
  • C08F2/46—Polymerisation initiated by wave energy or particle radiation
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
  • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
  • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
• • H10W70/60—
• • H10W74/10—
• • H10W74/40—

Definitions

• the present invention relates to a semiconductor encapsulant, and more particularly to a semiconductor encapsulant for a fan-out type wafer level package in which an arrangement region of external connection electrodes is larger than a semiconductor planar size. .
• WLP wafer level package
• the number of electrodes (terminals and bumps) for external connection of the semiconductor chip tends to increase. Therefore, the pitch of the electrodes for external connection of the semiconductor chip is small. Tend to be. However, it is not always easy to directly mount a semiconductor chip on which bumps are formed at a fine pitch on a circuit board.
• a region of the semiconductor sealing material is formed so as to be in contact with the outer periphery or a partial region of the semiconductor chip, and the rewiring layer connected to the electrode is formed in the region of the semiconductor sealing material. It has also been proposed to increase the pitch of the bumps.
• a WLP is called a fan-out type wafer level package (hereinafter sometimes abbreviated as FO-WLP) because the size of the bump arrangement area is larger than the size of the semiconductor chip.
• a semiconductor chip In FO-WLP, a semiconductor chip is embedded with a semiconductor sealing material. The circuit surface of the semiconductor chip is exposed to the outside, and a boundary between the semiconductor chip and the semiconductor sealing material is formed. A rewiring layer connected to the electrode of the semiconductor chip is also provided in the region of the semiconductor sealing material for embedding the semiconductor chip, and the bump is electrically connected to the electrode of the semiconductor chip through the rewiring layer.
• the pitch of the bumps can be set larger than the pitch of the electrodes of the semiconductor chip.
• a semiconductor chip or an electronic component is arranged at a certain interval on a support, embedded with a semiconductor sealing material, and the sealing material is heat-cured, and then the support.
• Pseudo wafer is produced by peeling from the wafer.
• a rewiring layer is formed from the semiconductor chip circuit surface of the pseudo wafer to the expanded 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.
• Patent Document 1 discloses a semiconductor package manufactured using a liquid sealing resin composition capable of suppressing warpage of a pseudo wafer that causes a decrease in productivity in WLP
• Patent Document 2 discloses warpage.
• An electronic component sealing resin sheet capable of suppressing the amount is disclosed.
• Patent Documents 3 to 5 have good wafer protection performance that enables wafers to be molded (wafer molding) at the same time even for large-diameter and thin-film wafers and at the same time suppresses warpage of the wafer after molding.
• a resin composition suitable for WLP is disclosed.
• attempts have been made to adjust the thickness of the support and the content of the inorganic filler in order to suppress the warpage of the wafer (Patent Document 6), or to use a laminated structure sealing material having a plurality of layers (patent). References 7 and 8).
• Patent Document 9 the thermal expansion between the semiconductor chip and the sealing material, which is the cause of the warp, is focused on the storage elastic modulus of the sealing resin. It has been proposed to use a resin sealing material that can relieve thermal stress caused by the difference in coefficients (Patent Document 10).
• the chip circuit surface is exposed from the semiconductor sealing material for the subsequent rewiring forming process. Therefore, there is a tendency that the semiconductor chip and the sealing resin in contact with the back side of the chip circuit surface are warped to protrude toward the chip circuit surface side due to the difference in thermal expansion coefficient. Such convex warpage may cause damage of the pseudo wafer in the subsequent transfer process and defocusing of patterning in the formation of the rewiring layer.
• the stress that contracts against the pseudo wafer acts by the heat treatment following the formation and development of the polymer film corresponding to the insulating layer.
• an object of the present invention is to provide a semiconductor sealing material that can reduce warpage of a wafer or package in a semiconductor wafer or semiconductor package, particularly a fan-out type wafer level package (FO-WLP).
• FO-WLP fan-out type wafer level package
• the present inventors have determined the order and degree of curing of each component in the encapsulating material for a semiconductor containing a thermosetting component and an active energy ray-curable component. Even if the direction of warping and the amount of warping are different in each processing step by adjusting according to the amount of line so that the stress opposite to the shrinkage stress acting on the package acts on each processing step It was found that a semiconductor package without warping could be realized. And, by controlling the amount of heat generated during photocuring and the amount of heat generated during thermosetting of the resin composition that constitutes the encapsulant, the shrinkage stress acting on the package is appropriately generated in each processing step to correct warpage. I learned that I can do it.
• the semiconductor encapsulant containing the thermosetting component and the active energy ray curable component is subjected to a heat treatment at 150 ° C. for 10 minutes, and the thermosetting reaction proceeds to some extent, but completely.
• a pseudo wafer such as FO-WLP in an unheated state
• the active energy ray curing reaction when irradiated with 1 J / cm 2 of ultraviolet rays including a wavelength of 351 nm at 25 ° C.
• the curing shrinkage of the active energy ray-curable component is promoted, and the warp stress is applied to correct the warp so as to cancel the warp stress inherent in the preformed pseudo-wafer. I found that I can do it.
• the present invention is based on such knowledge.
• the semiconductor sealing material according to the first embodiment of the present invention is a semiconductor sealing material including at least a thermosetting component (A) and an active energy ray-curable component (B),
• a calorific value ⁇ when a semiconductor encapsulant after heat treatment at 150 ° C. for 10 minutes in an environment not exposed to active energy rays is irradiated with 1 J / cm 2 of ultraviolet light containing a wavelength of 351 nm at 25 ° C. J / g) is 1 ⁇ ⁇ (J / g).
• the semiconductor encapsulant according to the second embodiment of the present invention is obtained by using a differential scanning calorimeter (DSC) from 25 ° C. to 230 ° C. in an environment not exposed to active energy rays.
• DSC differential scanning calorimeter
• the semiconductor encapsulant according to the third embodiment of the present invention is obtained by changing the semiconductor encapsulant after the heat treatment at 150 ° C. for 10 minutes in an environment where it is not exposed to the active energy ray.
• a calorific value ⁇ (J / g) when heated at 10 ° C. per minute from 25 ° C. to 230 ° C. with a differential scanning calorimeter (DSC) is 1 ⁇ ⁇ (J / g).
• the semiconductor sealing material according to [1] or [2].
• the semiconductor encapsulant according to the fourth embodiment of the present invention is any one of [1] to [3], which is in a liquid, granule, tablet, or sheet form. It is a sealing material for semiconductors.
• the semiconductor sealing material according to the fifth embodiment of the present invention is a sheet-shaped semiconductor sealing material laminated in two or more layers, and the material composition of each layer is different from each other. [4] Any one of the sealing materials for semiconductors.
• a semiconductor encapsulant according to the sixth embodiment of the present invention is used in contact with an outer periphery or a partial region of a semiconductor chip, and is any one of [1] to [5] It is a stopping material.
• a semiconductor encapsulant according to the seventh embodiment of the present invention is any one of [1] to [5] semiconductor encapsulant used for a fan-out type wafer level package.
• a method of manufacturing a fan-out type wafer level package according to the eighth embodiment of the present invention includes: A semiconductor encapsulant comprising at least a thermosetting component (A) and an active energy ray curable component (B), and subjected to a heat treatment at 150 ° C. for 10 minutes in an environment not exposed to active energy rays.
• the encapsulating material for semiconductors after that has a calorific value ⁇ (J / g) of 1 ⁇ ⁇ (J / g) when irradiated with 1 J / cm 2 of ultraviolet rays containing a wavelength of 351 nm at 25 ° C.
• the process of preparing the stop material The fan is heated by heating the semiconductor encapsulant so that the thermosetting reaction of the thermosetting component (A) in the semiconductor encapsulant has progressed to some extent but is not completely thermoset.
• the semiconductor chip when a semiconductor wafer is molded by heating using a semiconductor sealing material, and then the semiconductor chip circuit surface side is convexly formed by shrinkage after thermal curing of the semiconductor sealing material, the semiconductor chip By irradiating the active energy rays from the circuit surface side, the warpage of the pseudo wafer can be corrected by the volume shrinkage of the semiconductor sealing material existing between the semiconductor chips.
• the semiconductor encapsulant on the side opposite to the semiconductor chip circuit surface is irradiated by irradiating the surface opposite to the above with active energy rays. Warpage can be corrected by volumetric shrinkage of the material. Further, the amount of warpage correction can be adjusted by adjusting the irradiation amount of the active energy ray.
• the encapsulant for semiconductor according to the present invention contains a thermosetting component (A) and an active energy ray-curable component (B) as at least two kinds of components at 150 ° C. in an environment not exposed to active energy rays.
• the calorific value when irradiated with active energy rays is 1 J / g or more as described above.
• the active energy ray-curable component contained in the encapsulant on the side irradiated with the active energy ray is accelerated to cure and shrink and change the state of warpage. be able to.
• the calorific value ⁇ is more preferably 2 J / g or more, further preferably 3 J / g or more, and particularly preferably 4 J / g or more. As the calorific value ⁇ increases, curing shrinkage of the active energy ray-curable component can be promoted, but the upper limit is approximately 300 J / g.
• a calorific value ⁇ when a semiconductor encapsulant subjected to heat treatment at 150 ° C. for 10 minutes is irradiated with 1 J / cm 2 of ultraviolet rays containing a wavelength of 351 nm at 25 ° C.”
• the semiconductor encapsulant composition before curing is heated from 25 ° C. to 150 ° C. at 10 ° C./min, held at 150 ° C. for 10 minutes, and then cooled to 25 ° C. at a temperature decreasing rate of 10 ° C./min.
• the applied encapsulant composition for semiconductor was irradiated with 1 J / cm 2 of active energy rays having a wavelength of 351 nm using an optical differential scanning calorimetry apparatus (an apparatus combining a differential scanning calorimetry apparatus and an optical check apparatus). It shall mean the calorific value ⁇ (J / g) when measured.
• ⁇ J / g
• the semiconductor encapsulant before curing is heated from 25 ° C. to 230 ° C. at a rate of 10 ° C./min with a differential scanning calorimeter (DSC) in an environment where it is not exposed to active energy rays.
• DSC differential scanning calorimeter
• the calorific value ⁇ of the semiconductor sealing material is 1 J / g or more. Since the initial curing reaction proceeds rapidly by using the semiconductor sealing material containing the thermosetting component (A) and the active energy ray-curable component (B) having such a calorific value ⁇ , the FO— When a pseudo wafer such as WLP is formed, the shape is easily maintained.
• the upper limit of the heat generation amount ⁇ is not particularly limited, but active energy ray irradiation after the heat curing reaction Considering the adjustment of the curing shrinkage amount due to the above, the upper limit of the heat generation amount is about 300 J / g.
• the semiconductor encapsulant after the heat treatment at 150 ° C. for 10 minutes is applied to the unsealed semiconductor encapsulant in an environment where it is not exposed to active energy rays.
• the semiconductor encapsulant after the heat treatment that is, after the curing reaction of the thermosetting component (A) has progressed to some extent, contains a component whose calorific value ⁇ is 1 J / g or more. Even after heat treatment at 10 ° C.
• thermothermal curing reaction of the semiconductor sealing material is not completed, so that it is easy to maintain the shape when forming a pseudo wafer such as FO-WLP, It becomes easy to adjust the amount of cure shrinkage by irradiation with active energy rays after the heat curing reaction.
• thermosetting component (A) contained in the semiconductor sealing material is thermoset, the curing reaction of the active energy ray curable component (B) does not proceed, but the thermosetting component (A). Is completely cured, the molecular motion of the active energy ray-curable component (B) is restricted, so that it is considered that the curing reaction by active energy rays does not easily proceed.
• the active energy ray curing reaction after the thermal curing reaction is obtained by using a semiconductor encapsulant having a calorific value ⁇ of 1 J / g or more after heat treatment at 150 ° C. for 10 minutes.
• the amount of cure shrinkage can be adjusted.
• the upper limit of the calorific value ⁇ is not particularly limited, but the upper limit of the calorific value is about 300 J / g in consideration of the shape retention property of the pseudo wafer by the thermosetting reaction.
• the amount of reaction heat accompanying the curing reaction of the semiconductor sealing material can be measured using a DSC apparatus.
• DSC Q100 manufactured by TA Instruments can be used as the thermal DSC.
• the calorific value when the active energy ray is measured by irradiating the semiconductor sealing material with 1 J / cm 2 is a light in which a device (for example, an ultraviolet irradiation unit) that irradiates the DSC device with an active energy ray such as an ultraviolet ray is incorporated. It can be measured using a DSC apparatus.
• an optical DSC device for example, an active energy beam is exposed to a DSC module of DSC Q100 manufactured by TA Instruments Co., Ltd.
• thermosetting component (A) As the thermosetting component (A) contained in the semiconductor sealing material according to the present invention, a curing reaction is initiated by, for example, a thermosetting agent component, and a conventionally known material can be used without particular limitation. And cyclic ethers such as oxetane are preferably used. The cyclic ethers such as epoxy and oxetane shrink in volume due to the curing reaction, but as described later, when the thermosetting component (A) is cured, the adhesion with the pseudo wafer is improved. In addition, the adhesion between the semiconductor chip and the semiconductor sealing material can be improved.
• Epoxy resins include solid, semi-solid, and liquid epoxy resins from the pre-reaction shape. These can be used individually by 1 type or in combination of 2 or more types.
• solid epoxy resin an epoxidized product (trisphenol type epoxy resin) of a condensate of phenols such as EPPN-502H (trisphenol epoxy resin) manufactured by Nippon Kayaku Co., Ltd.
• DIC Dicyclopentadiene aralkyl epoxy resin such as Epiklon HP-7200H (dicyclopentadiene skeleton-containing polyfunctional solid epoxy resin) manufactured by KK; Epicron N660, Epicron N690 manufactured by DIC Corporation, EOCN-104S manufactured by Nippon Kayaku Co., Ltd. Novolac type epoxy resin; phenol novolac type epoxy resin such as DEN-431 manufactured by The Dow Chemical Company; biphenyl type epoxy resin such as YX-4000 manufactured by Mitsubishi Chemical Corporation; TX07 manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. 2 like phosphorus-containing epoxy resin; manufactured by Nissan Chemical Industries, tris TEPIC such Ltd. (2,3-epoxypropyl) isocyanurate.
• Semi-solid epoxy resins include DIC Corporation Epicron 860, Epicron 900-IM, Epicron EXA-4816, Epicron EXA-4822, Nippon Steel & Sumitomo Metal Corporation Epotot YD-134, Mitsubishi Chemical Corporation jER828, jER834, Examples include jER872, jER1001, bisphenol A type epoxy resins such as ELA-134 manufactured by Sumitomo Chemical Co., Ltd .; phenol novolac type epoxy resins such as Epicron N-740 manufactured by DIC Corporation.
• Liquid epoxy resins include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, phenol novolac type epoxy resin, tert-butyl-catechol type epoxy resin, glycidylamine type epoxy resin, aminophenol type epoxy resin And alicyclic epoxy resins.
• thermosetting component (A) can be used alone or in combination of two or more.
• the semiconductor encapsulant according to the present invention preferably contains a curing agent component capable of curing the thermosetting component (A).
• a curing agent component capable of curing the thermosetting component (A).
• thermosetting agent component those capable of causing the thermosetting component (A) to undergo ionic ring-opening polymerization or polyaddition polymerization reaction by heat can be used.
• the curing agent component capable of ionic ring-opening polymerization of the thermosetting component (A) imidazoles, benzylsulfonium salts, Lewis acid-amine complexes and the like can be used. Among these, it is desirable to use imidazoles from the viewpoints of adhesion to a pseudo wafer, storage stability, moisture resistance reliability, and the like.
• imidazoles examples include 2MZ, C11Z, 2PZ, 2E4MZ, 2P4MZ, 1B2MZ, 1B2PZ, 2MZ-CN, 2E4MZ-CN, 2PZ-CN, C11Z-CN, 2PZ-CNS, C11Z-CNS, 2MZ-A, and C11Z.
• -A, 2E4MZ-A, 2P4MHZ, 2PHZ, 2MA-OK, 2PZ-OK manufactured by Shikoku Kasei Kogyo Co., Ltd., product name
• those encapsulating these curing agents with a polyurethane-based or polyester-based polymer substance and making them into microcapsules are preferable because the pot life is extended. These may be used alone or in admixture of two or more.
• the amount of the imidazole is preferably 0.1 to 10% by mass, more preferably 0.5 to 10% by mass, and further preferably 1 to 10% by mass with respect to the thermosetting component (A). It is.
• benzylsulfonium salt Sanshin Chemical Industries, Ltd. Sun 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, SI-B5 can be used. These may be used alone or in admixture of two or more.
• the compounding amount of the benzylsulfonium salt is preferably 0.1 to 10% by mass, more preferably 0.5 to 10% by mass, and further preferably 1 to 10% by mass with respect to the thermosetting component (A). %.
• Lewis acid-amine complex known compounds such as a BF 3 -triethylamine complex and a BF 3 -pyridine complex can be used.
• the blending amount of the thermosetting component such as Lewis acid-amine complex is preferably 0.1 to 10% by mass, more preferably 0.5 to 10% by mass with respect to the thermosetting component (A). More preferably, it is 1 to 10% by mass.
• the thermosetting component (A) may be cured by a polyaddition polymerization reaction.
• the curing agent component capable of causing the polyaddition polymerization reaction of the thermosetting component (A) acid anhydrides, carboxylic acids, amines, phenols, hydrazides, polymercaptans, and the like can be used. Among them, it is desirable to use carboxylic acids, amines, and phenols from the viewpoints of adhesion to the pseudo wafer, storage stability, moisture resistance reliability, and the like.
• acid anhydrides examples include methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, hexahydrophthalic anhydride, methylheimic anhydride, pyromellitic dianhydride, benzophenonetetracarboxylic acid Anhydride, 3,4-dimethyl-6- (2-methyl-1-propenyl) -1,2,3,6-tetrahydrophthalic anhydride, 1-isopropyl-4-methyl-bicyclo [2.2.2 Oct-5-ene-2,3-dicarboxylic acid anhydride and the like can be used. These may be used alone or in admixture of two or more.
• thermosetting component (A) is an epoxy compound
• the ratio of the number of curable functional groups (epoxy groups) to the number of carboxylic acids generated from the acid anhydride groups (thermosetting) is preferably performed so that the number of the functional groups (A) / the number of carboxylic acids in the component (A) is 0.2 to 20, and more preferably 0.4 to 16.
• thermosetting component (A) when the thermosetting component (A) is other than an epoxy group, the ratio of the number of curing functional groups involved in the curing reaction to the number of carboxylic acids generated from the acid anhydride group (of the thermosetting component (A)) It can be calculated in the same manner from the number of curing functional groups / number of carboxylic acids.
• carboxylic acids examples include adipic acid, maleic acid, methyl tetrahydrophthalic acid, methyl hexahydrophthalic acid, hexahydrophthalic acid, methyl hymic acid, pyromellitic acid, benzophenone tetracarboxylic 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 A resin having a carboxyl group in the chain can be used.
• the ratio of the number of curing functional groups (epoxy groups) to the number of carboxyl groups (of the curing functional groups of the thermosetting component (A)) is preferably 0.2 to 20, and more preferably 0.4 to 16.
• thermosetting component (A) when the thermosetting component (A) is other than an epoxy group, the ratio of the number of curing functional groups involved in the curing reaction to the number of carboxyl groups (the number of curing functional groups of the thermosetting component (A) / carboxyl) It can be calculated in the same manner from the number of groups).
• the amine is not particularly limited as long as it is a compound having at least one primary or secondary amino group in the molecule.
• aromatic amines may be used. desirable.
• aromatic amines include diaminodiphenylmethane, diaminodiphenylsulfone, diaminodiphenyl sulfide, metaxylenediamine, 3,3′-diethyl-4,4′-diaminodiphenylmethane, 3,3 ′, 5,5′-tetraethyl.
• thermosetting component (A) is an epoxy compound
• the ratio of the number of cured functional groups (epoxy groups) to the number of active hydrogens is 0.
• the blending is desirably 2 to 20, more preferably 0.4 to 16.
• the thermosetting component (A) is other than an epoxy group
• the ratio of the number of curing functional groups involved in the curing reaction to the number of active hydrogens (the number of curing functional groups of the thermosetting component (A) / activity) It can be calculated similarly from the number of hydrogen).
• phenols include phenol novolac resins, alkylphenol volac resins, bisphenol A novolac resins, dicyclopentadiene type phenol resins, Xylok type phenol resins, terpene modified phenol resins, cresol / naphthol resins, polyvinyl phenols, phenol / naphthol resins, An ⁇ -naphthol skeleton-containing phenol resin, a triazine-containing cresol novolac resin, various polyfunctional phenol resins, and the like can be used. These can be used individually by 1 type or in mixture of 2 or more types.
• thermosetting component (A) is an epoxy compound
• the ratio of the number of functional groups (epoxy groups) to the number of phenolic hydroxyl groups Is desirably 0.2 to 20, more preferably 0.4 to 16.
• the ratio of the number of curing functional groups involved in the curing reaction to the number of phenolic hydroxyl groups (the number of curing functional groups of the thermosetting component (A) / The number can be calculated in the same manner from the number of phenolic hydroxyl groups.
• a cyanate ester resin or an active ester resin can be used as a curing agent component capable of polymerizing the thermosetting component (A) by a polyaddition polymerization reaction.
• the cyanate ester resin is a compound having two or more cyanate ester groups (—OCN) in one molecule. Any conventionally known cyanate ester resins can be used. Examples of the cyanate ester resin include phenol novolac 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, and bisphenol S type cyanate ester resin. Is mentioned. Further, it may be a prepolymer partially triazine.
• the active ester resin is a resin having two or more active ester groups in one molecule.
• the active ester resin can generally be obtained by a condensation reaction between a carboxylic acid compound and a hydroxy compound.
• an active ester compound obtained by using a phenol compound or a naphthol compound as the hydroxy compound is preferable.
• phenol compound or naphthol compound examples include hydroquinone, resorcin, bisphenol A, bisphenol F, bisphenol S, phenolphthaline, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, ⁇ -naphthol, ⁇ -naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucin, benzenetriol , Dicyclopentadienyl diphenol, phenol novolac and the like.
• curing accelerator When using carboxylic acids, acid anhydrides, amines, phenols, cyanate ester resins, active ester resins as curing agent components that can polymerize thermosetting component (A) by polyaddition polymerization reaction, curing accelerator May be used in combination.
• the curing accelerator the imidazoles can be used.
• 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, 2,4-diamino-6-xylyl-S-triazine; tributylphosphine Organic phosphines such as triphenylphosphine and tris-2-cyanoethylphosphine; tri-n-butyl (2,5-dihydroxyphenyl)
• Phosphonium salts benzyl trimethyl ammonium chloride, quaternary ammonium salts such as phenyl tributylammonium chloride; the polybasic acid anhydride. These 1 type can be used individually or in mixture of 2 or more types.
• the curing accelerator component is not essential, particularly when it is desired to accelerate the curing reaction, it is based on 100 parts by mass of the curing agent component capable of polymerizing the thermosetting component (A) by a polyaddition polymerization reaction with the heat described above. Preferably, it can be used in the range of 0.01 to 20 parts by mass.
• the content is preferably 10 to 550 ppm, more preferably 25 to 200 ppm in terms of metal with respect to 100 parts by mass of the curable component.
• the semiconductor sealing material according to the present invention includes an active energy ray-curable component (B).
• the active energy ray-curable component means a component that undergoes a curing reaction when irradiated with active energy rays.
• an active energy ray means the electromagnetic wave which has energy required for a hardening
• Such an active energy ray-curable component (B) can be selected from known materials.
• a curable component that can be cured by a radical addition polymerization reaction can be preferably used.
• radical addition polymerization means a reaction in which polymerization is initiated by radicals and an unsaturated compound having a double bond or triple bond is added to form a polymer.
• the curable component that can be cured by such radical addition polymerization reaction a compound having one or more ethylenically unsaturated groups in the molecule is preferable.
• thermosetting component (A) and the active energy ray curable component (B) as described above are contained in the encapsulant for semiconductor, so that when the encapsulant for semiconductor is cured, thermosetting is performed.
• the active component (A) and the active energy ray-curable component (B) can be separately cured. Therefore, when producing a pseudo wafer using the semiconductor sealing material, the irradiation amount of the active energy ray is adjusted according to the warping direction and the warping amount of the wafer, and is approximately the same as the warping stress inherent in the pseudo wafer. Can be generated on the irradiation surface side of the active energy ray.
• FO-WLP with reduced warpage can be obtained even when manufacturing FO-WLP with different materials, thicknesses, and patterns for the rewiring layer.
• the active energy ray-curable component (B) whose volume is shrunk by a radical addition polymerization reaction.
• the active energy ray-curable component (B) undergoes all of the curing reaction of the active energy ray-curable component by the heat energy when the thermosetting component (A) described above is cured and the generated heat of the curing reaction. It is preferable to use those that do not.
• radical addition polymerization-reactive components include, for example, conventionally known polyester (meth) acrylate, polyether (meth) acrylate, urethane (meth) acrylate, carbonate (meth) acrylate, epoxy (meth) ) Acrylate and the like.
• 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-methylol acrylamide and N, N-dimethylaminopropyl acrylamide; aminoalkyl acrylates such as N, N-dimethylaminoethyl acrylate and N, N-dimethylaminopropyl acrylate; hexanediol, trimethylolpropane, Polyhydric alcohols such as pentaerythritol, dipentaerythritol, tris-hydroxyethyl isocyanurate or the like Polyvalent acrylates such as id adduct, propylene oxide adduct, or ⁇ -caprolactone adduct; phenoxyalkyl
• maleimide compounds may be used as the active energy ray-curable component (B) that can be cured by radical addition polymerization reaction.
• a photo radical initiator described later may be used, or even if not used, the photo-dimerization reaction is caused by irradiation with active energy rays to warp the sealing material for semiconductor. The amount can also be reduced.
• the active energy ray-curable component (B) that can be cured by radical addition polymerization reaction the following compounds (1) to (11) may be used.
• a reaction product obtained by reacting a compound having a plurality of phenolic hydroxyl groups in one molecule with an alkylene oxide is reacted with an unsaturated group-containing monocarboxylic acid, and the resulting reaction product is converted to a polybasic acid.
• (Meth) acrylated acrylic-containing urethane resin (8) During the synthesis of a resin by polyaddition reaction of a diisocyanate with a carboxyl group-containing dialcohol compound and a diol compound, a compound having one isocyanate group and one or more (meth) acryloyl groups in the molecule is added, Terminal (meth) acrylated acrylic-containing urethane resin, (9) An acrylic-containing urethane resin obtained by adding a compound having one hydroxyl group and one or more (meth) acryloyl groups in the molecule during the synthesis of the resin of (5), and terminal (meth) acrylated, (10) An acrylic-containing 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 (5) above, and terminally (meth) acrylated; 11) An acrylic-containing polymer obtained by adding a compound having one epoxy group
• the above-mentioned active energy ray-curable component (B) is a calorific value when the temperature is raised from 25 ° C. to 230 ° C. at 10 ° C./min with a differential scanning calorimeter (DSC) in an environment where it is not exposed to active energy rays. It is preferable to use one having a J of substantially 0 J / g.
• DSC differential scanning calorimeter
• the semiconductor encapsulant according to the present invention preferably includes a curing agent component (hereinafter also referred to as a photocuring agent component) that can cure the above-described active energy ray-curable component (B).
• the photocuring agent component may be one capable of radical polymerization of the active energy ray-curable component (B) with active energy rays.
• photocuring agent component examples include bis- (2,6-dichlorobenzoyl) phenylphosphine oxide, bis- (2,6-dichlorobenzoyl) -2,5-dimethylphenylphosphine oxide, and 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) -phenyl Phosphine oxide (IGM Omnirad 819), 2,6-dimeth
• benzoins such as benzoin, benzyl, benzoin methyl ether, benzoin ethyl ether, benzoin n-propyl ether, benzoin isopropyl ether, benzoin n-butyl ether; benzoin alkyl ethers; benzophenone, p-methylbenzophenone, Michler's ketone, methyl Benzophenones such as benzophenone, 4,4′-dichlorobenzophenone, 4,4′-bisdiethylaminobenzophenone; acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2- Diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-1-propanone, 2-benzyl-2- Dimethylamin
• the photocuring agent component is preferably selected from substances that are difficult to evaporate or decompose by heating.
• the vapor pressure at 25 ° C. of the photocuring agent component is preferably 1 ⁇ 10 ⁇ 3 Pa or less, more preferably 5 ⁇ 10 ⁇ 4 Pa or less, and further preferably 1 ⁇ 10 ⁇ 4 Pa or less.
• the photocuring agent component having a vapor pressure of 25 ° C. of 1 ⁇ 10 ⁇ 4 Pa or less include Omnirad 819 (IGM Resins), IRGACURE 379, IRGACURE OXE01 (BASF Japan Ltd.) Etc.
• the thermal decomposition temperature of the photocuring agent component is preferably 150 ° C. or higher, more preferably 155 ° C.
• photocuring agent component having a high thermal decomposition temperature, it is possible to effectively suppress the photocuring agent component from being deactivated during the thermal reaction of the semiconductor sealing material.
• photocuring agent component examples include Omnirad 819 (manufactured by IGM Resins), IRGACURE 379, IRGACURE OXE01 (manufactured by BASF Japan Ltd.), and the like.
• oxime esters hereinafter referred to as “oxime ester photopolymerization initiator”
• ⁇ -aminoacetophenone photopolymerization initiator ⁇ -aminoacetophenone photopolymerization initiator
• photopolymerization initiators selected from the group consisting of acylphosphine oxides (hereinafter referred to as “acylphosphine oxide photopolymerization initiators”).
• oxime ester photopolymerization initiator examples include commercially available products such as CGI-325, IRGACURE OXE01, IRGACURE OXE02 manufactured by BASF Japan, and N-1919 manufactured by ADEKA Co., Ltd.
• the photopolymerization initiator having two oxime ester groups in the molecule is not easily evaporated or decomposed by heating and can generate a plurality of radicals having higher reactivity, so that the warp correction can be carried out more efficiently. Therefore, it can be suitably used.
• Specific examples of such a photopolymerization initiator include oxime ester compounds having a carbazole structure represented by the following general 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).
• Y and Z are each a hydrogen atom, an alkyl group having 1 to 17 carbon atoms, or a carbon number of 1), and is substituted by an alkylamino group having a C 1-8 alkyl group or a dialkylamino group.
• anthryl group is 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.
• Ar is an oxime ester compound wherein phenylene, naphthylene, thiophene or thienylene.
• the blending amount of the oxime ester photopolymerization initiator is preferably 0.01 to 5 parts by mass with respect to 100 parts by mass of the polyether compound containing an ethylenically unsaturated group in the molecule.
• ⁇ -aminoacetophenone photopolymerization initiators include 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 Omnirad 907 manufactured by IGM Resins, IRGACURE 369, IRGACURE 379 manufactured by BASF Japan Ltd., and the like.
• acylphosphine oxide photopolymerization initiator examples include the above compounds.
• examples of commercially available products include IRGACURE TPO manufactured by BASF Japan Ltd., Omnirad 819 manufactured by IGM Resins, and the like.
• an oxime ester-based photopolymerization initiator as a photocuring agent component can not only obtain sufficient sensitivity even in a small amount, but also reduce contamination of equipment such as a drying furnace because the photopolymerization initiator is less volatile. Can do.
• an acylphosphine oxide photopolymerization initiator because it can improve the deep curability at the time of photoreaction and can exhibit more effective warp correction force even in a thick semiconductor encapsulant.
• photocuring agent component Commercially available products may be used as the photocuring agent component.
• IRGACURE 389 and IRGACURE 784 manufactured by BASF Japan Ltd. can be suitably used.
• the active energy ray-curable component (B) is a part of the curing reaction of the active energy ray-curable component due to the thermal energy generated when the thermosetting component (A) is cured or the generated curing reaction heat.
• the photocuring agent component is not substantially activated (generates radicals) by thermal energy or generated curing reaction heat.
• Examples of such a light curing agent component include oxime compounds such as Irgacure IRGACURE 379, Irgacure IRGACURE 784, IRGACURE OXE01 manufactured by BASF Japan Ltd., and Omnirad (omnirad) 819 manufactured by IGM Resins, and a carbazole structure represented by the above general formula. And oxime ester compounds having
• the amount of the photocuring agent component is preferably 1 to 25 parts by mass, more preferably 5 to 20 parts by mass, and still more preferably 10 to 20 parts by mass with respect to 100 parts by mass of the active energy ray-curable component (B). It is. In particular, when the oxime ester photopolymerization initiator is used, the amount of the photopolymerization initiator is 0.01 to 5 parts by mass with respect to 100 parts by mass of the polyether compound containing an ethylenically unsaturated group in the molecule. It is preferable that
• a photoinitiator or sensitizer when a photocuring agent component is included as a curing agent component in the semiconductor sealing material, a photoinitiator or sensitizer may further be included.
• the photoinitiator assistant and sensitizer include benzoin compounds, acetophenone compounds, anthraquinone compounds, thioxanthone compounds, ketal compounds, benzophenone compounds, tertiary amine compounds, and xanthone compounds.
• a photoinitiator and a sensitizer may be used individually by 1 type, and may be used as a mixture of 2 or more types. Of the above, thioxanthone compounds and tertiary amine compounds are preferred.
• a thioxanthone compound is preferable from the viewpoint of the deep part curability of the semiconductor sealing material.
• a thioxanthone compound such as 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, and 2,4-diisopropylthioxanthone.
• the semiconductor sealing material according to the present invention may be in the form of liquid, granule, tablet, or sheet, but when processed into a film (or sheet), the film (or sheet).
• a film property-imparting polymer component (C) that makes it easy to maintain the shape may be included.
• a film property-imparting polymer component (C) include thermoplastic polyhydroxy polyether resins, phenoxy resins that are condensates of epichlorohydrin and various bifunctional phenol compounds, or hydroxyl groups of the hydroxy ether moiety present in the skeleton.
• 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 .
• the value of a weight average molecular weight (Mw) can be measured with the following measuring apparatus and measurement conditions by the gel permeation chromatography method (GPC) method (polystyrene standard).
• GPC gel permeation chromatography method
• Measuring device “Waters 2695” manufactured by Waters Detector: “Waters 2414” manufactured by Waters, RI (differential refractometer)
• Column “HSPgel Column, HR MB-L, 3 ⁇ m, 6 mm ⁇ 150 mm” manufactured by Waters ⁇ 2 + “HSPgel Column, HR1, 3 ⁇ m, 6 mm ⁇ 150 mm” manufactured by Waters ⁇ 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 ⁇ l
• Sample concentration 0.7 wt%
• the polyvinyl acetal resin can be obtained, for example, by acetalizing a polyvinyl alcohol resin with an aldehyde.
• the aldehyde is not particularly limited, and examples thereof include formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde and the like.
• phenoxy resin examples include FX280 and FX293 manufactured by Nippon Steel & Sumitomo Metal Corporation, YX8100, YL6954, and YL6974 manufactured by Mitsubishi Chemical Corporation.
• polyvinyl acetal resin examples include SLECK KS series manufactured by Sekisui Chemical Co., Ltd.
• examples of the polyamide resin include KS5000 series manufactured by Hitachi Chemical Co., Ltd. and BP series manufactured by Nippon Kayaku Co., Ltd.
• polyamideimide resin examples include KS9000 series manufactured by Hitachi Chemical Co., Ltd.
• thermoplastic polyhydroxypolyether resin When a thermoplastic polyhydroxypolyether resin has a fluorene skeleton, it has a high glass transition point and excellent heat resistance, so it maintains a low coefficient of thermal expansion due to a semi-solid or solid epoxy resin and maintains its glass transition point. The resulting cured film has a low thermal expansion coefficient 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 (C) may be obtained by block copolymerization of the monomers constituting the above-described components.
• the block copolymer is a copolymer having a molecular structure in which two or more kinds 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.
• the center Y is a soft block and the glass transition temperature (Tg) is low, and both outer side X or X' is a hard block What is comprised by the polymer unit whose glass transition temperature (Tg) is higher than a center Y block is preferable.
• the glass transition temperature (Tg) is measured by differential scanning calorimetry (DSC).
• X or X ′ is composed of polymer units having a Tg of 50 ° C. or more, and the glass transition temperature (Tg) of Y is More preferred is a block copolymer consisting of polymer units having a Tg of X or X ′ or less.
• X or X ′ is compatible with the thermosetting component (A) or the active energy ray curable component (B). Are preferable, and those having low compatibility with the thermosetting component (A) or the active energy ray curable component (B) are preferable.
• phenoxy resins polyvinyl acetal resins, thermoplastic polyhydroxy polyether resins having a fluorene skeleton, and block copolymers are preferable.
• the ratio of the film property-imparting polymer component (C) occupying all components constituting the semiconductor sealing material is particularly limited. Rather, it is preferably 2 to 40 parts by mass, more preferably 5 to 35 parts by mass when the total of all components is 100 parts by mass.
• the semiconductor sealing material according to the present invention may contain an inorganic filler component (D).
• an inorganic filler component (D) for example, FO-WLP can be easily cut by dicing.
• FO-WLP can be easily cut by dicing.
• the inorganic filler component (D) is exposed in the portion scraped by the laser light, and the reflected light is diffused to exhibit a color close to white.
• the warpage correction material for FO-WLP contains a colorant component (E) described later, a difference in contrast is obtained between the laser marking portion and other portions, and the marking (printing) becomes clear. is there.
• an ultraviolet ray containing a wavelength of 351 nm at 25 ° C. is applied to the semiconductor sealing material after heat treatment at 150 ° C. for 10 minutes in an environment where it is not exposed to active energy rays at 1 J / cm 2.
• the inorganic filler component (D) preferably has an average particle size of 0.01 to 15 ⁇ m, more preferably 0.02 to 12 ⁇ m, and particularly preferably 0.03 to 10 ⁇ m.
• the average particle size is the number average particle size calculated as the arithmetic average value of 20 major axis diameters of 20 inorganic fillers (D) randomly selected with an electron microscope.
• the content of the inorganic filler component (D) is the sum of the curable components (A) and (B) contained in the semiconductor sealing material, both the curing agent components, and the film-providing polymer component (C). Is preferably 10 to 400 parts by mass, more preferably 20 to 350 parts by mass, and particularly preferably 30 to 300 parts by mass.
• the sealing material for semiconductor after being subjected to heat treatment at 150 ° C. for 10 minutes in an environment not exposed to active energy rays at 25 ° C.
• the calorific value ⁇ (J / g) when irradiating ultraviolet rays including 351 nm with 1 J / cm 2 is preferable because it tends to be 1 ⁇ ⁇ (J / g).
• the colorant component (E) may be contained in the semiconductor sealing material according to the present invention.
• the colorant component (E) it is possible to prevent malfunction of the semiconductor device due to infrared rays or the like generated from the surrounding device when the semiconductor chip on which the semiconductor sealing material is disposed is incorporated in the device.
• a semiconductor sealing material is engraved by means such as laser marking, marks such as characters and symbols are easily recognized. That is, in a semiconductor chip on which a semiconductor sealing material is formed, a product number or the like is usually printed on the surface of the protective film by a laser marking method (a method in which the surface of the protective film is scraped off by laser light and printed).
• a laser marking method a method in which the surface of the protective film is scraped off by laser light and printed.
• organic or inorganic pigments and dyes can be used singly or in combination of two or more.
• black pigments are preferred from the viewpoint of electromagnetic wave and infrared shielding properties.
• the black pigment include carbon black, perylene black, iron oxide, manganese dioxide, aniline black, activated carbon, and the like, but are not limited thereto.
• Carbon black is particularly preferable from the viewpoint of preventing malfunction of the semiconductor device.
• pigments or dyes such as red, blue, green, and yellow can be mixed to obtain black or a black color close thereto.
• red colorants examples include monoazo, disazo, azo lake, benzimidazolone, perylene, diketopyrrolopyrrole, condensed azo, anthraquinone, and quinacridone. Specific examples include the following: It is done. PigmentRed 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, 193, 210, 245, 253, 258, 266, 267, 268, 269 and the like, disazo red colorants such as PigmentRed 37, 38, 41, and PigmentRed 48: 1, 48: 2.
• blue colorants include phthalocyanine series and anthraquinone series, and pigment series are compounds classified as Pigment, specifically: Pigment Blue 15, Pigment Blue 15: 1, Pigment Blue 15: 2, Pigment Blue 15: 3, Pigment Blue 15: 4. Pigment Blue 15: 6, Pigment Blue 16, Pigment Blue 60, and the like.
• the dye system include Solvent Blue 35, Solvent Blue 63, Solvent Blue 68, Solvent Blue 70, Solvent Blue 83, Solvent Blue 87, Solvent Blue 94, Solvent Blue 97, Solvent Blue 122, Solvent Blue 70, Solvent Blue 70, and Solvent Blue 70
• metal-substituted or unsubstituted phthalocyanine compounds can also be used.
• the green colorant there are similarly phthalocyanine, anthraquinone, perylene, and the like. Specifically, PigmentGreen 7, PigmentGreen 36, SolventGreen 3, SolventGreen 5, SolventGreen 20, SolventGreen 28, and the like can be used. In addition to the above, a metal-substituted or unsubstituted phthalocyanine compound can also be used.
• yellow colorants examples include monoazo, disazo, condensed azo, benzimidazolone, isoindolinone, anthraquinone, and the like.
• colorants such as purple, orange, brown and black may be added for the purpose of adjusting the color tone.
• the warpage correction layer is also light-transmissive for alignment. It is preferable to have.
• the colorant component (E) can be selected with appropriate consideration.
• the compounding amount of the colorant component (E) is excellent in light transmittance to the deep part, and as a result, a curing contained in the semiconductor sealing material of the semiconductor sealing material from the viewpoint of obtaining a more preferable warp correction layer.
• the amount is preferably 0.1 to 35 parts by mass. More preferably, it is in the range of 0.5 to 25 parts by mass, particularly preferably 1 to 15 parts by mass.
• the sealing agent for semiconductor according to the present invention includes a coupling agent component having a functional group that reacts with an inorganic substance and a functional group that reacts with an organic functional group in order to improve at least one of adhesiveness and adhesion to a semiconductor chip. (F) may be included. Moreover, the water resistance can be improved without impairing the heat resistance of the semiconductor sealing material by including the coupling agent component (F).
• Examples of such coupling agents include titanate coupling agents, aluminate coupling agents, silane coupling agents, and the like. Of these, silane coupling agents are preferred.
• Examples of organic groups contained in the silane coupling agent include vinyl groups, epoxy groups, styryl groups, methacryloxy groups, acryloxy groups, amino groups, ureido groups, chloropropyl groups, mercapto groups, polysulfide groups, and isocyanate groups. Can be mentioned.
• 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 trade names; manufactured by Shin-Etsu Chemical Co., Ltd.) be able to. These may be used alone or in combination of two or more.
• additives may be added to the semiconductor sealing material according to the present invention as necessary.
• Various additives include leveling agents, plasticizers, oxidizing agents, antioxidants, ion scavengers, gettering agents, chain transfer agents, release agents, rust inhibitors, adhesion promoters, ultraviolet absorbers, thermal polymerization inhibitors.
• Additives commonly used in the field of electronic materials such as thickeners and antifoaming agents may be contained.
• the semiconductor encapsulant according to the present invention can contain an organic solvent.
• the organic solvent is used to adjust the viscosity when synthesizing a polyether compound containing an ethylenically unsaturated group in the molecule, mixing each component, and applying the obtained semiconductor sealing material to a substrate or a support film. Can be used for.
• organic solvent examples include ketones, aromatic hydrocarbons, glycol ethers, glycol ether acetates, esters, alcohols, aliphatic hydrocarbons, petroleum solvents, and the like.
• ketones such as methyl ethyl ketone and cyclohexanone, aromatic hydrocarbons such as toluene, xylene, and 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, propano , Ethylene glycol, alcohols such as propylene glycol, octan
• the thickness of the encapsulant for semiconductor of the present invention is not particularly limited when it is in the form of a film (or sheet), but is preferably 3 to 500 ⁇ m, more preferably 5 to 450 ⁇ m, and particularly preferably 7 to 400 ⁇ m. is there.
• the semiconductor sealing material according to the present invention includes, for example, a cyclic ether compound as the thermosetting component (A), and one or more ethylenically unsaturated groups in the molecule as the active energy ray-curable component (B).
• a cyclic ether compound as the thermosetting component (A)
• one or more ethylenically unsaturated groups in the molecule as the active energy ray-curable component (B).
• it contains the compound, it has initial adhesion, and therefore, when uncured, it is easily bonded by pressing against a pseudo-wafer or a chip.
• a cured film (warp correction layer) having high adhesion and high warp correction power can be finally formed.
• the cured film (warp correction layer) formed using the semiconductor sealing material according to the present invention is excellent in 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 semiconductor sealing material may have a single layer structure or a multilayer structure.
• the semiconductor sealing material 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-component or two-component or more.
• the semiconductor encapsulant When making a dry film, the semiconductor encapsulant is diluted with an organic solvent and adjusted to an appropriate viscosity, comma coater, blade coater, lip coater, rod coater, squeeze coater, reverse coater, transfer roll coater, gravure coater, A film can be obtained by applying a uniform thickness on a support film with a spray coater or the like, and drying usually at a temperature of 50 to 130 ° C. for 1 to 30 minutes.
• the coating film thickness is not particularly limited, but is generally 5 to 150 ⁇ m, preferably 10 to 60 ⁇ m in terms of the dry film thickness after drying, in that a semiconductor sealing material having a more preferable warp correction capability can be obtained. It is suitably selected within the range of
• 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. Also, release on one or both sides of a release paper substrate made of a polyester film such as polyethylene terephthalate (PET) or polyethylene naphthalate (PEN), a polyolefin film such as stretched polypropylene film (OPP), or a plastic film such as polyimide film. You may use what formed the layer.
• the release layer is not particularly limited as long as it has a release property, and examples thereof include silicone resins, organic resin-modified silicone resins, and fluororesins.
• the thickness of the support film is not particularly limited, but is generally appropriately selected within the range of 10 to 150 ⁇ m.
• 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.
• a peelable cover film for example, a polyethylene film, a polytetrafluoroethylene film, a polypropylene film, a surface-treated paper, or the like can be used.
• the adhesive force between the membrane and the cover film is made smaller than the adhesive force between the membrane and the support film.
• the semiconductor sealing material of the present invention is adjusted to a viscosity suitable for a coating method using, for example, an organic solvent, and on a substrate, a dip coating method, a flow coating method, a roll coating method, a bar coater method, a screen printing method, a curtain A film shape can be formed by coating by a method such as a coating method and volatile drying (temporary drying) of an organic solvent contained in the composition at a temperature of about 60 to 100 ° C.
• the volatile drying performed after the semiconductor sealing material of the present invention is applied is a hot air circulation drying furnace, an IR furnace, a hot plate, a convection oven or the like (a hot air in a dryer using an air heating type heat source using steam).
• a hot air circulation drying furnace, an IR furnace, a hot plate, a convection oven or the like a hot air in a dryer using an air heating type heat source using steam.
• the semiconductor sealing material When the semiconductor sealing material is in the form of a film, it may be in the form of a laminated film provided with at least two layers containing the above-described components. When it is set as a laminated film, it is preferable that the composition of the sealing material for semiconductor which comprises each layer is mutually different. In particular, by changing the type and blending ratio of the active energy ray-curable component (B) and / or the type and blending amount of the curing component of the active energy ray-curable component (B) in each layer, the active energy ray The amount of cure shrinkage on the front and back surfaces can be controlled in a wider range by irradiation of.
• the active energy ray-curable component in each layer of the laminated film according to the warping direction and the warping amount ( By adjusting the type and blending ratio of B) or the type and blending amount of the curing agent component, a desired warp correction force can be expressed.
• the semiconductor encapsulant When the semiconductor encapsulant is in the form of a laminated film as described above, at least one layer constituting the semiconductor encapsulant, preferably all layers, at 150 ° C. in an environment that is not exposed to active energy rays.
• the amount of heat generated when the semiconductor sealing material after the heat treatment for 10 minutes is irradiated with 1 J / cm 2 of ultraviolet light containing a wavelength of 351 nm at 25 ° C. is preferably 1 J / g or more.
• the state of warpage can be changed by accelerating cure shrinkage of the active energy ray-curable component contained in the semiconductor sealing material on the side irradiated with the active energy ray.
• thermosetting component (A) is cured to some extent by heat to perform molding (preliminary molding)
• one side or both sides of the pseudo wafer is formed. Irradiation with active energy rays enables correction in consideration of the direction of warpage and the amount of warpage.
• the semiconductor encapsulant of the present invention forms a region of the semiconductor encapsulant so as to be in contact with the outer periphery or a partial region of the semiconductor chip, and the rewiring layer connected to the electrode is encapsulated in the semiconductor
• the fan-out type wafer level package also provided in the material region, it is possible to realize a wafer level package without warping.
• parts and “%” mean parts by mass. Further, the production of the sealing material for semiconductor and the subsequent measurement were performed in an environment not exposed to active energy rays unless otherwise specified.
• reaction solution was cooled to room temperature, and 1.56 parts of 89% phosphoric acid was added to and mixed with the reaction solution to neutralize potassium hydroxide.
• the nonvolatile content was 62.1% and the hydroxyl value was 182.2 g / eq.
• a novolak-type cresol resin propylene oxide reaction solution was obtained. This was an average of 1.08 moles of alkylene oxide added per equivalent of phenolic hydroxyl group.
• reaction solution was cooled to room temperature, neutralized with 35.35 parts of a 15% aqueous sodium hydroxide solution, and then washed with water. Thereafter, toluene was distilled off while substituting 118.1 parts of diethylene glycol monoethyl ether acetate (carbitol acetate) with an evaporator to obtain a novolak acrylate resin solution.
• ⁇ Preparation of semiconductor sealing material 1> The following components were dissolved and dispersed in methyl ethyl ketone to prepare a composition solution 1a for a sealing material having a solid content mass concentration of 20%.
• Phenoxy resin FX293 made by Nippon Steel & Sumikin Co., Ltd.
• 50 parts ⁇ Resolution 70.4 parts of resin solution
• Polyfunctional solid epoxy resin containing dicyclopentadiene skeleton (Epiclon HP-7200H made by DIC Corporation) 30 parts ⁇ Bisphenol A type Epoxy resin (jER828, manufactured by Mitsubishi Chemical Corporation) 10 parts, phenol novolac type epoxy resin (DEN-431, manufactured by The Dow Chemical Company) 10 parts, carbon black (carbon MA-100, manufactured by Mitsubishi Chemical Corporation) 10 parts, spherical silica (Admatechs Co., Ltd.
• the protective film-forming encapsulant composition solution 1a was applied to a polyethylene terephthalate film (PET film) having a release treatment on the surface and dried at 100 ° C. for 10 minutes to produce a semiconductor encapsulant 1a having a thickness of 50 ⁇ m.
• PET film polyethylene terephthalate film
• a sealing material composition solution 1b having a solid content mass concentration of 20%.
• Phenoxy resin FX293 made by Nippon Steel & Sumikin Co., Ltd.
• 50 parts ⁇ Resolution 70.4 parts of resin solution
• Polyfunctional solid epoxy resin containing dicyclopentadiene skeleton Epiclon HP-7200H made by DIC Corporation
• 30 parts ⁇ Bisphenol A type Epoxy resin (jER828, manufactured by Mitsubishi Chemical Corporation) 10 parts, phenol novolac type epoxy resin (DEN-431, manufactured by The Dow Chemical Company) 10 parts, carbon black (carbon MA-100, manufactured by Mitsubishi Chemical Corporation) 10 parts ⁇ Spherical silica (Admatechs Co., Ltd.
• Admafine SO-E2) 200 parts ⁇ Aluminum hydroxide (Showa Denko Co., Ltd. Hygielite 42M) 150 parts ⁇ Silane coupling agent (Shin-Etsu Chemical Co., Ltd. KBM-403) 2 parts, anthraquinone 2 parts, 2-phenylimidazole (2PZ, manufactured by Shikoku Chemicals Co., Ltd.) 2 parts, urethane acrylate oligomer (DPHA-40H, manufactured by Nippon Kayaku Co., Ltd.) 10 parts, photo radical polymerization initiator (Irgacure 784) 1.5 parts
• the protective film-forming encapsulant composition solution 1b was applied to a polyethylene terephthalate film (PET film) having a release treatment on the surface and dried at 100 ° C. for 10 minutes to produce a semiconductor encapsulant sheet 1b having a thickness of 50 ⁇ m. .
• PET film polyethylene terephthalate film
• Two sheets of semiconductor encapsulant sheet 1a are laminated using a roll laminator, one side of the peeled PET film is peeled off, and the semiconductor encapsulant sheet 1a is further laminated on the peeled surface to encapsulate the semiconductor.
• a sheet in which three stop material sheets 1a were laminated was produced.
• the same process was performed using the semiconductor sealing material sheet 1b, and the sheet
• one side of the PET film that has been peeled from the sheet on which three semiconductor encapsulant sheets 1a are laminated is peeled off, and the sheet is also peeled off from the sheet on which three semiconductor encapsulant sheets 1b are laminated.
• One side of the PET film subjected to the above is peeled off, the semiconductor encapsulant sheet 1a and the semiconductor encapsulant sheet 1b are bonded together, and the three semiconductor encapsulant sheets 1a and the semiconductor encapsulant sheet 1b 3 were laminated in this order to produce a semiconductor sealing material 1 having a total thickness of 300 ⁇ m.
• ⁇ Preparation of semiconductor sealing material 2> The following components are blended, heated at 70 ° C. for 4 minutes in a roll kneader, then heated at 100 ° C. for 6 minutes, and melt-kneaded for 10 minutes in total under reduced pressure (0.01 kg / cm 2 ). Produced.
• Dicyclopentadiene skeleton-containing polyfunctional solid epoxy resin (Epiclon HP-7200H manufactured by DIC Corporation) 30 parts ⁇ Bisphenol A type epoxy resin (jER828 manufactured by Mitsubishi Chemical Corporation) 10 parts ⁇ Phenol novolac type epoxy resin (The Dow Chemical Company DEN-431) 10 parts Carbon Black (Mitsubishi Chemical Corporation Carbon MA-100) 10 parts, spherical silica (Admatechs Co., Ltd. Admafine SO-E2) 500 parts, silane coupling agent (Shin-Etsu Chemical Co., Ltd. KBM-403) 2 parts, 2-phenylimidazole (Shikoku Chemicals Co., Ltd.
• the obtained kneaded material 2 is arranged so as to be sandwiched between two 50 ⁇ m cover films (Teijin Purex film), and the kneaded material is formed into a sheet by a flat plate pressing method. A stop material 2 was obtained.
• ⁇ Preparation of semiconductor sealing material 3> The following components were blended, heated at 70 ° C. for 4 minutes in a roll kneader, then heated at 100 ° C. for 6 minutes, and melt-kneaded for 10 minutes in total under reduced pressure (0.01 kg / cm 2 ).
• Produced. ⁇ Bisphenol A type epoxy resin (jER1001 manufactured by Mitsubishi Chemical Corporation) 30 parts ⁇ Phenol novolac type epoxy resin (DEN-431 manufactured by The Dow Chemical Company) 10 parts ⁇ C. I. Pigment Blue 15: 3 0.8 part C.I. I. Pigment Yellow 147 0.55 part ⁇ Paligen Red K3580 1.5 part ⁇ Spherical silica (Admafine Co., Ltd.
• the obtained kneaded material 3 is arranged so as to be sandwiched between two 50 ⁇ m PET films (Teijin Purex film), and the kneaded material is formed into a sheet shape by a flat plate pressing method. A stop material 3 was obtained.
• Dicyclopentadiene skeleton-containing polyfunctional solid epoxy resin (Epiclon HP-7200H manufactured by DIC Corporation) 30 parts ⁇ Bisphenol A type epoxy resin (jER828 manufactured by Mitsubishi Chemical Corporation) 10 parts ⁇ Phenol novolac type epoxy resin (The Dow DEN-431, manufactured by Chemical Company, 10 parts, carbon black (Carbon MA-100, manufactured by Mitsubishi Chemical Corporation) 10 parts, spherical silica (Admafine, Inc., Admafine SO-E2) 600 parts, titanium oxide (Ishihara Sangyo) CR-90 made by Co., Ltd.
• the obtained kneaded product 4 is arranged so as to be sandwiched between two 50 ⁇ m cover films (Teijin Purex film), and the kneaded product is formed into a sheet by a flat plate pressing method. A stop material 4 was obtained.
• ⁇ Preparation of semiconductor sealing material 5> The following components were blended, heated at 70 ° C. for 4 minutes in a roll kneader, then heated at 100 ° C. for 6 minutes, and melt-kneaded for 10 minutes in total under reduced pressure (0.01 kg / cm 2 ).
• Produced. ⁇ Dicyclopentadiene skeleton-containing polyfunctional solid epoxy resin (Epiclon HP-7200H manufactured by DIC Corporation) 30 parts ⁇ Bisphenol A type epoxy resin (jER828 manufactured by Mitsubishi Chemical Corporation) 10 parts ⁇ Phenol novolac type epoxy resin (The Dow DEN-431, manufactured by Chemical Company, Ltd.
• the obtained kneaded product 5 is placed so as to be sandwiched between two 50 ⁇ m cover films (Teijin Purex film), and the kneaded product is formed into a sheet by a flat plate pressing method. A stop material 5 was obtained.
• a semiconductor encapsulant 6 having a thickness of 300 ⁇ m was produced in the same manner as in the semiconductor encapsulant 1 except that acrylate and a radical photopolymerization initiator were not used.
• a semiconductor encapsulant 7 having a thickness of 300 ⁇ m was produced in the same manner as in the semiconductor encapsulant 2 except that acrylate and a radical photopolymerization initiator were not used.
• a semiconductor encapsulant 8 having a thickness of 300 ⁇ m was produced in the same manner as in the semiconductor encapsulant 3 except that acrylate and a radical photopolymerization initiator were not used.
• a semiconductor encapsulant 9 having a thickness of 300 ⁇ m was produced in the same manner as in the semiconductor encapsulant 4 except that acrylate and a radical photopolymerization initiator were not used.
• a semiconductor encapsulant 10 having a thickness of 300 ⁇ m was produced in the same manner as in the semiconductor encapsulant 5 except that acrylate and a radical photopolymerization initiator were not used.
• the semiconductor sealing materials 1 to 10 are put in a DSC apparatus, heated from 25 ° C. to 150 ° C. at a rate of 10 ° C./min, held at 150 ° C. for 10 minutes, and then cooled down at 10 ° C./min to 25 Then, the temperature was raised from 25 ° C. to 230 ° C. at 10 ° C./min, and the reaction heat ⁇ at that time was measured. As a result, it was confirmed that a reaction heat quantity of 1 J / g or more was generated in any of the semiconductor encapsulants.
• the semiconductor sealing material was formed into a sheet shape of 50 mm ⁇ 50 mm square and a thickness of 300 ⁇ m, and a laminate was prepared by sandwiching each of the both sides with a 1 mm thick SUS plate. This laminate was placed on a hot plate, heated at 10 ° C./minute, and further heated at 150 ° C. for 10 minutes to react the thermosetting component. The SUS plate and the PET film were removed, and the obtained sheet-like sealing material having a thickness of 50 mm ⁇ 50 mm and a thickness of 300 ⁇ m was placed on a flat plate, and it was confirmed that there was no corner warping.
• An active energy ray of 1 J / cm 2 was irradiated on one side of the sheet-like encapsulant after thermosetting using a high-pressure mercury lamp in an environment of 25 ° C., and the presence or absence of warp deformation of the sheet-like encapsulant was observed.
• the semiconductor encapsulants 1 and 6 irradiated active energy rays to the semiconductor encapsulant sheet 1a surface and the semiconductor encapsulant sheet 6a surface.
• the warping of the four corners was measured with a metal ruler.
• a heat-cured sheet-shaped semiconductor encapsulant was prepared by heating at 150 ° C. for 10 minutes as described above to react with the thermosetting component, and the reaction heat amount ⁇ upon irradiation with active energy rays by Photo-DSC. (J / g) was measured. Photo-DSC was measured under the following conditions.
• ⁇ Photo-DSC device Measured with a combination of DSC Q100 manufactured by TA Instruments and light source device Qseries PCA using an aluminum sample pan under a nitrogen gas atmosphere at 25 ° C.

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