KR102403104B1 - semiconductor encapsulant - Google Patents

Abstract

Provided is a semiconductor encapsulant capable of reducing warpage of a semiconductor wafer or a semiconductor package, particularly a wafer or package in a fan-out type wafer level package (FO-WLP). A semiconductor encapsulant comprising at least a thermosetting component (A) and an active energy ray-curable component (B), in an environment not exposed to active energy rays, after heat-treating at 150 ° C. for 10 minutes It is characterized in that the calorific value α (J/g) when 1 J/cm ² of ultraviolet light having a wavelength of 351 nm is irradiated at 25° C. is 1≤α (J/g).

Description

semiconductor encapsulant

The present invention relates to a semiconductor encapsulant, and more particularly, to a fan-out type wafer-level package encapsulant in which the arrangement area of the external connection electrode is larger than the flat size of the semiconductor. .

In recent years, the demand for miniaturization is increasing in the field of semiconductor circuits and the like, and in order to meet the demand, semiconductor circuits are sometimes mounted in a chip size package close to the chip size thereof. As one of the means for realizing a chip size package, a package method called a wafer level package (hereinafter, sometimes abbreviated as WLP) has been proposed, which is joined to a wafer level and fragmented. WLP is attracting 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.

However, with the miniaturization and high integration of the semiconductor chip, the number of external connection electrodes (terminals, bumps) of the semiconductor chip tends to increase, and therefore the pitch of the external connection electrodes of the semiconductor chip tends to decrease. . However, it is not always easy to directly mount the semiconductor chip in which bumps are formed at a fine pitch on a circuit board.

In response to the above problems, forming a region of the semiconductor encapsulant so as to contact the outer periphery or a part of the semiconductor chip, and providing a redistribution layer connected to the electrode also in the region of the semiconductor encapsulant to increase the pitch of the bumps has been proposed. Such 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 large compared to the size of the semiconductor chip.

In FO-WLP, a semiconductor chip is embedded with a semiconductor encapsulant. The circuit surface of the semiconductor chip is exposed to the outside, and a boundary between the semiconductor chip and the semiconductor encapsulant is formed. The redistribution layer connected to the electrode of the semiconductor chip is provided also in the area|region of the sealing material for semiconductors embedding a semiconductor chip, and a bump is electrically connected to the electrode of a semiconductor chip through a redistribution layer. The pitch of such bumps can be set large with respect to the electrode pitch of the semiconductor chip.

In addition, it is also conceivable to accommodate not only semiconductor chips but also a plurality of electronic components in one package, or to embed a plurality of semiconductor chips in a semiconductor encapsulant to form one semiconductor component. In such a package, a plurality of electronic components are embedded with a semiconductor encapsulant. The redistribution layer connected to the electrode of an electronic component is provided in the sealing material for semiconductors which embeds a some electronic component, and a bump is electrically connected to the electrode of an electronic component through the redistribution layer. Also in this case, since the size of the bump arrangement area becomes large compared to the size of the semiconductor chip, it can be called FO-WLP.

In such a package, in general, semiconductor chips or electronic components are placed on a support at regular intervals, buried using a semiconductor encapsulant, and after the encapsulant is heat-cured, it is peeled off from the support to form a pseudo wafer. is produced Subsequently, a redistribution layer is formed over the semiconductor sealing material region extended from the semiconductor chip circuit surface of the pseudo wafer. In this way, the bump pitch can be set larger than the electrode pitch of the semiconductor chip.

As described above, since WLP or FO-WLP has a structure in which layers containing different materials are stacked, warpage may occur in semiconductor wafers or semiconductor chips during the package forming process, affecting productivity and quality. Because of this, various countermeasures are employed. For example, Patent Document 1 discloses a semiconductor package produced using a liquid encapsulating resin composition capable of suppressing warpage of a pseudo wafer that causes a decrease in productivity in WLP, and Patent Document 2 suppresses the amount of warpage. A resin sheet for sealing electronic components that can be used is disclosed.

Further, in Patent Documents 3 to 5, it is possible to collectively mold (wafer mold) a wafer even for a large-diameter and thin wafer, and at the same time, it is suitable for WLP having good wafer protection performance that can suppress the warpage of the wafer after molding A resin composition is disclosed. Moreover, in order to suppress the curvature of a wafer, it is tried to adjust the thickness of a support body, and content of an inorganic filler (patent document 6), or to use the sealing material of the laminated structure which has multiple layers (patent document 7, 8).

In addition, by adjusting the hardness of the sealing resin to suppress warpage (Patent Document 9), or paying attention to the storage elastic modulus of the sealing resin, the thermal stress generated from the difference in the thermal expansion coefficient between the semiconductor chip and the encapsulant, which is the cause of the warpage, can be alleviated. It is proposed to use the existing resin encapsulant (patent document 10).

Japanese Patent Laid-Open No. 2012-209453 Japanese Patent Laid-Open No. 2014-36097 Japanese Patent Laid-Open No. 2013-95915 Japanese Patent Laid-Open No. 2015-50447 Japanese Patent Laid-Open No. 2015-50399 Japanese Patent Laid-Open No. 2015-90926 Japanese Patent Laid-Open No. 2015-53341 Japanese Patent Laid-Open No. 2014-197670 Japanese Patent Laid-Open No. 2015-53469 Japanese Patent Laid-Open No. 2015-86359

By the way, in the formation process of the pseudo wafer of FO-WLP, the chip circuit surface is exposed from the sealing material for semiconductors for the subsequent rewiring formation process after that. Therefore, from the difference in the thermal expansion coefficient of a semiconductor chip and the sealing resin which contact|connects the back side of a chip circuit surface, it exists in the tendency for a chip circuit surface to warp convexly. Such convex curvature may cause damage to the pseudo wafer in the subsequent transfer step or defocus of patterning in the formation of the redistribution layer.

On the other hand, in the step of forming the redistribution layer on the circuit surface side of the semiconductor chip, the heat treatment subsequent to the formation and development of the polymer film corresponding to the insulating layer exerts a shrinking stress on the pseudo wafer. It tends to bend concavely toward the chip circuit surface side. Such concave warpage may cause damage to the pseudo wafer in the subsequent transfer step, out of focus in marking on mold resin, etc., and possibly lowering the mounting yield after processing into a semiconductor chip.

As described above, in WLP and FO-WLP, not only the cause of warpage due to the material of the encapsulant, but also the shrinkage stress acting on the package in each processing step, such as each sealing step and the redistribution layer forming step, is different. It is necessary to consider not only the amount but also the direction of the deflection. Therefore, there was a limit in responding to the methods of curvature suppression and warpage correction proposed in the aforementioned prior patent documents.

Accordingly, an object of the present invention is to provide a semiconductor encapsulant capable of reducing warpage of a semiconductor wafer or a semiconductor package, particularly a wafer or package in a fan-out type wafer level package (FO-WLP).

The present inventors, with respect to the above problems, in a semiconductor encapsulant comprising a thermosetting component and an active energy ray-curable component, the order and curing degree of curing each component is adjusted by the amount of heat or active energy ray, It has been found that, by allowing a stress opposite to the shrinkage stress acting on the package in each processing step to act, a semiconductor package without warpage can be realized even when the direction of warpage and the amount of warpage are different in each machining step. And, by controlling the amount of heat generated at the time of photocuring or heat curing of the resin composition constituting the encapsulant, the shrinkage stress acting on the package in each processing step is appropriately generated and warpage can be corrected. More specifically, heat treatment for a semiconductor encapsulant containing a thermosetting component and an active energy ray-curable component is performed at 150° C. for 10 minutes, and the thermosetting reaction has progressed to some extent, but is not completely thermosetted. By preforming a pseudo wafer such as FO-WLP, and then irradiating 1 J/cm ² of ultraviolet light including a wavelength of 351 nm in 25 ° C. to facilitate the active energy ray curing reaction, active energy ray curing It has been discovered that warpage can be corrected by accelerating the cure shrinkage of the component and applying the stress caused by the cure shrinkage to offset the warpage stress inherent in the preformed pseudo-wafer. This invention is based on the related knowledge.

[1] The sealing material for semiconductors according to the first embodiment of the present invention is a sealing material for semiconductors comprising at least a thermosetting component (A) and an active energy ray-curable component (B),

In an environment not exposed to active energy rays, the amount of heat generated when the semiconductor encapsulant after heat treatment at 150° C. for 10 minutes is irradiated with 1 J/cm ² of ultraviolet rays having a wavelength of 351 nm at 25° C. (J/g) It is characterized in that 1≤α (J/g).

[2] In the semiconductor encapsulant according to the second embodiment of the present invention, under an environment not exposed to active energy rays, the semiconductor encapsulant is subjected to a differential scanning calorimeter (DSC) from 25 ° C to 230 ° C at 10 ° C per minute It is the sealing material for semiconductors of [1], wherein the calorific value β (J/g) when the temperature is raised is 1≤β (J/g).

[3] The sealing material for semiconductors according to the third embodiment of the present invention is not exposed to active energy rays, the sealing material for semiconductors after heat treatment at 150 ° C. for 10 minutes in an environment not exposed to active energy rays [1] or [2], in which the calorific value γ (J/g) when heated at 10° C. per minute from 25° C. to 230° C. by a differential scanning calorimeter (DSC) is 1 ≤ γ (J/g) under the environment [1] or [2] of semiconductor encapsulants.

[4] The semiconductor encapsulant according to the fourth embodiment of the present invention is the semiconductor encapsulant according to any one of [1] to [3], in any one of liquid, granular, tablet form, and sheet form.

[5] The semiconductor encapsulant according to the fifth embodiment of the present invention is a sheet-like semiconductor encapsulant laminated in two or more layers, and the material composition of each layer is different from each other, in any one of [1] to [4] It is an encapsulant for semiconductors.

[6] The semiconductor encapsulant according to the sixth embodiment of the present invention is the semiconductor encapsulant according to any one of [1] to [5], which is used in contact with the outer periphery or a part of the semiconductor chip.

[7] The semiconductor encapsulant according to the seventh embodiment of the present invention is the semiconductor encapsulant according to any one of [1] to [5], which is used for a fan-out type wafer level package.

[8] A method for manufacturing a fan-out type wafer level package according to an eighth embodiment of the present invention,

A semiconductor encapsulant comprising at least a thermosetting component (A) and an active energy ray-curable component (B), in an environment not exposed to active energy rays, after heat-treating at 150 ° C. for 10 minutes A step of preparing a semiconductor encapsulant having a calorific value α (J/g) of 1 ≤ α (J/g) when irradiated with 1 J/cm ² of ultraviolet light having a wavelength of 351 nm at 25° C.;

By heating the semiconductor encapsulant, the thermosetting reaction of the thermosetting component (A) in the semiconductor encapsulant has progressed to some extent, but is not completely thermosetted, so that the fan-out type wafer level package is manufactured. a process of forming a wafer; and

By irradiating an active energy ray to the semiconductor encapsulant of the pseudo wafer, curing shrinkage of the active energy ray-curable component (B) in the semiconductor encapsulant is accelerated, and cured to offset the bending stress inherent in the pseudo wafer. The process of correcting warpage by applying stress by contraction

It is a method of manufacturing a fan-out type wafer-level package comprising a.

According to the present invention, after forming a pseudo wafer by heating using a semiconductor encapsulant, when the semiconductor chip circuit surface side is convex by shrinkage after thermal curing of the semiconductor encapsulant, active energy from the semiconductor chip circuit surface side By irradiating a line|wire, the curvature of a pseudo wafer can be corrected by volume contraction of the sealing material for semiconductors which exists between each semiconductor chip. On the other hand, in the case of bending concave toward the chip circuit surface in the rewiring forming step, by irradiating the surface opposite to the above with active energy rays, the bending is prevented by volume contraction of the semiconductor encapsulant on the opposite side to the semiconductor chip circuit surface. can be corrected Moreover, the amount of curvature correction can also be adjusted by adjusting the irradiation amount of an active energy ray.

The sealing material for semiconductors according to the present invention contains a thermosetting component (A) and an active energy ray-curable component (B) as at least two components, and is heated at 150° C. for 10 minutes in an environment not exposed to active energy rays. The amount of heat generated when the semiconductor encapsulant after the treatment is irradiated with 1 J/cm ² of ultraviolet rays having a wavelength of 351 nm in 25° C. is 1≤α (J/g). As in the present invention, the amount of heat generated when active energy ray irradiation is performed after further heat treatment, that is, after the curing reaction of the thermosetting component (A) has progressed to some extent, is 1 J/g or more active energy ray-curable component as described above. By being included, the cure shrinkage of the active energy ray-curable component contained in the sealing material of the side irradiated with an active energy ray can be accelerated|stimulated, and the state of curvature can be changed. The calorific value α is more preferably 2 J/g or more, still more preferably 3 J/g or more, and particularly preferably 4 J/g or more. Although the cure shrinkage of an active energy ray-curable component can be accelerated|stimulated so that calorific value (alpha) is large, an upper limit is about 300 J/g.

In the present specification, "the amount of heat generated when the sealing material for semiconductors after heat treatment at 150° C. for 10 minutes is irradiated with 1 J/cm ² of ultraviolet rays having a wavelength of 351 nm at 25° C.” is the semiconductor sealing material before curing The material composition was heated at 10°C/min from 25°C to 150°C, maintained at 150°C for 10 minutes, and then cooled to 25°C at a temperature drop rate of 10°C/min. The calorific value α (J/g) when measured by irradiating 1 J/cm ² of an active energy ray having a wavelength of 351 nm using a measuring device (a device combining a differential scanning calorimetry device and a light irradiation device) . In addition, as a means for raising the temperature from 25°C to 150°C at 10°C/min and holding it at 150°C for 10 minutes, and a means for cooling it to 25°C at a temperature-fall rate of 10°C/min, a hot plate, DSC, etc. are mentioned. .

In addition, in the present invention, under an environment that is not exposed to active energy rays of the sealing material for semiconductors before curing, the temperature of the sealing material for semiconductors when heated from 25° C. to 230° C. by a differential scanning calorimeter (DSC) at 10° C./min. It is preferable that the calorific value (beta) is 1 J/g or more. By using a semiconductor encapsulant comprising the thermosetting component (A) and the active energy ray-curable component (B) having such a calorific value β, the initial curing reaction proceeds quickly, so when forming a pseudo wafer such as FO-WLP, the It becomes easier to maintain the shape. Since the curing reaction is accelerated when the semiconductor encapsulant is heated from room temperature, the upper limit of the heating value β is not particularly limited. Then, the upper limit of the calorific value is about 300 J/g.

Moreover, in this invention, the sealing material for semiconductors after heat-processing at 150 degreeC for 10 minutes to the sealing material for semiconductors before hardening under the environment which is not exposed to an active energy ray, with a differential scanning calorimeter (DSC) from 25 degreeC to 230 It is preferable that the calorific value γ when the temperature is raised to °C at 10 °C/min is 1 J/g or more. In this way, in the semiconductor encapsulant after the heat treatment, that is, after the curing reaction of the thermosetting component (A) has progressed to some extent, the heating value γ is 1 J/g or more. Since the thermosetting reaction of the semiconductor encapsulant is not completed, the shape can be easily maintained when forming a pseudo wafer such as FO-WLP, and the curing shrinkage by active energy ray irradiation after the heat curing reaction Easy to adjust. Even if the thermosetting component (A) contained in the sealing material for semiconductors is thermosetted, the curing reaction of the active energy ray-curable component (B) does not stop, but when the thermosetting component (A) is completely cured, active energy ray curability Since the molecular motion of component (B) is restricted, it is thought that hardening reaction by an active energy ray becomes difficult to advance. As in the present invention, by making a semiconductor encapsulant having a calorific value γ of 1 J/g or more after heat treatment at 150° C. for 10 minutes, it is possible to easily advance the active energy ray curing reaction after the thermosetting reaction, and to adjust the amount of curing shrinkage make it Although the upper limit of the calorific value γ is not particularly limited, the upper limit of the calorific value is about 300 J/g in consideration of the shape retention of the pseudo wafer by the thermosetting reaction.

The measurement of the heat of reaction accompanying the hardening reaction of the sealing material for semiconductors can be performed using a DSC apparatus. For example, as thermal DSC, TA Instruments DSC Q100 can be used. In addition, the calorific value when measured by irradiating 1 J/cm ² of active energy ray to the semiconductor encapsulant is optical DSC incorporating a device (for example, ultraviolet irradiation unit) that irradiates active energy rays such as ultraviolet rays to the DSC device. It can be measured using the device. As an optical DSC device, for example, an environment not exposed to active energy rays by introducing active energy rays from a light source device PCA for optical DSC having a built-in high-pressure mercury lamp into a DSC module of DSC Q100 manufactured by TA Instruments through a dual light guide. The heat of reaction at the time of the thermosetting reaction under the conditions or the heat of reaction at the time of the photocuring reaction at the time of irradiating a predetermined amount of an active energy ray can be measured quantitatively. Hereinafter, each component which comprises the sealing material for semiconductors by this invention is demonstrated.

<Thermosetting component (A)>

The thermosetting component (A) contained in the semiconductor encapsulant according to the present invention is, for example, a curing reaction is initiated by a thermosetting agent component, etc., and conventionally known materials can be used without particular limitation, but epoxy or oxetane, etc. It is preferable to use cyclic ethers. Cyclic ethers such as epoxy and oxetane shrink in volume due to curing reaction, but as described later, when the thermosetting component (A) is cured, adhesion to the pseudo wafer is improved, so the strength of the pseudo wafer is improved. Together, it is possible to improve the adhesion between the semiconductor chip and the semiconductor encapsulant.

There are solid, semi-solid, and liquid epoxy resins from the shape before the reaction. These can be used individually by 1 type or in combination of 2 or more type. Examples of the solid epoxy resin include an epoxidized product of a condensate of an aromatic aldehyde having a phenolic hydroxyl group with phenols such as EPPN-502H (trisphenol epoxy resin) manufactured by Nippon Kayaku Co., Ltd. (trisphenol-type epoxy resin); Dicyclopentadiene aralkyl type epoxy resins, such as DIC Corporation Epiclon HP-7200H (dicyclopentadiene skeleton containing polyfunctional solid epoxy resin); Novolac-type epoxy resins, such as DIC Corporation Epiclon N660, Epiclon N690, and Nippon Kayaku Co., Ltd. EOCN-104S; Phenol novolak-type epoxy resins, such as DEN-431 by The Dow Chemical Company; Biphenyl type epoxy resins, such as Mitsubishi Chemical Corporation YX-4000; Phosphorus containing epoxy resins, such as TX0712 by the Shin-Nittetsu Sumikin Chemical Co., Ltd.; Tris(2,3-epoxypropyl)isocyanurate, such as TEPIC by Nissan Chemical Industry Co., Ltd., etc. are mentioned.

As a semi-solid epoxy resin, DIC Corporation Epiclon 860, Epiclon 900-IM, Epiclon EXA-4816, Epiclon EXA-4822, Shinnitetsu Sumikin Co., Ltd. Ephototo YD-134, Mitsubishi Chemical bisphenol-A epoxy resins such as jER828, jER834, jER872, jER1001 manufactured by KK, ELA-134 manufactured by Sumitomo Chemical Co., Ltd.; Phenol novolak-type epoxy resins, such as DIC Corporation Epiclon N-740, etc. are mentioned.

Examples of the liquid epoxy resin include 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 An epoxy resin, an alicyclic epoxy resin, etc. are mentioned.

Said thermosetting component (A) can be used individually by 1 type or in combination of 2 or more type.

It is preferable that the sealing material for semiconductors by this invention contains the hardening|curing agent component which can harden said thermosetting component (A). As a thermosetting agent component, the thing which can make a thermosetting component (A) ionic ring-opening polymerization or polyaddition polymerization reaction by heat can be used.

As a 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. Especially, it is preferable to use imidazole from a viewpoint, such as adhesive force with a pseudo wafer, storage stability, moisture-resistance reliability, etc.

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 (manufactured by Shikoku Chemical Co., Ltd., product name) and the like, and compounds obtained by adding these imidazoles to an epoxy resin are mentioned. In addition, microencapsulation by coating these curing agents with a polyurethane-based or polyester-based polymer material or the like is preferable because the pot life is prolonged. These can also be used individually or in mixture of 2 or more types.

As a compounding quantity of imidazole, it is preferable to mix|blend 0.1-10 mass % with respect to a thermosetting component (A), More preferably, it is 0.5-10 mass %, More preferably, it is 1-10 mass %. By mix|blending the imidazole which is a hardening|curing agent component which can carry out ionic ring-opening polymerization in the said range, sclerosis|hardenability and storage stability can be made compatible.

As benzylsulfonium salt, Sanshin Chemical Co., 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 can also be used individually or in mixture of 2 or more types.

As a compounding quantity of a benzylsulfonium salt, it is preferable to mix|blend 0.1-10 mass % with respect to a thermosetting component (A), More preferably, it is 0.5-10 mass %, More preferably, it is 1-10 mass %. By mix|blending the benzylsulfonium salt which is a hardening|curing agent component which can carry out ionic ring-opening polymerization in the said range, sclerosis|hardenability and storage stability can be made compatible.

Moreover, as a Lewis acid-amine complex, well-known things, such as a BF ₃ -triethylamine complex and a BF ₃ -pyridine complex, can be used.

As a compounding quantity of thermosetting agent components, such as a Lewis acid-amine complex, it is preferable to mix|blend 0.1-10 mass % with respect to the thermosetting component (A), More preferably, it is 0.5-10 mass %, More preferably, 1-10 mass %to be. By mix|blending in the said range, such as the Lewis acid-amine complex which is a hardening|curing agent component which can be ionic ring-opening polymerization, sclerosis|hardenability and storage stability can be made compatible.

You may harden a thermosetting component (A) by polyaddition polymerization reaction. As a curing agent component capable of subjecting the thermosetting component (A) to a polyaddition polymerization reaction, acid anhydrides, carboxylic acids, amines, phenols, hydrazides, polymercaptans and the like can be used. Especially, it is preferable to use carboxylic acids, amines, and phenols from viewpoints, such as adhesive force with a pseudo wafer, storage stability, moisture resistance reliability, etc.

Examples of the acid anhydrides include methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, hexahydrophthalic anhydride, methylhymic anhydride, pyromellitic dianhydride, benzophenonetetracarboxylic dianhydride, and 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 can also be used individually or in mixture of 2 or more types.

As the compounding amount of the acid anhydride, for example, when the thermosetting component (A) is an epoxy compound, the ratio of the number of curing functional groups (epoxy groups) to the number of carboxylic acids generated from the acid anhydride group (curing functional groups of the thermosetting component (A)) It is preferable to mix|blend so that the number / number of carboxylic acids) may be 0.2-20, More preferably, it is 0.4-16. By making the compounding quantity of an acid anhydride into the said range, hardening reaction can advance effectively. On the other hand, 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 and the number of carboxylic acids generated from the acid anhydride group (number of curing functional groups in the thermosetting component (A)/carbox) number of acids) can be calculated in the same way.

Examples of the carboxylic acids include adipic acid, maleic acid, methyltetrahydrophthalic acid, methylhexahydrophthalic acid, hexahydrophthalic acid, methylhymic acid, pyromellitic acid, benzophenonetetracarboxylic acid, and 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-dicarboxyl An acid, a resin having a carboxyl group in the side chain, or the like can be used.

As the compounding amount of the carboxylic acid, when the thermosetting component (A) is an epoxy compound, the ratio of the number of curing functional groups (epoxy groups) to the number of carboxyl groups (the number of curing functional groups in the thermosetting component (A)/number of carboxyl groups) is 0.2 to It is preferable to mix|blend so that it may become 20, More preferably, it is 0.4-16. By making the compounding quantity of carboxylic acid into the said range, hardening reaction can advance effectively. On the other hand, 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)/number of carboxyl groups) can

Although it will not specifically limit as long as it is a compound which has at least one primary or secondary amino group in a molecule|numerator as amines, From a viewpoint of storage stability and heat resistance of hardened|cured material, aromatic amines are preferable. Examples of the aromatic amines include 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, 2,2-bis(4-aminophenyl)-hexafluoropropane, 2,4-diaminotoluene, 1,4-dia Minobenzene, 1,3-diaminobenzene, diethyltoluenediamine, dimethyltoluenediamine, anilines, alkylated anilines, N-alkylated anilines, etc. can be used. These can also be used individually or in mixture of 2 or more types.

As the blending amount of the amines, when the thermosetting component (A) is an epoxy compound, it is preferable to blend so that 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 to 20, , more preferably 0.4 to 16. By making the compounding quantity of amines into the said range, hardening reaction can advance effectively. On the other hand, when the thermosetting component (A) is other than an epoxy group, from the ratio of the number of curing functional groups involved in the curing reaction and the number of active hydrogens (the number of curing functional groups of the thermosetting component (A)/number of active hydrogens), the same can be calculated.

As phenols, phenol novolak resin, alkylphenol novolak resin, bisphenol A novolak resin, dicyclopentadiene type phenol resin, Xylok type phenol resin, terpene modified phenol resin, cresol/naphthol resin, polyvinyl phenols , phenol/naphthol resin, α-naphthol skeleton-containing phenol resin, triazine-containing cresol novolak 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.

As the compounding amount of phenols, when the thermosetting component (A) is an epoxy compound, the ratio of the number of curing functional groups (epoxy groups) to the number of phenolic hydroxyl groups (number of epoxy groups/number of phenolic hydroxyl groups) is 0.2 to 20. It is preferable, More preferably, it is 0.4-16. By making the compounding quantity of phenols into the said range, hardening reaction can advance effectively. On the other hand, when the thermosetting component (A) is other than an epoxy group, from the ratio of the number of curing functional groups involved in the curing reaction and the number of phenolic hydroxyl groups (the number of curing functional groups in the thermosetting component (A) / the number of phenolic hydroxyl groups) can be calculated in the same way.

In addition to the above, as a curing agent component capable of polymerizing the thermosetting component (A) by polyaddition polymerization, a cyanate ester resin or an active ester resin can also be used. Cyanate ester resin is a compound which has two or more cyanate ester groups (-OCN) in 1 molecule. Any conventionally known cyanate ester resin can be used. As 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 cyanide Nate ester resin and bisphenol S type|mold cyanate ester resin are mentioned. Moreover, the prepolymer by which a part was triazined may be sufficient.

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 of a carboxylic acid compound and a hydroxy compound. Especially, the active ester compound obtained using a phenol compound or a naphthol compound as a hydroxy compound is preferable. Examples of the phenolic compound or naphthol compound include hydroquinone, resorcin, bisphenol A, bisphenol F, bisphenol S, phenolphthalline, 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, trihydroxybenzo and phenone, tetrahydroxybenzophenone, phloroglucin, benzenetriol, dicyclopentadienyldiphenol, and phenol novolac.

When using carboxylic acids, acid anhydrides, amines, phenols, cyanate ester resins, and active ester resins as a curing agent component capable of polymerizing the thermosetting component (A) by polyaddition polymerization, a curing accelerator is used together You can do it. The above imidazoles can be used as the curing accelerator. Further, guanamines such as acetoguanamine and benzoguanamine; Organic acid salts and/or epoxides of polyamines such as diaminodiphenylmethane, m-phenylenediamine, m-xylenediamine, diaminodiphenylsulfone, dicyandiamide, urea, urea derivatives, melamine, and polybasic hydrazide. duct; amine complexes of boron trifluoride; triazine derivatives such as ethyldiamino-S-triazine, 2,4-diamino-S-triazine, and 2,4-diamino-6-xylyl-S-triazine; organic phosphines such as tributylphosphine, triphenylphosphine, and tris-2-cyanoethylphosphine; phosphonium salts such as tri-n-butyl (2,5-dihydroxyphenyl) phosphonium bromide and hexadecyl tributyl phosphonium chloride; quaternary ammonium salts such as benzyltrimethylammonium chloride and phenyltributylammonium chloride; The said polybasic acid anhydride is mentioned. These 1 type can be used individually or in mixture of 2 or more types.

Although the curing accelerator component is not essential, especially when it is desired to accelerate the curing reaction, it is preferable with respect to 100 parts by mass of the curing agent component capable of polymerizing the thermosetting component (A) by the polyaddition polymerization reaction with the above-described heat. Preferably, it can be used in the range of 0.01-20 mass parts. When using a metal catalyst as a hardening accelerator component, 10-550 ppm is preferable and, as for the content, in conversion of a metal with respect to 100 mass parts of sclerosing|hardenable components, 25-200 ppm is preferable.

<Active energy ray-curable component (B)>

The sealing material for semiconductors by this invention contains an active energy ray-curable component (B). An active energy ray-curable component means the component in which hardening reaction advances by irradiating an active energy ray. In addition, in this specification, an active energy ray means the electromagnetic wave which has the energy required for a hardening|curing agent component to excite from a ground state to a transition state, For example, an electron beam, an ultraviolet-ray, visible light, etc. are meant. As such an active energy ray-curable component (B), although it can select from well-known materials, For example, a sclerosing|hardenable component which can be hardened|cured by radical addition polymerization reaction can be used preferably. In the present specification, radical addition polymerization means a reaction in which polymerization is initiated by radicals, and an unsaturated compound having a double bond or a triple bond is added to form a polymer. As a curable component which can be hardened|cured by such radical addition polymerization reaction, the compound which has one or more ethylenically unsaturated groups in a molecule|numerator is preferable.

In the sealing material for semiconductors, when a thermosetting component (A) and an active energy ray-curable component (B) as described above are included to cure the sealing material for semiconductors, a thermosetting component (A) and an active energy ray-curable component (B) can each be cured separately. Therefore, when manufacturing a pseudo wafer using the semiconductor encapsulant, the amount of irradiation of the active energy ray is adjusted according to the bending direction and amount of the wafer, and the contractile stress of the same degree as the bending stress inherent in the pseudo wafer, the active energy It can be generated on the irradiated side of the line. As a result, even in the case of manufacturing FO-WLPs having different materials, thicknesses, and patterns of the redistribution layer, FO-WLPs with reduced warpage can be obtained. From the viewpoint of controlling the amount of shrinkage of the sealing material for semiconductors according to the amount of curvature, it is preferable that the active energy ray-curable component (B) uses a thing whose volume shrinks by radical addition polymerization reaction. In addition, as the active energy ray-curable component (B), all of the curing reaction of the active energy ray-curable component does not proceed by heat energy or heat of curing reaction generated when curing the thermosetting component (A). it is preferable

Specific examples of the radical addition polymerization reactive component include, for example, commonly known polyester (meth) acrylate, polyether (meth) acrylate, urethane (meth) acrylate, carbonate (meth) acrylate, epoxy (meth) ) acrylates and the like. 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; acrylamides such as N,N-dimethylacrylamide, N-methylolacrylamide, and N,N-dimethylaminopropylacrylamide; aminoalkyl acrylates such as N,N-dimethylaminoethyl acrylate and N,N-dimethylaminopropyl acrylate; Polyhydric alcohols, such as hexanediol, trimethylolpropane, pentaerythritol, dipentaerythritol, and tris-hydroxyethyl isocyanurate, or these ethylene oxide adducts, propylene oxide adducts, or ε-caprolactone adducts, etc. of polyvalent acrylates; polyhydric acrylates such as phenoxyacrylate, bisphenol A diacrylate, and ethylene oxide adducts or propylene oxide adducts of these phenols; polyvalent acrylates of glycidyl ethers such as glycerin diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, and triglycidyl isocyanurate; Not limited to the above, acrylates and melamine acrylates obtained by directly acrylated polyols such as polyether polyols, polycarbonate diols, hydroxyl-terminated polybutadiene, and polyester polyols or urethane acrylates through diisocyanate, and At least any 1 type of each methacrylate corresponding to the said acrylate, etc. are mentioned. Among the above, suitable acrylic equivalent is 500 or less, More preferably, it is 300 or less, It is preferable that it is especially less than 200.

Moreover, you may use the following maleimide compounds as an active-energy-ray-curable component (B) which can be hardened|cured by radical addition polymerization reaction. For example, N-methylmaleimide, N-ethylmaleimide, N-n-propylmaleimide, N-isopropylmaleimide, N-n-butylmaleimide, N-isobutylmaleimide, N-sec-butylmaleimide, N-tert-butylmaleimide, N-n-hexylmaleimide, N-n-dodecylmaleimide, N-allylmaleimide, N-benzylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide, N-nitrophenyl Maleimide, N-hydroxyphenylmaleimide, N-methoxyphenylmaleimide, N-ethoxyphenylmaleimide, N-monochlorophenylmaleimide, N-dichlorophenylmaleimide, N-monomethylphenylmaleimide, N -Dimethylphenylmaleimide, N-ethylphenylmaleimide, ethylenebismaleimide, N,N'-m-phenylenebismaleimide, N,N'-p-phenylenebismaleimide, N,N'-hexa Methylenebismaleimide, N,N'-p,p'-diphenyldimethylsilylbismaleimide, N,N'-p,p'-diphenylmethanebismaleimide, N,N'-p,p'- Diphenyletherbismaleimide, N,N'-p,p'-diphenylthioetherbismaleimide, N,N'-diphenylsulfonebismaleimide, N,N'-dicyclohexylmethanebismaleimide; N,N'-m-xylylenebismaleimide, N,N'-p,p'-benzophenonebismaleimide, N,N'-(3,3'-dichloro-p,p'-biphenyl Ren) bismaleimide etc. are mentioned. When a maleimide compound is used as the active energy ray-curable component (B), a photoradical initiator described later may be used, and even if not used, the amount of warpage of the semiconductor encapsulant may be reduced by performing a photodimerization reaction by irradiation with active energy ray. have.

As an active energy ray-curable component (B) which can be hardened|cured by radical addition polymerization reaction other than the above, you may use the compound similar to the following (1)-(11).

(1) An unsaturated group-containing obtained by reacting a reaction product obtained by reacting a compound having a plurality of phenolic hydroxyl groups in one molecule with an alkylene oxide with an unsaturated group-containing monocarboxylic acid, and reacting a polybasic acid anhydride with the reaction product obtained polymer,

(2) an acryl-containing polymer obtained by reacting (meth)acrylic acid with a bifunctional or higher polyfunctional epoxy resin to add a dibasic acid anhydride to a hydroxyl group present in a side chain;

(3) an acryl-containing polymer obtained by reacting (meth)acrylic acid with a polyfunctional epoxy resin in which the hydroxyl group of the bifunctional epoxy resin is further epoxidized with epichlorohydrin, and adding dibasic acid anhydride to the generated hydroxyl group;

(4) An unsaturated group-containing polymer obtained by reacting a reaction product obtained by reacting a compound having a plurality of phenolic hydroxyl groups with a cyclic carbonate compound in one molecule, and reacting a polybasic acid anhydride with a reaction product obtained by reacting an unsaturated group-containing monocarboxylic acid ,

(5) acryl-containing urethane resin by polyaddition reaction of diisocyanate and (meth)acrylate of a bifunctional epoxy resin or partial 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) During the synthesis of a resin by polyaddition reaction of diisocyanate, a carboxyl group-containing dialcohol compound and a diol compound, a compound having one hydroxyl group and one or more (meth)acryloyl group in the molecule is added to the terminal ( meth) acrylated acrylic-containing urethane resin;

(8) During the synthesis of a resin by polyaddition reaction of diisocyanate, 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 to the 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 group in the molecule during the synthesis of the resin of the above (5) and (meth)acrylated terminal;

(10) an acryl-containing urethane resin obtained by adding a compound having one isocyanate group and one or more (meth)acryloyl groups in a molecule during the synthesis of the resin of (5) above and (meth)acrylated terminals; and

(11) An acrylic-containing polymer obtained by adding a compound having one epoxy group and one or more (meth)acryloyl group in one molecule to the resin of (1) to (10) above

etc. can be used individually or in combination of 2 or more types, or in combination with the monomer which has one or more ethylenically unsaturated groups in the above-mentioned molecule|numerator.

The above-described active energy ray-curable component (B) has a calorific value of substantially 0 J/min when heated from 25° C. to 230° C. by a differential scanning calorimeter (DSC) at 10° C./min in an environment not exposed to active energy rays. It is preferable to use g. By using the active energy ray-curable component (B) to which the active energy ray curing reaction does not proceed when heat treatment is performed in order to advance the thermosetting reaction of the thermosetting component (A), further curing shrinkage due to active energy ray irradiation It becomes easy to perform adjustment (that is, adjustment of the amount of warpage).

It is preferable that the sealing material for semiconductors by this invention contains the hardening|curing agent component (henceforth a photocuring agent component) which can harden said active-energy-ray-curable component (B). As a photocuring agent component, what can radically polymerize an active energy ray-curable component (B) with an active energy ray may be sufficient.

Moreover, as a photocuring agent component, bis-(2,6-dichlorobenzoyl)phenylphosphine oxide, bis-(2,6-dichlorobenzoyl)-2,5-dimethylphenylphosphine oxide, bis-(2), for example ,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 (Omnirad (Omnirad) 819 manufactured by IGM Resins), 2,6-dimethoxybenzoyldiphenylphosphine oxide, 2,6-dichlorobenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoylphenylphosphine methyl ester, 2-methylbenzoyldiphenylphosphine oxide, pivaloylphenylphosphinic acid isopropyl ester, 2,4,6-trimethylbenzoyldiphenylphosphine oxide (BASF) acylphosphine oxides such as IRGACURE TPO (manufactured by Japan Corporation); 1-Hydroxy-cyclohexylphenylketone, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1 -{4-[4-(2-Hydroxy-2-methyl-propionyl)-benzyl]phenyl}-2-methyl-propan-1-one, 2-hydroxy-2-methyl-1-phenylpropane- hydroxyacetophenones such as 1-one; benzoins such as benzoin, benzyl, benzoin methyl ether, benzoin ethyl ether, benzoin n-propyl ether, benzoin isopropyl ether, and benzoin n-butyl ether; benzoin alkyl ethers; benzophenones such as benzophenone, p-methylbenzophenone, Michler ketone, methylbenzophenone, 4,4'-dichlorobenzophenone, and 4,4'-bisdiethylaminobenzophenone; Acetophenone, 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- acetophenones such as (dimethylamino)-2-[(4-methylphenyl)methyl)-1-[4-(4-morpholinyl)phenyl]-1-butanone and N,N-dimethylaminoacetophenone; Thioxanthone, 2-ethyl thioxanthone, 2-isopropyl thioxanthone, 2,4-dimethyl thioxanthone, 2,4-diethyl thioxanthone, 2-chlorothioxanthone, 2,4-di thioxanthone such as isopropyl thioxanthone; anthraquinones such as anthraquinone, chloroanthraquinone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 1-chloroanthraquinone, 2-amylanthraquinone, and 2-aminoanthraquinone; ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; benzoic acid esters such as ethyl-4-dimethylaminobenzoate, 2-(dimethylamino)ethylbenzoate, and p-dimethylbenzoic acid ethyl ester; 1,2-octanedione,1-[4-(phenylthio)-,2-(O-benzoyloxime)], ethanone,1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbox oxime esters such as bazol-3-yl]-,1-(O-acetyloxime); Bis(η5-2,4-cyclopentadien-1-yl)-bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium, bis(cyclopentadienyl)- titanocenes such as bis[2,6-difluoro-3-(2-(1-phyll-1-yl)ethyl)phenyl]titanium; phenyldisulfide 2-nitrofluorene, butyroin, anisoinethyl ether, azobisisobutyronitrile, tetramethylthiuram disulfide, etc. are mentioned. The photocuring agent component which can superpose|polymerize said active energy ray-curable component (B) by radical addition polymerization reaction may be used individually by 1 type, and may be used in combination of 2 or more type.

In addition, the photocuring agent component is preferably selected from substances that are difficult to evaporate or decompose by heating. Specifically, the vapor pressure of the photocuring agent component at 25°C is preferably 1×10 ^-3 Pa or less, more preferably 5×10 ^-4 Pa or less, and still more preferably 1×10 ^-4 Pa or less. Examples of the photocuring agent component having a vapor pressure of 1×10 ⁻⁴ Pa or less at 25° C. include Omnirad (Omnirad) 819 (manufactured by IGM Resins), IRGACURE 379, IRGACURE OXE01 (manufactured by BASF Japan Co., Ltd.). Moreover, 150 degreeC or more is preferable, as for the thermal decomposition temperature of a photocuring agent component, 155 degreeC or more is more preferable, and 160 degreeC or more is still more preferable. By using the photocuring agent component with a high thermal decomposition temperature, it can suppress effectively that the photocuring agent component deactivates at the time of the thermal reaction of the sealing material for semiconductors. As such a photocuring agent component, Omnirad (Omnirad) 819 (made by IGM Resins), IRGACURE 379, IRGACURE OXE01 (made by BASF Japan Corporation) etc. are mentioned, for example.

Among these, oxime esters (hereinafter referred to as “oxime ester-based photopolymerization initiators”), α-aminoacetophenones which are one of acetophenones (hereinafter referred to as “α-aminoacetophenone-based photopolymerization initiators”), and acyl It is preferable to use at least one type of photoinitiator selected from the group consisting of phosphine oxides (hereinafter, referred to as "acyl phosphine oxide-based photoinitiators"). As a commercial item as an oxime ester type|system|group photoinitiator, BASF Japan Corporation CGI-325, IRGACURE OXE01, IRGACURE OXE02, ADEKA Corporation N-1919, etc. are mentioned. In addition, the photoinitiator having two oxime ester groups in the molecule is also difficult to evaporate or decompose by heating, and since it can generate a plurality of radicals having higher reactivity, warpage correction can be performed more efficiently. can be used appropriately. As a specific example of such a photoinitiator, the oxime ester compound which has a carbazole structure represented by the following general formula is mentioned.

In the formula, X is 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 (alkyl group having 1 to 17 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an amino group, an alkoxy group having 1 to 8 carbon atoms An alkylamino group having an alkyl group or substituted with 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 or dialkylamino group having an alkyl group having 1 to 8 carbon atoms) represents a hydrogen atom, each of Y and Z is an alkyl group having 1 to 17 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a halogen group, a phenyl group, a phenyl group (an alkyl group having 1 to 17 carbon atoms, 1 to 8 carbon atoms). of an alkoxy group, an amino group, an alkylamino group having an alkyl group of 1 to 8 carbon atoms, or a dialkylamino group of substituted by an alkylamino group or dialkylamino group having an alkyl group of 8), an anthryl group, a pyridyl group, a benzofuryl group, or a benzothienyl group, and Ar is 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 preferably as an oxime ester compound having a carbazole structure represented by the above general formula, in the formula, X and Y are each a methyl group or an ethyl group, Z is methyl or phenyl, n is 0, Ar is phenylene, It is an oxime ester compound which is naphthylene, thiophene or thienylene.

It is preferable that the compounding quantity of an oxime ester system photoinitiator shall be 0.01-5 mass parts with respect to 100 mass parts of polyether compounds containing an ethylenically unsaturated group in a molecule|numerator.

Specific examples of the α-aminoacetophenone-based photopolymerization initiator 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, etc. are mentioned. As a commercial item, IGM Resins company Omnirad 907, BASF Japan Corporation IRGACURE 369, IRGACURE 379, etc. are mentioned.

As an acylphosphine oxide type|system|group photoinitiator, the said compound is mentioned. As a commercial item, IRGACURE TPO by BASF Japan Corporation, Omnirad 819 by IGM Resins, etc. are mentioned.

When an oxime ester-based photoinitiator is used as the photocuring agent component, sufficient sensitivity can be obtained even with a small amount, and since volatilization of the photoinitiator is small, contamination of equipment such as a drying furnace can be reduced.

In addition, the use of an acylphosphine oxide-based photopolymerization initiator is preferable from the viewpoint that more effective warpage correction force can be expressed even in a thick semiconductor encapsulant in order to improve deep-part curability at the time of photoreaction.

Moreover, you may use what is marketed as a photocuring agent component, for example, IRGACURE 389 by BASF Japan Corporation, and IRGACURE 784 can be used suitably.

As described above, in the active energy ray-curable component (B), part or all of the curing reaction of the active energy ray-curable component does not proceed by heat energy or heat of curing reaction generated when curing the thermosetting component (A). It is preferable to use Therefore, it is preferable that the photocuring agent component also does not substantially activate (generate a radical) by thermal energy or the heat of hardening reaction which generate|occur|produces. As such a photocuring agent component, an oxime compound such as Irgacure IRGACURE 379, IRGACURE 784, IRGACURE OXE01 manufactured by BASF Japan Co., Ltd., Omnirad 819 manufactured by IGM Resins, carbazole represented by the general formula The oxime ester compound etc. which have a structure are mentioned.

Preferably the compounding quantity of a photocuring agent component is 1-25 mass parts with respect to 100 mass parts of active energy ray-curable components (B), More preferably, it is 5-20 mass parts, More preferably, it is 10-20 mass parts. It is preferable that the compounding quantity of a photoinitiator in the case of using especially an oxime ester type photoinitiator sets it as 0.01-5 mass parts with respect to 100 mass parts of polyether compounds containing an ethylenically unsaturated group in a molecule|numerator.

In this invention, when a photocuring agent component is contained as a hardening|curing agent component in the sealing material for semiconductors, a photoinitiation adjuvant or a sensitizer may be contained further. As a photoinitiation adjuvant and a sensitizer, a benzoin compound, an acetophenone compound, an anthraquinone compound, a thioxanthone compound, a ketal compound, a benzophenone compound, a tertiary amine compound, a xanthone compound, etc. are mentioned. A photoinitiation adjuvant and a sensitizer may be used individually by 1 type, and may be used as a mixture of 2 or more types. Among the above, a thioxanthone compound and a tertiary amine compound are preferable. It is preferable from the point of deep-part sclerosis|hardenability of the sealing material for semiconductors that especially a thioxanthone compound is contained. Especially, it is preferable to contain thioxanthone compounds, such as 2, 4- dimethyl thioxanthone, 2, 4- diethyl thioxanthone, 2-chloro thioxanthone, and 2, 4- diisopropyl thioxanthone. do.

The encapsulant for semiconductor according to the present invention may be in any form of liquid, granular, tablet or sheet, but when processed into a film (or sheet) form, the film (or sheet) shape is easily maintained. You may also contain a polymer component (C). Examples of the film property imparting polymer component (C) include a thermoplastic polyhydroxypolyether resin, a phenoxy resin that is a condensate of epichlorohydrin and various difunctional phenol compounds, or a hydroxyl group of a hydroxyether moiety present in its skeleton with various acids. and phenoxy resins, polyvinyl acetal resins, polyamide resins, polyamideimide resins, and block copolymers esterified using anhydride or acid chloride. These polymers may be used individually by 1 type or in combination of 2 or more type. In order to maintain the film (or sheet) shape, the weight average molecular weight (Mw) of these polymers is usually 2×10 ⁴ or more, preferably 2×10 ⁴ to 3×10 ⁶ .

In addition, in this specification, the value of a weight average molecular weight (Mw) can be measured on the following measuring apparatus and measurement conditions by the gel permeation chromatography (GPC) method (polystyrene standard).

Measuring device: "Waters 2695" made by Waters

Detector: "Waters 2414" made by Waters, 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

Measuring conditions:

Column temperature: 40°C

RI detector set temperature: 35℃

Developing solvent: tetrahydrofuran

Flow rate: 0.5ml/min

Sample volume: 10 μl

Sample concentration: 0.7wt%

Polyvinyl acetal resin is obtained by acetalizing polyvinyl alcohol resin with an aldehyde, for example. It does not specifically limit as said aldehyde, For example, formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde etc. are mentioned.

Specific examples of the phenoxy resin include FX280 and FX293 manufactured by Shinnitetsu Sumikin, YX8100, YL6954, and YL6974 manufactured by Mitsubishi Chemical.

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

As polyamideimide resin, Hitachi Chemical Co., Ltd. KS9000 series etc. are mentioned.

When the thermoplastic polyhydroxypolyether resin has a fluorene skeleton, it has a high glass transition point and excellent heat resistance, and thus maintains its glass transition point while maintaining a low coefficient of thermal expansion by a semi-solid or solid epoxy resin, The resulting cured film has both a low coefficient of thermal expansion and a high glass transition point in a good balance. Moreover, since the thermoplastic polyhydroxypolyether resin has a hydroxyl group, it shows favorable adhesiveness with respect to a pseudo wafer.

The film property imparting polymer component (C) may be one obtained by block copolymerization of the monomers constituting the above-described component. The block copolymer is a copolymer of a molecular structure in which two or more types of polymers having different properties are linked by a covalent bond to form a long chain. The block copolymer is preferably an X-Y-X type block copolymer or an X-Y-X' type block copolymer. Among the X-Y-X type and X-Y-X' type block copolymers, the central Y is a soft block and the glass transition temperature (Tg) is low, and both outer X or X' are hard blocks and the glass transition temperature (Tg) is the center It is preferable to be comprised by the polymer unit higher than the Y block. The glass transition temperature (Tg) is measured by differential scanning calorimetry (DSC).

In addition, among the X-Y-X type and X-Y-X' type block copolymer, X or X' contains a polymer unit having a Tg of 50° C. or higher, and the glass transition temperature (Tg) of Y is a polymer having a Tg of X or X′ or less. Block copolymers comprising units are more preferred. In addition, among the X-Y-X type and X-Y-X' type block copolymer, it is preferable that X or X' has high compatibility with the thermosetting component (A) or the active energy ray-curable component (B), and Y is the thermosetting component (A) ) or a low compatibility with an active energy ray-curable component (B) is preferable. As described above, it is thought that a specific structure in the matrix is easily exhibited by using a block copolymer in which the blocks at both ends are compatible with the matrix (curable component) and the central block is incompatible with the matrix (curable component).

Among the aforementioned various film properties imparting polymer components (C), phenoxy resins, polyvinyl acetal resins, thermoplastic polyhydroxypolyether resins having a fluorene skeleton, and block copolymers are preferable.

When the film property imparting polymer component (C) is added to the semiconductor encapsulant of the present invention, the ratio of the film property imparting polymer component (C) to the total components constituting the semiconductor encapsulant is not particularly limited, When the sum total of all components is 100 mass parts, it is preferable that it is 2-40 mass parts, More preferably, it is 5-35 mass parts.

The inorganic filler component (D) may be contained in the sealing material for semiconductors by this invention. By containing the inorganic filler component (D), for example, FO-WLP can be easily cut into pieces (dicing). In addition, by laser marking the protective film, the inorganic filler component (D) is exposed to the portion cut out by the laser beam, and the reflected light is diffused, so that a color close to white is shown. Thereby, when the curvature corrector for FO-WLP contains the coloring agent component (E) mentioned later, a contrast difference is obtained in a laser marking part and another part, and there exists an effect that a marking (printing) becomes clear.

As the inorganic filler component (D), in an environment not exposed to active energy rays, the semiconductor encapsulant after heat treatment at 150 ° C. for 10 minutes is irradiated with 1 J/cm ² of ultraviolet rays having a wavelength of 351 nm at 25 ° C. If the calorific value α (J/g) of is in the range where 1≤α (J/g), conventionally known ones can be used without limitation, for example, silica, alumina, talc, aluminum hydroxide, calcium carbonate, Neuburg Silica, glass powder, clay, magnesium carbonate, natural mica, synthetic mica, barium sulfate, barium titanate, hydrotalcite, mineral wool, aluminum silicate, calcium silicate, zinc oxide, titanium oxide, iron oxide, silicon carbide, boron nitride, etc. powder, beads obtained by spheroidizing them, single crystal fiber, glass fiber, and the like, may be used alone or in combination of two or more. Among these, silica, alumina, and titanium oxide are preferable.

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 addition, let the average particle diameter in this specification measure the major axis diameter of 20 inorganic fillers (D) randomly selected with an electron microscope, and let it be the number average particle diameter computed as the arithmetic mean value.

When the content of the inorganic filler component (D) is 100 parts by mass of the curable components (A) and (B) contained in the semiconductor encapsulant, the curing agent component of both, and the film-providing polymer component (C) , To this, Preferably it is 10-400 mass parts, More preferably, it is 20-350 mass parts, Especially preferably, it is 30-300 mass parts. When the content of the inorganic filler component (D) is within 400 parts by mass, in an environment not exposed to active energy rays, the semiconductor encapsulant after heat treatment at 150° C. for 10 minutes is ultraviolet light containing a wavelength of 351 nm in 25° C. It is preferable because the calorific value α (J/g) when irradiated with 1 J/cm ² tends to be 1≤α (J/g).

The coloring agent component (E) may be contained in the sealing material for semiconductors by this invention. When the semiconductor chip which has arrange|positioned the sealing material for semiconductors is assembled into an apparatus by containing a coloring agent component (E), the malfunction of the semiconductor device by infrared rays etc. which generate|occur|produce from a peripheral device can be prevented. Moreover, when it engraves on the sealing material for semiconductors by means, such as laser marking, it becomes easy to recognize marks, such as a character and a symbol. That is, in a semiconductor chip with a semiconductor encapsulant formed thereon, the product number and the like are usually printed on the surface of the protective film by a laser marking method (a method of printing by scraping the protective film surface with laser light), but the semiconductor encapsulant contains a colorant By doing so, the contrast difference between the portion cut off by the laser beam of the protective film and the portion that is not is sufficiently obtained, and visibility is improved.

As a colorant component (E), although an organic or inorganic pigment and dye can be used individually by 1 type or in combination of 2 or more types, Among these, a black pigment is preferable at the point of electromagnetic wave and infrared rays shielding property. As a black pigment, although carbon black, perylene black, iron oxide, manganese dioxide, aniline black, activated carbon, etc. are used, it is not limited to these. Carbon black is particularly preferable from the viewpoint of preventing malfunction of the semiconductor device. Moreover, instead of carbon black, pigments or dyes, such as red, blue, green, and yellow, can also be mixed and it can also be set as black or the black type color close|similar to it.

Examples of the red colorant include monoazo, disazo, azolake, benzimidazolone, perylene, diketopyrrolopyrrole, condensed azo, anthraquinone, quinacridone, and the like. thing can be heard 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, 193, 210, 245, 253, 258, 266, 267, 268, 269 monoazo red colorants, pigment red 37, 38, 41 disazo red Colorant, 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 Monoazolake red colorants such as :1, 58:4, 63:1, 63:2, 64:1, 68, Pigment Red 171, Pigment Red 175, Pigment Red 176, Pigment Red 185, Pigment Benzimidazolone-based red colorants such as Ment Red 208, Solvent Red 135, Solvent Red 179, Pigment Red 123, Pigment Red 149, Pigment Red 166, Pigment Red 178, Pigment Red 179, Perylene-based red colorants such as Pigment Red 190, Pigment Red 194, and Pigment Red 224, Diketopyrrolo such as Pigment Red 254, Pigment Red 255, Pigment Red 264, Pigment Red 270, and Pigment Red 272 Condensed azo red colorants such as pyrrole red colorants, Pigment Red 220, Pigment Red 144, Pigment Red 166, Pigment Red 214, Pigment Red 220, Pigment Red 221, and Pigment Red 242, Pigment Red Anthraquinone-based red colorants such as 168, Pigment Red 177, Pigment Red 216, Solvent Red 149, Solvent Red 150, Solvent Red 52, and Solvent Red 207, Pigment Red 122, Pigment Red 202, Pigment Red 206, and quinacridone-based red colorants such as Pigment Red 207 and Pigment Red 209.

As the blue colorant, there are phthalocyanine-based, anthraquinone-based, and the like, and pigment-based 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, etc. are mentioned. For the dye system, 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 136, solvent blue 67 , Solvent Blue 70, etc. may be used. In addition to these, a metal-substituted or unsubstituted phthalocyanine compound can also be used.

As the green colorant, there are phthalocyanine-based, anthraquinone-based, and perylene-based similarly, and specifically, Pigment Green 7, Pigment Green 36, Solvent Green 3, Solvent Green 5, Solvent Green 20, solvent green 28, etc. can be used. In addition to the above, a metal-substituted or unsubstituted phthalocyanine compound may also be used.

Examples of the yellow colorant include monoazo, disazo, condensed azo, benzimidazolone, isoindolinone, anthraquinone, and the like, and specific examples thereof include the following. Anthraquinone-based yellow colorants such as Solvent Yellow 163, Pigment Yellow 24, Pigment Yellow 108, Pigment Yellow 193, Pigment Yellow 147, Pigment Yellow 199 and Pigment Yellow 202, Pig Isoindolinone-based yellow colorants such as Pigment Yellow 110, Pigment Yellow 109, Pigment Yellow 139, Pigment Yellow 179, and Pigment Yellow 185, Pigment Yellow 93, Pigment Yellow 94, Pigment Yellow 95, Pigment Yellow 128, Pigment Yellow 155, Pigment Yellow 166, Condensed azo yellow colorants such as Pigment Yellow 180, Pigment Yellow 120, Pigment Yellow 151, Pigment Yellow 154, Pigment Yellow 156, Pigment Yellow 175, Pigment Benzimidazolone-based yellow colorants such as Ment Yellow 181, Pigment Yellow 1, 2, 3, 4, 5, 6, 9, 10, 12, 61, 62, 62:1, 65, 73, 74, 75, Monoazo yellow colorants such as 97, 100, 104, 105, 111, 116, 167, 168, 169, 182, 183, Pigment Yellow 12, 13, 14, 16, 17, 55, 63, 81, 83, Disazo yellow colorants such as 87, 126, 127, 152, 170, 172, 174, 176, 188, and 198 can be used.

Moreover, you may add colorants, such as purple, tea color, brown, and black, for the purpose of adjusting color tone. Specifically, Pigment Violet 19, 23, 29, 32, 36, 38, 42, Solvent Violet 13, 36, C. I. Pigment Orange 1, C. I. Pigment Orange 5, C. I. Pig Pigment Orange 13, C. I. Pigment Orange 14, C. I. Pigment Orange 16, C. I. Pigment Orange 17, C. I. Pigment Orange 24, C. I. Pigment Orange 34, C. I. Pigment Orange 36, C. I. Pigment Orange 38, C. I. Pigment Orange 40, C. I. Pigment Orange 43, C. I. Pigment Orange 46, C. I. Pigment Orange 49, C. I. Pigment Orange 51, C. I. Pigment Orange 61, C. I. Pigment Orange 63, C. I. Pigment Orange 64, C. I. Pigment Orange 71, C. I. Pigment Orange 73, C. I. Pigment Brown 23, C. I. Pigment Brown 25, C. I. Pigment Black 1, C. I. Pigment Black 7, and the like.

In addition, when the through electrode is formed in the fan-out area of the FO-WLP, it is necessary to laser process the fan-out area and the warpage correcting layer for FO-WLP at the same time. It is preferable to have Even in such a case, a colorant component (E) can be selected by considering it appropriately.

The compounding quantity of a coloring agent component (E) is excellent in the light transmittance to a deep part, and, as a result, from a viewpoint that a more preferable curvature correcting layer is obtained, curable components (A) and (B) contained in the sealing material for semiconductors of the sealing material for semiconductors. ), the curing agent component, and the film imparting polymer component (C) in a total of 100 parts by mass, preferably 0.1 to 35 parts by mass, more preferably 0.5 to 25 parts by mass, particularly preferably is in the range of 1 to 15 parts by mass.

The sealing material for semiconductors according to the present invention contains a coupling agent component (F) having a functional group that reacts with an inorganic material and a functional group that reacts with an organic functional group in order to improve at least one of adhesion to a semiconductor chip and adhesiveness it may be Moreover, the water resistance can be improved, without impairing the heat resistance of the sealing material for semiconductors by containing a coupling agent component (F). As such a coupling agent, a titanate type coupling agent, an aluminate type coupling agent, a silane coupling agent, etc. are mentioned. 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, a ureido group, a chloropropyl group, a mercapto group, a polysulfide group, an isocyanate group, etc. can be heard As a silane coupling agent, a commercially available thing 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 brand names; Shin-Etsu Chemical Co., Ltd. make) etc. are mentioned. . These may be used individually by 1 type, and may use 2 or more types together.

Various additives may be mix|blended with the sealing material for semiconductors by this invention as needed other than an above-described component. Various additives include leveling agents, plasticizers, oxidizing agents, antioxidants, ion trapping agents, gettering agents, chain transfer agents, release agents, rust inhibitors, adhesion promoters, ultraviolet absorbers, thermal polymerization inhibitors, thickeners, antifoaming agents, etc. in the field of electronic materials. It may contain a well-known and usual additive.

An organic solvent can be contained in the sealing material for semiconductors by this invention. The organic solvent can be used for synthesizing a polyether compound containing an ethylenically unsaturated group in a molecule, mixing each component, and adjusting the viscosity at the time of applying the obtained sealing material for semiconductors to a substrate or a support film.

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

More specifically, 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 Glycol ethers such as carbitol, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, triethylene glycol monoethyl ether, ethyl acetate, butyl acetate, dipropylene glycol methyl ether acetate, propylene glycol Esters such as methyl ether acetate, propylene glycol ethyl ether acetate, and propylene glycol butyl ether acetate, alcohols such as ethanol, propanol, ethylene glycol, and propylene glycol, aliphatic hydrocarbons such as octane and decane, petroleum ether, petroleum naphtha, hydrogenated petroleum Petroleum solvents, such as naphtha and solvent naphtha, etc. are mentioned. An organic solvent may be used individually by 1 type, and may be used in combination of 2 or more type.

Although the thickness of the sealing material for semiconductors of this invention is not specifically limited when making it into a film (or sheet-like) shape, Preferably it is 3-500 micrometers, More preferably, it is 5-450 micrometers, Especially preferably, it is 7- 400 μm.

When the sealing material for semiconductors according to the present invention contains, for example, a cyclic ether compound as the thermosetting component (A), and a compound having at least one ethylenically unsaturated group in the molecule as the active energy ray-curable component (B) , since it has initial adhesiveness, in an uncured state, it is easily adhered by pressing on a pseudo wafer, chip, or the like. Moreover, when pressing, you may give any means of a heating and pressurization with respect to the sealing material for semiconductors. And finally, through another curing reaction, it is possible to form a cured film (curvature correction layer) with high adhesion and warpage correcting power. The cured film (curvature correction layer) formed using the sealing material for semiconductors by this invention is excellent also in adhesive strength, and can maintain sufficient protective function even under severe high temperature and high humidity conditions. In addition, a single-layer structure may be sufficient as the curvature correction layer obtained by hardening|curing the sealing material for semiconductors, and a multilayer structure may be sufficient as it.

The sealing material for semiconductors of this invention may be used as a dry film, and may be used as it is in a liquid state. When using as a liquid, one-component or two-component or more may be sufficient.

In the case of dry film formation, the semiconductor encapsulant is diluted with an organic solvent and adjusted to an appropriate viscosity, followed by a comma coater, blade coater, lip coater, rod coater, squeeze coater, reverse coater, transfer roll coater, gravure coater, spray coater, etc. A film can be obtained by coating it with a uniform thickness on the support film and drying it at a temperature of 50 to 130° C. for 1 to 30 minutes.

Although there is no restriction|limiting in particular about the coating film thickness, From the point of obtaining the sealing material for semiconductors which has a more preferable curvature correction capability, it is the film thickness of the dry film after drying in general, 5-150 micrometers, Preferably it is the range of 10-60 micrometers. is appropriately selected from

As a support body film, conventionally well-known things, such as a separate paper, a separate film, a separation paper, a peeling film, and a release paper, can be used suitably. In addition, one or both sides of a substrate for release paper including a polyester film such as polyethylene terephthalate (PET) or polyethylene naphthalate (PEN), a polyolefin film such as an oriented polypropylene film (OPP), and a plastic film such as a polyimide film You may use the thing in which the mold release layer was formed. Although it will not specifically limit if it is a material which has mold release property as a mold release layer, For example, a silicone resin, organic resin modified silicone resin, a fluororesin, etc. are mentioned.

Although there is no restriction|limiting in particular about the thickness of a support film, Generally, it selects suitably in the range of 10-150 micrometers.

After forming the sealing material for semiconductors into a film on a support body film, you may laminate|stack a peelable cover film on the surface of a film|membrane for the objective, such as adhesion prevention of the dust to the surface of a film|membrane further. As a peelable cover film, a polyethylene film, a polytetrafluoroethylene film, a polypropylene film, the surface-treated paper etc. can be used, for example. In consideration of peeling of the cover film, the adhesion between the film and the cover film is made smaller than the adhesion between the film and the support film.

The semiconductor encapsulant of the present invention is, for example, adjusted to a viscosity suitable for the coating method with 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 coating method A film shape can be formed by apply|coating by the method of these etc. and volatilizing-drying (provisionally drying) the organic solvent contained in the composition at the temperature of about 60-100 degreeC.

The volatilization drying performed after the semiconductor encapsulant of the present invention is applied is a hot air circulation drying furnace, an IR furnace, a hot plate, a convection oven, etc. It can be carried out using the method of making countercurrent contact and the method of spraying from a nozzle to a support body).

When making the sealing material for semiconductors into a film form, it is good also as a form of laminated|multilayer film provided with the layer containing an above-described component in at least two or more layers. When setting it as a laminated|multilayer film, it is preferable to mutually make the composition of the sealing material for semiconductors which comprises each layer different. In particular, in each layer, by changing the type or compounding ratio of the active energy ray-curable component (B) and/or the type or compounding amount of the curing agent component of the active energy ray-curable component (B), the surface and the back surface by irradiation with active energy ray It is also possible to control the cure shrinkage of For example, when the bending direction and the amount of warpage of the pseudo wafer in the case of using the conventional sealing material for semiconductors are known in advance, the active energy ray-curable component (B) of each layer of the laminated film according to the bending direction and amount of warpage By adjusting the compounding ratio or the type or compounding amount of the curing agent component, it is possible to express a desired bending correction force.

When the semiconductor encapsulant is in the form of a laminated film as described above, at least one layer, preferably all of the layers constituting the semiconductor encapsulant, under an environment not exposed to active energy rays, heat treatment at 150° C. for 10 minutes It is preferable that the amount of heat generated when 1J/cm ² of ultraviolet light containing a wavelength of 351 nm is irradiated to the encapsulant for semiconductors after performing at 25° C. is 1 J/g or more. The cure shrinkage of the active energy ray-curable component contained in the sealing material for semiconductors on the side irradiated with an active energy ray can be accelerated|stimulated, and the state of curvature can be changed.

As described above, according to the semiconductor encapsulant of the present invention, the thermosetting component (A) is cured to some extent by heat to perform mold molding (pre-molding), and then by irradiating one or both surfaces of the pseudo wafer with active energy rays, Calibration can be performed in consideration of the direction and amount of warpage. The semiconductor encapsulant of the present invention is a fan-out type wafer level in which a region of the semiconductor encapsulant is formed so as to be in contact with the outer periphery or part of the semiconductor chip, and a redistribution layer connected to the electrode is also provided in the region of the semiconductor encapsulant. By being used for the package, a wafer-level package without warpage can be realized.

Example

Hereinafter, although an Example demonstrates this invention, this invention is not limited to these Examples. In addition, unless otherwise indicated, "part" and "%" shall mean a mass part. In addition, production of the sealing material for semiconductors and the measurement after that were performed in the environment which is not exposed to an active energy ray unless there is particular notice.

<Preparation of resin solution (Re1)>

119.4 parts of novolak-type cresol resin (Showa Denko Co., Ltd., Shonol CRG951, OH equivalent: 119.4), 1.19 parts of potassium hydroxide, in an autoclave equipped with a thermometer, a nitrogen introduction device and alkylene oxide introduction device, and a stirring device And 119.4 parts of toluene were thrown in, the inside of the system was replaced with nitrogen while stirring, and the temperature was raised by heating. Then, 63.8 parts of propylene oxide were dripped gradually, and it was made to react at 125-132 degreeC, and 0-4.8 kg/cm< ² > for 16 hours. Thereafter, the mixture was cooled to room temperature and mixed with 1.56 parts of 89% phosphoric acid to the reaction solution to neutralize potassium hydroxide, and a propylene oxide reaction solution of a novolak-type cresol resin having a nonvolatile content of 62.1% and a hydroxyl value of 182.2 g/eq. got As for this, 1.08 moles of alkylene oxides were added on average per equivalent of phenolic hydroxyl group.

293.0 parts of an alkylene oxide reaction solution of the obtained novolak-type cresol resin, 43.2 parts of acrylic acid, 11.53 parts of methanesulfonic acid, 0.18 parts of methylhydroquinone and 252.9 parts of toluene were put into a reactor equipped with a stirrer, a thermometer and an air intake tube, and air It was allowed to react at 110°C for 12 hours while stirring by blowing at a rate of 10ml/min. The water produced by the reaction was an azeotrope with toluene, and 12.6 parts of water flowed out. Then, it cooled to room temperature, and the obtained reaction solution was neutralized with 35.35 parts of 15% sodium hydroxide aqueous solution, and then, it washed with water. Then, it distilled off while substituting 118.1 parts of diethylene glycol monoethyl ether acetate (carbitol acetate) for toluene by an evaporator, and the novolak-type acrylate resin solution was obtained.

Next, 332.5 parts of the obtained novolac-type acrylate resin solution and 1.22 parts of triphenylphosphine are put into a reactor equipped with a stirrer, a thermometer and an air suction tube, and while stirring by blowing air at a rate of 10 ml/min, tetrahydrophthalic acid 60.8 parts of anhydrides were gradually added, and it was made to react at 95-101 degreeC for 6 hours, and after cooling, the acid value of 88 mgKOH/g of a solid, and the acryl containing polyether compound solution of 70.9% of solid content: resin solution (Re1) was obtained.

<Production of encapsulant 1 for semiconductor>

The following components were melt|dissolved and disperse|distributed in methyl ethyl ketone, and the composition solution 1a for sealing materials of 20% of solid content mass concentration was prepared.

・Phenoxy resin (FX293, manufactured by Shinnitetsu Sumikin Co., Ltd.) 50 copies

・70.4 parts of resin solution Re1

・Dicyclopentadiene skeleton-containing polyfunctional solid epoxy resin

(DIC Corporation Epiclone HP-7200H) 30 copies

・Bisphenol A type epoxy resin

(JER828 made by Mitsubishi Chemical Co., Ltd.) 10 copies

·Phenol novolac type epoxy resin

(DEN-431 made by The Dow Chemical Company) 10 copies

・10 copies of Carbon Black (Carbon MA-100 manufactured by Mitsubishi Chemical Co., Ltd.)

· spherical silica

(Admapine SO-E2 made by Admatex, Inc.) 200 copies

・Aluminum hydroxide (High Delight 42M manufactured by Showa Denko Co., Ltd.) 150 parts

・Silane coupling agent (KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd.) 2 parts

・Anthraquinone 2 parts

・2-Phenylimidazole (Shikoku Kasei Kogyo Co., Ltd. 2PZ) 2 copies

· Urethane acrylate oligomer

(DPHA-40H manufactured by Nippon Kayaku Co., Ltd.) 10 copies

Trimethylolpropane triacrylate

(TMPTA manufactured by Nippon Kayaku Co., Ltd.) 10 copies

・2 parts of radical photopolymerization initiator (Irgacure 784)

The composition solution 1a for a protective film-forming encapsulant was applied to a polyethylene terephthalate film (PET film) subjected to a peeling treatment on the surface, and dried at 100° C. for 10 minutes to prepare a semiconductor encapsulant 1a having a thickness of 50 μm.

Then, the following components were melt|dissolved and disperse|distributed in methyl ethyl ketone, and the composition solution 1b for sealing materials of 20% of solid content mass concentration was prepared.

・Phenoxy resin (FX293, manufactured by Shinnitetsu Sumikin Co., Ltd.) 50 copies

・70.4 parts of resin solution Re1

・Dicyclopentadiene skeleton-containing polyfunctional solid epoxy resin

(DIC Corporation Epiclone HP-7200H) 30 copies

・Bisphenol A type epoxy resin

(JER828 made by Mitsubishi Chemical Co., Ltd.) 10 copies

·Phenol novolac type epoxy resin

(DEN-431 made by The Dow Chemical Company) 10 copies

・Carbon black

(Mitsubishi Chemical Co., Ltd. Carbon MA-100) 10 copies

· spherical silica

(Admapine SO-E2 made by Admatex, Inc.) 200 copies

・Aluminum hydroxide (High Delight 42M manufactured by Showa Denko Co., Ltd.) 150 parts

・Silane coupling agent (KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd.) 2 parts

・Anthraquinone 2 parts

・2-Phenylimidazole (Shikoku Kasei Kogyo Co., Ltd. 2PZ) 2 copies

· Urethane acrylate oligomer

(DPHA-40H manufactured by Nippon Kayaku Co., Ltd.) 10 copies

・1.5 parts of radical photopolymerization initiator (Irgacure 784)

The protective film-forming encapsulant composition solution 1b was applied to a polyethylene terephthalate film (PET film) having a peeling treatment on the surface, and dried at 100° C. for 10 minutes to prepare a semiconductor encapsulant sheet 1b having a thickness of 50 μm.

Using a roll laminator, two sheets of encapsulant sheet 1a for semiconductors were put together, one side of the PET film subjected to the peeling treatment was peeled off, and the encapsulant sheet 1a for semiconductors was further applied to the peeled side to encapsulant sheet 1a for semiconductors. A sheet in which three were laminated was prepared. Moreover, the same process was performed using the sealing material sheet 1b for semiconductors, and the sheet|seat on which 3 sheets of the sealing material sheet 1b for semiconductors were laminated|stacked was produced.

Next, one side of the PET film subjected to the peeling treatment was peeled from the sheet on which the encapsulant sheet 1a for semiconductor was laminated with 3 sheets, and the PET film subjected to the peeling treatment also from the sheet on which the encapsulant sheet 1b for semiconductor was laminated with 3 sheets. One side is peeled off, the semiconductor encapsulant sheet 1a and the semiconductor encapsulant sheet 1b are laminated together, and 3 semiconductor encapsulant sheet 1a and 3 semiconductor encapsulant sheet 1b are laminated in this order, total thickness 300 A semiconductor encapsulant 1 of μm was prepared.

<Production of semiconductor encapsulant 2>

The following components were blended, heated at 70 ° C. for 4 minutes, then at 100 ° C. for 6 minutes with a roll kneader, and melt-kneaded under reduced pressure (0.01 kg/cm ² ) for a total of 10 minutes to prepare a kneaded product 2.

・Dicyclopentadiene skeleton-containing polyfunctional solid epoxy resin

(DIC Corporation Epiclone HP-7200H) 30 copies

・Bisphenol A type epoxy resin

(JER828 made by Mitsubishi Chemical Co., Ltd.) 10 copies

·Phenol novolac type epoxy resin

(DEN-431 made by The Dow Chemical Company) 10 copies

・10 copies of Carbon Black (Carbon MA-100 manufactured by Mitsubishi Chemical Co., Ltd.)

· spherical silica

(Admapine SO-E2 made by Admatex, Inc.) 500 copies

・Silane coupling agent (KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd.) 2 parts

・2-Phenylimidazole (Shikoku Kasei Kogyo Co., Ltd. 2PZ) 2 copies

· Urethane acrylate oligomer

(Nippon Kayaku Co., Ltd. UX-5000) 10 copies

Trimethylolpropane triacrylate

(TMPTA manufactured by Nippon Kayaku Co., Ltd.) 10 copies

・2 parts of radical photopolymerization initiator (Irgacure 784)

・Anthraquinone 2 parts

The obtained kneaded material 2 is sandwiched between two 50 µm cover films (Teijin Purex film), and the kneaded material is formed into a sheet by a flat plate press method, and a sheet-like semiconductor encapsulant having a thickness of 300 µm got 2

<Production of encapsulant 3 for semiconductor>

The following components were blended, heated at 70 ° C. for 4 minutes, and then at 100 ° C. for 6 minutes with a roll kneader, and melt-kneaded under reduced pressure (0.01 kg/cm ² ) for a total of 10 minutes to prepare a kneaded product 3 .

・Bisphenol A type epoxy resin

(JER1001 made by Mitsubishi Chemical Co., Ltd.) 30 copies

・Phenol novolac type epoxy resin

(DEN-431 made by The Dow Chemical Company) 10 copies

·C. I. Pigment Blue 15:3 0.8 parts

·C. I. Pigment Yellow 147 0.55 parts

·Paliogen Red K3580 1.5 parts

· spherical silica

(Admafine SO-E2 made by Admatex, Inc.) 400 copies

・Silane coupling agent (KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd.) 2 parts

・2-Phenylimidazole (Shikoku Kasei Kogyo Co., Ltd. 2PZ) 2 copies

・Urethane acrylate oligomer

(DPHA-40H manufactured by Nippon Kayaku Co., Ltd.) 20 copies

· 2 parts of radical photopolymerization initiator (compound of formula 1)

The obtained kneaded material 3 was sandwiched between two 50 µm PET films (Teijin Purex Film), and the kneaded material was formed into a sheet by a flat plate press method, and a sheet-like semiconductor encapsulant having a thickness of 300 µm got 3

<Production of encapsulant 4 for semiconductor>

The following components were blended, heated at 70° C. for 4 minutes, then at 100° C. for 6 minutes with a roll kneader, and melt-kneaded under reduced pressure (0.01 kg/cm ² ) for a total of 10 minutes to prepare a kneaded product 4.

・Dicyclopentadiene skeleton-containing polyfunctional solid epoxy resin

(DIC Corporation Epiclone HP-7200H) 30 copies

・Bisphenol A type epoxy resin

(JER828 made by Mitsubishi Chemical Co., Ltd.) 10 copies

·Phenol novolac type epoxy resin

(DEN-431 made by The Dow Chemical Company) 10 copies

・Carbon black

(Mitsubishi Chemical Co., Ltd. Carbon MA-100) 10 copies

· spherical silica

(Admapine SO-E2 made by Admatex, Inc.) 600 copies

・Titanium oxide (CR-90 manufactured by Ishihara Sangyo Co., Ltd.) 15 copies

・Silane coupling agent (KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd.) 2 parts

・2-Phenylimidazole (Shikoku Kasei Kogyo Co., Ltd. 2PZ) 2 copies

・Urethane acrylate oligomer

(DPHA-40H manufactured by Nippon Kayaku Co., Ltd.) 20 copies

・2 parts of radical photopolymerization initiator (Irgacure 784)

The obtained kneaded material 4 was sandwiched between two 50 µm cover films (Teijin Purex film), and the kneaded material was formed into a sheet by a flat plate press method, and a sheet-like semiconductor encapsulant having a thickness of 300 µm got 4

<Production of encapsulant 5 for semiconductor>

The following components were blended, heated at 70° C. for 4 minutes, then at 100° C. for 6 minutes with a roll kneader, and melt-kneaded under reduced pressure (0.01 kg/cm ² ) for a total of 10 minutes to prepare a kneaded product 5.

・Dicyclopentadiene skeleton-containing polyfunctional solid epoxy resin

(DIC Corporation Epiclone HP-7200H) 30 copies

・Bisphenol A type epoxy resin

(JER828 made by Mitsubishi Chemical Co., Ltd.) 10 copies

・Phenol novolac type epoxy resin

(DEN-431 made by The Dow Chemical Company) 10 copies

・Carbon black

(Mitsubishi Chemical Co., Ltd. Carbon MA-100) 10 copies

· spherical silica

(Admapine SO-E2 made by Admatex, Inc.) 500 copies

・Silane coupling agent (KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd.) 2 parts

・2-Phenylimidazole (Shikoku Kasei Kogyo Co., Ltd. 2PZ) 2 copies

・Urethane acrylate oligomer

(Nippon Kayaku Co., Ltd. UX-5000) 20 copies

- 2 parts of radical photopolymerization initiator (compound of Formula 1 above)

・Anthraquinone 3 parts

・Antioxidant (Adecastab AO-60) 1 part

The obtained kneaded material 5 was sandwiched between two 50 µm cover films (Teijin Purex film), and the kneaded material was formed into a sheet by a flat plate press method, and a sheet-like semiconductor encapsulant having a thickness of 300 µm got 5.

<Production of encapsulant 6 for semiconductor>

Except not using an acrylate and a radical photopolymerization initiator, it operated in the same manner as in the semiconductor encapsulant 1 to prepare a semiconductor encapsulant 6 having a thickness of 300 µm.

<Production of encapsulant 7 for semiconductor>

Except not using an acrylate and a radical photopolymerization initiator, it operated similarly to the sealing material 2 for semiconductors, and produced the sealing material 7 for semiconductors with a thickness of 300 micrometers.

<Production of encapsulant 8 for semiconductor>

Except not using an acrylate and a radical photopolymerization initiator, it operated similarly to the sealing material 3 for semiconductors, and produced the sealing material 8 for semiconductors with a thickness of 300 micrometers.

<Production of encapsulant 9 for semiconductor>

Except not using an acrylate and a radical photopolymerization initiator, it operated similarly to the sealing material 4 for semiconductors, and produced the sealing material 9 for semiconductors with a thickness of 300 micrometers.

<Production of encapsulant 10 for semiconductor>

Except not using the acrylate and the radical photopolymerization initiator, it operated in the same manner as in the semiconductor encapsulant 5, to prepare a semiconductor encapsulant 10 having a thickness of 300 µm.

<Measurement of heat of reaction during heating of semiconductor encapsulant>

With respect to the sealing materials for semiconductors 1-10 obtained as mentioned above, in order to measure the amount of reaction heat at the time of heating in the environment which is not exposed to an active energy ray, DSC measurement was performed. The amount of reaction heat was measured using a DSC measuring apparatus (DSC Q100 manufactured by TA Instruments) in a nitrogen gas atmosphere using an aluminum sample pan.

<Confirmation of reaction heat during heating of semiconductor encapsulant>

The semiconductor encapsulants 1 to 10 were put in a DSC device, and the temperature was raised from 25°C to 230°C at 10°C/min, and the heat of reaction β at that time was measured. As a result, also in any sealing material for semiconductors, it was confirmed that the amount of reaction heat of 1 J/g or more generate|occur|produced.

<Confirmation of reaction heat by reheating after heating of semiconductor encapsulant>

In addition, the semiconductor encapsulant 1 to 10 are put in the DSC device, the temperature is raised from 25 ° C to 150 ° C at 10 ° C / min, maintained at 150 ° C for 10 minutes, and then returned to 25 ° C by lowering the temperature at 10 ° C / min. , the temperature was further increased from 25°C to 230°C at 10°C/min, and the heat of reaction γ at that time was measured. As a result, also in any sealing material for semiconductors, it was confirmed that the amount of reaction heat of 1 J/g or more generate|occur|produced.

<Measurement of warpage change of encapsulant for semiconductor>

The semiconductor encapsulant was molded into a sheet shape having a thickness of 300 µm in a square of 50 mm × 50 mm, and further sandwiched between SUS plates having a thickness of 1 mm from both surfaces to prepare a laminate. This laminate was loaded on a hot plate, the temperature was raised at 10°C/min, 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 encapsulant having a thickness of 300 µm after thermosetting was flatly stacked in a 50 mm×50 mm square, and it was confirmed that there was no curvature of the angle.

One side of the sheet-like encapsulant after thermosetting was irradiated with an active energy ray of 1J/cm ² using a high-pressure mercury lamp under an environment of 25° C., and the presence or absence of bending deformation of the sheet-like encapsulant was observed. At this time, the semiconductor encapsulant 1 and 6 were irradiated with active energy rays to the semiconductor encapsulant sheet 1a surface and the semiconductor encapsulant sheet 6a surface. When the surface irradiated with an active energy ray contracted and deform|transformed into a concave shape, the curvature of 4 corners was measured with a metal regular. When the sum of the values of the four curvatures was 4 mm or more, it was judged as pass (Good), when it was 8 mm or more, it was pass (very good), and when it was less than 4 mm, it was judged as bad (Bad). The results are shown in Tables 1 and 2.

<Measurement of heat of reaction α when irradiated with actinic light of a semiconductor encapsulant>

Prepare a sheet-like semiconductor encapsulant after thermosetting in which the thermosetting component was reacted by heating at 150° C. for 10 minutes as described above, and measure the heat of reaction α (J/g) when irradiated with active energy rays in Photo-DSC did Photo-DSC was measured under the following conditions.

·Photo-DSC device: Measured using a combination of DSC Q100 manufactured by TA Instruments and Qseries PCA light source device, and an aluminum sample pan at 25°C in a nitrogen gas atmosphere

Light source: high pressure mercury lamp (no wavelength cut filter)

· Illuminance: 3.7W/cm ² The sample was irradiated with light through a filter which attenuated 1% from this illuminance using a dual light guide.

- Integrated photometer: Using ORC's UV-351, the irradiation time at which the accumulated light amount of wavelength 351 nm becomes 1 J/cm ² was confirmed, and the irradiation time of Photo-DSC was set.

The results of the heat of reaction (J/g) upon irradiation with active energy rays were as shown in Tables 1 and 2.

As shown in Table 1, when an active energy ray is irradiated to a sheet-like encapsulant after heat curing at 150° C. for 10 minutes, the reaction heat α (J/g) at the time of irradiation with active energy ray is 1 J/g or more. 1 to 5 were able to confirm the change of the curvature of 4 mm or more in all by irradiating an active energy ray to the single side|surface of a sheet-like sealing material. On the other hand, as shown in Table 2, when an active energy ray was irradiated to the sheet-like sealing material after heat curing at 150° C. for 10 minutes, the amount of reaction heat α (J/g) at the time of irradiation with active energy ray was less than 1 J/g. In Examples 1 to 5, even if one side of the sheet-like sealing material was irradiated with an active energy ray, a change in curvature of 4 mm or more could not be confirmed.

Claims (7)

As a semiconductor encapsulant used for a fan-out type wafer level package containing at least a thermosetting component (A) and an active energy ray-curable component (B),
In an environment not exposed to active energy rays, the amount of heat generated when the semiconductor encapsulant after heat treatment at 150° C. for 10 minutes is irradiated with 1 J/cm ² of ultraviolet rays having a wavelength of 351 nm at 25° C. (J/g) 1 ≤ α (J / g), characterized in that, a semiconductor encapsulant used in a fan-out type wafer-level package. The heating value β (J/g) of claim 1, wherein the semiconductor encapsulant is heated from 25° C. to 230° C. at 10° C./min using a differential scanning calorimeter (DSC) under an environment not exposed to active energy rays. is 1≤β (J/g), a semiconductor encapsulant used in a fan-out type wafer-level package. The differential scanning calorimeter according to claim 1 or 2, wherein the semiconductor encapsulant after heat treatment at 150° C. for 10 minutes under an environment not exposed to active energy rays is subjected to an environment not exposed to active energy rays ( DSC), the amount of heat generated when the temperature is raised from 25°C to 230°C at 10°C/min. (J/g) is 1≤γ(J/g). . The semiconductor encapsulant for use in a fan-out type wafer-level package according to claim 1 or 2, which is in any form of liquid, granular, tablet, or sheet. The semiconductor encapsulant according to claim 1 or 2, which is a sheet-like semiconductor encapsulant laminated in two or more layers, and each layer has a different material composition, and is used for a fan-out type wafer level package. The semiconductor encapsulant according to claim 1 or 2, which is used in contact with the outer periphery or a part of the semiconductor chip, and is used in a fan-out type wafer level package. A method for manufacturing a fan-out type wafer-level package, comprising:
A semiconductor encapsulant comprising at least a thermosetting component (A) and an active energy ray-curable component (B), in an environment not exposed to active energy rays, after heat-treating at 150 ° C. for 10 minutes A step of preparing a semiconductor encapsulant having a calorific value α (J/g) of 1≤α (J/g) when 1 J/cm ² of ultraviolet light including a wavelength of 351 nm is irradiated at 25° C.;
By heating the semiconductor encapsulant, the thermosetting reaction of the thermosetting component (A) in the semiconductor encapsulant has progressed to some extent, but is not completely thermosetted, so that the fan-out type wafer level package is manufactured. a process of forming a wafer; and
By irradiating an active energy ray to the semiconductor encapsulant of the pseudo wafer, curing shrinkage of the active energy ray-curable component (B) in the semiconductor encapsulant is accelerated, and cured to offset the bending stress inherent in the pseudo wafer. Process of correcting warpage by applying stress by contraction
A method of manufacturing a fan-out type wafer-level package comprising a.