JP2009097014A - Liquid resin composition for sealing, electronic component device and wafer level chip size package - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a liquid resin composition for sealing which exhibits low warpage even when applied to an electronic component device such as a wafer level chip size package requiring low warpage and which has reliability such as excellent strength, thermal shock resistance and humidity resistance, and has excellent workability or the like, and to provided an electronic component device and a wafer level chip size package each equipped with an element sealed by the liquid resin composition for sealing. <P>SOLUTION: The liquid resin composition for sealing contains an inorganic filler (A) containing porous silica particles having the surface coated with an inorganic compound. The modulus of elasticity of the cured material of the liquid resin composition for sealing at 25°C is 6-15 GPa. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to an encapsulating liquid resin composition, and an electronic component device and a wafer level chip size package comprising an element encapsulated with the encapsulating liquid resin composition.

  Conventionally, in the field of element sealing of electronic component devices such as transistors and ICs, resin sealing has been the mainstream in terms of productivity, cost, etc., and epoxy resin molding materials have been widely used. This is because the epoxy resin is balanced in various properties such as electrical properties, moisture resistance, heat resistance, mechanical properties, and adhesiveness with inserts.

  On the other hand, in recent years, in order to reduce the cost, high integration, high performance, and high functionality of electronic component devices, device wiring has been miniaturized, multi-layered, multi-pinned, and high density has been achieved by making packages smaller and thinner. Progressing. Accordingly, electronic component devices having almost the same size as IC elements, that is, CSP (Chip Size Package) have been widely used.

  Under such circumstances, a wafer level chip size package that performs resin sealing in a wafer state is attracting attention as an effective package for high-density mounting. This wafer level chip size package is a silicon element in which fine wiring is applied as a semiconductor element, and rewiring and electrodes for leading out external connection terminals are formed on the surface, and bumps are formed on the electrodes or leads are connected. The surface of the wafer is sealed with an epoxy resin composition, soldered to bumps or leads, and then the silicon wafer is cut into individual elements to obtain products. This method is used to seal a large number of elements at one time by transfer molding using a solid epoxy resin composition or printing molding using a liquid epoxy resin composition in the state of a wafer, and then separating them into individual pieces. Compared with the method of sealing after separating the elements into individual pieces, the production can be greatly rationalized. However, in a wafer level chip size package, the sealed wafer is likely to warp, and this warpage is a problem in each process such as subsequent conveyance, grinding, inspection, singulation, etc. There is a problem that causes fluctuations. In the semiconductor field, in order to further reduce the cost, the wafer diameter tends to increase further, and reducing the warpage of the wafer after sealing is an important issue in spreading the wafer level chip size package. It has become.

  The warpage of the wafer is affected by the molding shrinkage of the epoxy resin composition used for sealing and the stress generated by the mismatch between the thermal expansion coefficients of the silicon wafer and the epoxy resin composition, and also reduces the reliability of the package. There is a fear. Therefore, it is necessary to reduce the stress in the epoxy resin composition used for such applications, and in general, the molding shrinkage of the epoxy resin composition is reduced, the inorganic filler is highly filled to reduce the thermal expansion coefficient, It is effective to reduce the elastic modulus by using a flexible agent or a flexible resin.

  However, only the method of bringing the thermal expansion coefficient closer to the wafer by highly filling with an inorganic filler increases the elastic modulus of the cured product itself, so that the stress reduction is insufficient and there is a limit to reducing warpage.

Therefore, for example, Patent Document 1 and Patent Document 2 disclose a liquid resin composition containing a silicone-modified epoxy resin as a main component and having a cured product having an elastic modulus at room temperature of 5 GPa or less. On the other hand, Patent Document 3 discloses a resin composition containing a thermosetting resin having a dihydrobenzoxazine ring which is excellent in heat resistance and storage stability, and has high strength and flexibility.
JP 2003-238651 A Japanese Patent Laid-Open No. 2003-238652 Japanese Patent No. 3900317

  Patent Document 1 and Patent Document 2 propose a technique in which a silicone resin is used as a base resin, thereby reducing the elastic modulus of the cured product and reducing warpage by stress relaxation. However, since the main component of the resin composition is composed of a soft resin skeleton with a low elastic body, the mechanical strength is lowered, it becomes difficult to uniformly grind the sealing resin, or the sealing resin is applied during wafer dicing. In addition to the problem that the grinding wheel is likely to occur, the grinding wheel and the dicing blade used in these processes are likely to be clogged during the process, and the wear is significantly increased. Furthermore, there is a drawback that the moisture resistance reliability is lowered due to a decrease in glass transition temperature and strength.

  On the other hand, in the method using a thermosetting resin having a dihydrobenzoxazine ring described in Patent Document 3, a sealing resin composition excellent in mechanical properties, low water absorption, and storage stability is obtained. In addition, thermosetting resins having a dihydrobenzoxazine ring are characterized by low cure shrinkage during ring-opening polymerization. However, Patent Document 3 does not describe a liquid resin composition that can be used for manufacturing a wafer level chip size package by a printing method.

  As described above, the sealing liquid resin composition used for the wafer level chip size package can reduce stress and suppress warpage of the wafer while exhibiting high strength, high reliability and good processability. Although desired, no effective solution has been found.

  The present invention has been made in view of such circumstances, and even when applied to an electronic component device that requires low warpage such as a wafer level chip size package, the warpage can be suppressed to a small level, and the strength, thermal shock resistance, moisture resistance, An object of the present invention is to provide a sealing liquid resin composition having excellent reliability such as processability, and an electronic component device and a wafer level chip size package comprising an element sealed with the sealing liquid resin composition. And

  The present invention is (1) a sealing liquid resin composition comprising an inorganic filler (A) containing porous silica particles whose surface is coated with an inorganic compound, the sealing liquid resin composition It is related with the liquid resin composition for sealing whose elastic modulus in 25 degreeC of the hardened | cured material of a thing is 6-15GPa.

In addition, the present invention provides: (2) The sealing liquid according to (1), wherein the specific surface area of the porous silica particles whose surfaces are coated with an inorganic compound is 0.5 to 10.0 m ² / g. The present invention relates to a resin composition.

  Moreover, this invention is (3) The liquid resin composition for sealing as described in said (1) or (2) whose compressive strength of the porous silica particle by which the said surface was coat | covered with the inorganic compound is 30-1500 Mpa. About.

  The present invention also includes (4) a liquid epoxy resin (B), a phenol resin (C), an elastomer (D) and an organic solvent (E), wherein the liquid epoxy resin (B) is a silicone-modified epoxy resin. The liquid resin composition for sealing according to any one of (1) to (3), wherein 30% by mass or more is contained.

  Moreover, this invention relates to the liquid resin composition for sealing as described in said (4) characterized by containing the compound (F) which further has (5) dihydrobenzoxazine ring.

Moreover, this invention is (6) The liquid resin composition for sealing as described in said (4) or (5) whose said silicone modified epoxy resin is an epoxy resin which has a siloxane structure shown by the following general formula (I). Related to things.

(R ¹ and R ² in the general formula (I) represent an alkyl group or an aryl group, and may be the same or different, and n is an integer of 1 or more.)
In addition, the present invention provides that the blending ratio of the liquid epoxy resin (B) is 30 to 83% by mass with respect to the total amount of the components (7) (B), (C) and (F), The compounding ratio of the compound (F) having 8.5 to 63% by mass, the compounding ratio of the phenol resin (C) is 2 to 35% by mass, and the total amount of the component (C) and the component (F) On the other hand, it is related with the liquid resin composition for sealing as described in said (5) or (6) whose compounding ratio of a phenol resin (C) is 10-50 mass%.

  The present invention is also (8) silicone rubber particles in which the elastomer (D) is crosslinked and formed by a hydrosilylation reaction of an alkenyl group-containing organopolysiloxane and a SiH group-containing organohydrogenpolysiloxane in a liquid epoxy resin. It is related with the liquid resin composition for sealing as described in any one of said (4)-(7).

  The present invention also relates to (9) the liquid resin composition for sealing according to (8), wherein the silicone rubber particles have an average particle size of 0.1 to 2 μm.

  In the present invention, (10) the elastomer (D) is a core / shell type silicone polymer particle containing a core layer made of a solid silicone polymer and a shell layer made of an organic polymer. It is related with the liquid resin composition for sealing as described in any one of-(7).

The present invention also provides (11) [RR′SiO _2/2 ] units, wherein the core / shell type silicone polymer particles have units consisting of [RSiO _3/2 ] and / or [SiO _4/2 ]. (Wherein R represents an alkyl group having 6 or less carbon atoms, an aryl group, or a substituent having a carbon double bond at the terminal, and R ′ represents an alkyl group or aryl group having 6 or less carbon atoms). The liquid resin composition for sealing according to the above (10), comprising a core layer made of a silicone polymer and a shell layer made of an organic polymer obtained by vinyl polymerization.

  The present invention also relates to (12) the sealing liquid resin composition according to (10) or (11), wherein the organic polymer is an acrylic polymer.

  Moreover, this invention is the said (13) 1-50 mass parts with respect to the total of 100 mass parts of (B) component, (C) component, and (F) component (B), the compounding quantity of the said elastomer (D). It is related with the liquid resin composition for sealing as described in any one of 4)-(12).

  The present invention also relates to (14) an electronic component device comprising an element sealed with the sealing liquid resin composition according to any one of (1) to (13).

  Moreover, this invention relates to the liquid resin composition for sealing as described in any one of said (1)-(13) used for sealing of (15) wafer level chip size package.

  The present invention also relates to (16) a wafer level chip size package comprising an element sealed with the sealing liquid resin composition according to any one of (1) to (13).

  According to the present invention, even when applied to an electronic component device that requires low warpage such as a wafer level chip size package, the warpage is suppressed to a small level, and reliability such as strength, thermal shock resistance, moisture resistance, and workability are reduced. It is possible to provide an electronic component device and a wafer level chip size package comprising a liquid resin composition for sealing excellent in the above, and an element sealed with the liquid resin composition for sealing.

  The liquid resin composition for sealing according to the present invention is a liquid resin composition for sealing containing an inorganic filler (A) containing porous silica particles whose surfaces are coated with an inorganic compound. The elastic modulus at 25 ° C. of the cured product of the liquid resin composition for stopping is 6 to 15 GPa.

  In the present invention, it is important to set the elastic modulus at 25 ° C. of the cured product obtained by curing the encapsulating liquid resin composition to be in the range of 6 to 15 GPa. The processability of the liquid resin composition for use can be improved. The elastic modulus is preferably 6 to 14 GPa, and more preferably 6 to 12 GPa. In order to reduce the warpage of the wafer when the liquid resin composition for sealing is printed on the wafer and cured by heating, it is effective to lower the elastic modulus of the cured product to reduce the stress. However, when the elastic modulus at 25 ° C. of the cured product is less than 6 GPa, the warp can be reduced but the workability is deteriorated. In particular, the grinding wheel and dicing blade are significantly worn during the resin grinding process and the dicing process. On the other hand, when the elastic modulus at 25 ° C. exceeds 15 GPa, the warpage becomes large. Especially, in a thin wafer level chip size package, after grinding the resin surface and the back surface (wafer surface), in addition to warping after heat curing, In addition, warping after reflow in the solder ball mounting process or the like becomes significant. Thus, in the present invention, it is important to set the elastic modulus at 25 ° C. of the cured product of the encapsulating liquid resin composition within the above range, and to achieve the object of the present invention outside the range. It is not possible.

  In order for the elastic modulus at 25 ° C. of the cured liquid resin composition for sealing to be in the range of 6 to 15 GPa, for example, the blending amount of the inorganic filler, the blending amount of the elastomer, the blending of the silicone-modified epoxy resin It can adjust by adjusting quantity, using a polyfunctional epoxy resin or a hardening | curing agent. Specifically, when the compounding amount of the inorganic filler is increased, the elastic modulus is increased, and when the compounding amount of the elastomer and the silicone-modified epoxy resin is increased, the elastic modulus is decreased. Further, by using a polyfunctional epoxy resin or a curing agent, the elastic modulus can be increased by increasing the crosslink density of the cured product of the encapsulating liquid resin composition. By using these methods alone or in combination, it is possible to adjust the elastic modulus at 25 ° C. of the cured liquid resin composition for sealing to an appropriate range.

  Here, the elastic modulus of the cured product is a storage elastic modulus when measured using a dynamic viscoelasticity measuring apparatus (frequency 10 Hz), and the liquid resin composition for sealing is heated and cured into a sheet of about 290 μm thickness. Then, this sheet was cut into 4 mm × 34 mm to prepare a test piece, and using a dynamic viscoelasticity measuring device DVE type (manufactured by Rheology Co., Ltd.), continuous vibration was performed with a sine wave having a distance between chucks of 25 mm and a frequency of 10 Hz. It can be measured by measuring the strain amount 5 μm, automatic static load, temperature rising rate 3 ° C./min, temperature range 20-250 ° C., and reading the storage elastic modulus at 25 ° C.

(A) Component: Inorganic filler (A-1) Porous silica particles whose surface is coated with an inorganic compound The inorganic filler (A) contained in the sealing liquid resin composition of the present invention has an inorganic compound on the surface. It is important to contain the porous silica particles (A-1) coated with the above, thereby suppressing the increase in the viscosity of the liquid resin composition for sealing, and suppressing the wear of the grind wheel and the dicing blade. It can be good. When porous silica particles whose surface is not coated are used, the specific surface area is large, so that the viscosity of the encapsulating liquid resin composition is remarkably increased, making it difficult to apply onto the wafer, resulting in poor processability. In addition, even when a solvent is added to reduce the viscosity, the amount of the solvent added increases, so that voids and significant film loss occur after heat curing, resulting in poor reliability of the cured product.

Surface specific surface area of the porous silica particles coated with the inorganic compound is not particularly limited, but is preferably 0.5~10.0m ² / g, more preferably 0.5~8.0m ² / g, 0 More preferably, it is from 6 to 6.0 m ² / g. When the specific surface area is 0.5 m ² / g or more, there are few irregularities on the surface of the porous silica particles, so the adhesion to the resin is low, and when it is 10.0 m ² / g or less, the sealing liquid resin There is an effect of suppressing an increase in the viscosity of the composition. Here, the specific surface area of the porous silica particles is measured by a BET method using nitrogen.

  The compressive strength of the porous silica particles whose surface is coated with an inorganic compound is not particularly limited, but is preferably 30 to 1500 MPa, more preferably 70 to 1200 MPa, and still more preferably 100 to 1000 MPa. When the compressive strength is less than 30 MPa, the porous silica particles may be collapsed during the production process of the sealing liquid resin composition. When the compressive strength is more than 1500 MPa, the grinding wheel and the dicing blade may be significantly worn. is there. Here, the compressive strength is measured when the particle breaks when measured with a micro compression tester (manufactured by Shimadzu Corporation, MCMT-200) at a load speed constant of 1 and a load speed of 0.029 to 0.27 gf / s. Compressive strength of

  The average particle diameter of the porous silica particles whose surface is coated with an inorganic compound is not particularly limited, but it is preferable to use a plurality of types of porous silica particles having different average particle diameters from the viewpoint of increasing the filling amount.

  The shape of the porous silica particles whose surface is coated with an inorganic compound is not particularly limited, and examples thereof include a spherical shape, a square shape, and an indefinite shape, and a spherical shape is preferable.

  The porous silica particle whose surface is coated with an inorganic compound is obtained by coating the surface of the porous silica particle with an inorganic compound by a known method, for example, a method described in JP-A-2006-176343. is there.

  The inorganic compound that covers the porous silica particles is preferably an inorganic oxide, and more preferably an inorganic oxide containing silicon. Specific examples of such inorganic oxides include silicon oxide, calcium oxide, and titanium oxide. Among these, inorganic oxides containing silicon are preferable, and for example, silicon dioxide is preferable. When the compound that coats the porous silica particles is an organic substance, there is a concern that the coating layer may swell or dissolve when an organic solvent is added to the sealing liquid resin composition, and the water absorption of the cured product increases. There is a risk that reliability will be reduced. The porous silica particles whose surface is coated with an inorganic compound are not particularly limited, but are produced by a known method as disclosed in, for example, JP-A-2006-176343. As an example, a method in which a solution in which an inorganic compound is dissolved or dispersed is added to a suspension in which porous silica particles are dispersed, and the surface of the porous silica particles is coated with the inorganic compound.

(A-2) Other inorganic fillers The liquid resin composition for sealing of the present invention includes (A) an inorganic filler other than porous silica particles (A-1) whose surface is coated with an inorganic compound. Other inorganic fillers (A-2) can be blended.

  As described above, from the viewpoint of increasing the filling amount, it is preferable to use a plurality of types of particles having different average particle diameters. However, in that case, a plurality of types of porous silica particles (A-1) may be used. The fine silica particles (A-1) and other inorganic fillers (A-2) may be used in combination.

  Other inorganic fillers include, for example, silica such as fused silica and crystalline silica, alumina such as calcium carbonate, clay and alumina oxide, silicon nitride, silicon carbide, boron nitride, calcium silicate, potassium titanate, aluminum nitride, and beryllia. , Powders of zirconia, zircon, fosterite, steatite, spinel, mullite, titania, or the like, or beads made of these particles, glass fibers, and the like. Furthermore, examples of the inorganic filler having a flame retardant effect include aluminum hydroxide, magnesium hydroxide, zinc borate, and zinc molybdate. Among these, fused silica is preferable from the viewpoint of reducing the linear expansion coefficient, and alumina is preferable from the viewpoint of high thermal conductivity. The shape of the other inorganic filler is preferably spherical from the viewpoints of high filling and fluidity / penetration into the fine gap of the liquid resin composition for sealing. Silica is preferably pretreated with a coupling agent from the viewpoint of fluidity and storage stability of the encapsulating liquid resin composition. These other inorganic fillers may be used alone or in combination of two or more.

  The average particle size of the other inorganic filler (A-2) is preferably a particle size in a range different from that of the porous silica particles (A-1) in order to have a particle size distribution from the viewpoint of increasing the filling amount.

  Moreover, when using together the porous silica particle (A-1) by which the surface was coat | covered with the inorganic compound, and other inorganic fillers (A-2), the porous silica particle by which the surface was coat | covered with the inorganic compound ( The blending ratio of the porous silica particles (A-1) whose surface is coated with an inorganic compound is 50% by mass or more with respect to the total amount of A-1) and other inorganic fillers (A-2). It is preferably 55% by mass, more preferably 60% by mass or more. When the said mixture ratio is less than 50 mass%, there exists a possibility that abrasion of a grinding wheel or a dicing blade may increase.

  The blending ratio of the inorganic filler (A) is not particularly limited, but is 70 to 94% by mass with respect to the total amount of the inorganic filler (A) and the components (B) to (E) described later. Is preferable, 80-93 mass% is more preferable, and 80-90 mass% is especially preferable. When the blending amount of the inorganic filler (A) is less than 70% by mass, the warp tends to increase because the effect of reducing the thermal expansion coefficient is reduced. On the other hand, when it exceeds 94% by mass, the viscosity of the liquid resin composition for sealing tends to decrease, so that the printing workability tends to decrease. When the amount of the organic solvent added to decrease the viscosity is increased, voids are generated. In addition, there is a possibility that the reliability of the cured product is impaired due to problems such as significant film reduction.

  The sealing liquid resin composition of the present invention further contains a liquid epoxy resin (B), a phenol resin (C), an elastomer (D), an organic solvent (E), and a compound (F) having a dihydrobenzoxazine ring. be able to.

(B) component: liquid epoxy resin Although the liquid epoxy resin (B) used for the liquid resin composition for sealing of this invention will not be specifically limited if it is liquid at room temperature (5-30 degreeC), A elasticity modulus is reduced. From the viewpoint of making it, the silicone-modified epoxy resin (B-1) is preferably contained in an amount of 30% by mass or more, more preferably 35% by mass or more, and even more preferably 40% by mass or more. It is particularly preferable to contain at least mass%.

(B-1) Silicone-modified epoxy resin The silicone-modified epoxy resin (B-1) contained in the liquid epoxy resin (B) may be anything, but a siloxane structure represented by the following general formula (I) It is preferable to have.

In the general formula (I), R ¹ and R ² are alkyl groups or aryl groups, which may be the same or different. Specifically, a methyl group, an ethyl group, a propyl group, an isopropyl group, Examples thereof include alkyl groups such as butyl group, isobutyl group, tert-butyl group, hexyl group, octyl group and decyl group; aryl groups such as phenyl group, xylyl group and tolyl group; among these, methyl group or A phenyl group is preferred, and a methyl group is more preferred. In general formula (I), n is an integer of 1 or more. Examples of commercially available commercially available silicone-modified epoxy resins having a siloxane structure represented by the general formula (I) include ALBIFLEX296, ALBIFLEX348, XP544 (trade names manufactured by Hanse Chemie) and the like.

  In addition, as other silicone-modified epoxy resins, the epoxy resin having a siloxane structure represented by the formula (I) and a substituent capable of reacting with an epoxy group such as a phenolic hydroxyl group, amino group, carboxyl group, and thiol group Obtained by reacting with a compound having no siloxane structure; and an epoxy resin having no siloxane structure, such as bisphenol A type, bisphenol F type, and bisphenol AD type epoxy resin, and phenolic Those having a substituent capable of reacting with an epoxy group such as a hydroxyl group, an amino group, a carboxyl group, and a thiol group, and obtained by reacting with a compound having a siloxane structure represented by the formula (I); It is done.

Among these, those obtained by reacting an epoxy resin represented by the following general formula (II) with a bifunctional phenol are preferable.

In the general formula (II), R ¹ and R ² are alkyl groups or aryl groups, which may be the same or different. Specifically, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, Examples thereof include alkyl groups such as isobutyl group, tert-butyl group, hexyl group, octyl group and decyl group; aryl groups such as phenyl group, xylyl group and tolyl group; among these, methyl group is preferable. In general formula (II), n is an integer greater than or equal to 1, 25 or less are preferable and 15 or less are more preferable. Commercially available commercially available epoxy resins represented by the general formula (II) include KF-105, X-22-163, X22-163A (trade names manufactured by Shin-Etsu Chemical Co., Ltd.), TSL9906 (GE Toshiba). And the epoxy equivalent is 1000 g / eq. The following is preferable, and 600 g / eq. The following is more preferable. These epoxy resins may be used alone or in combination of two or more.

  The bifunctional phenol used in the reaction is not particularly limited as long as it has two phenolic hydroxyl groups in one molecule. For example, monocyclic bifunctional phenols such as hydroquinone, resorcinol, catechol, terpene diphenol, etc. Bisphenols such as bisphenol A, bisphenol F, bisphenol AD and bisphenol S, dihydroxybiphenyls such as 4,4′-dihydroxybiphenyl, dihydroxyphenyl ethers such as bis (4-hydroxyphenyl) ether and the phenol skeleton Introducing a straight chain alkyl group, branched alkyl group, aryl group, hydroxyalkyl group, allyl group, cycloaliphatic group, etc. into the aromatic ring, straight chain alkyl group, branched alkyl on the carbon atom in the center of these bisphenol skeletons Group, ants Groups, substituted aryl groups, cycloaliphatic groups, polycyclic bifunctional phenols into which an alkoxycarbonyl group and the like are introduced, and these may be used alone or in combination of two or more. .

  The silicone-modified epoxy resin is, for example, mixed with an epoxy resin represented by the general formula (II) and a bifunctional phenol, and if necessary, a catalyst is added, and an organic solvent is further added as necessary to cause a heat reaction. Can be obtained. Examples of the catalyst include 1,8-diazabicyclo [5,4,0] undecene-7, 1,5-diazabicyclo [4,3,0] nonene-5, 5,6-dibutylamino-1,8-diazabicyclo [5]. , 4, 0] undecene-7 and other cycloamidine compounds, derivatives thereof, tertiary amines such as triethylamine, triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, 2-methylimidazole, 2-ethyl-4 -Imidazoles such as methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, organics such as tributylphosphine, methyldiphenylphosphine, triphenylphosphine, diphenylphosphine, phenylphosphine Phosphine Tetraphenylphosphonium · tetraphenyl borate, triphenyl phosphine tetraphenyl borate, 2-ethyl-4-methylimidazole · tetraphenyl borate, a tetraphenyl boron salts such as N- methylmorpholine tetraphenylborate. These may be used alone or in combination of two or more. As for the equivalent ratio of the epoxy resin and the bifunctional phenol in the reaction, the ratio of epoxy equivalent / hydroxyl equivalent is preferably 1-5.

  Moreover, the silicone modification | denaturation obtained from reaction of the silicone modified epoxy resin which has a short chain siloxane and n is about 1-3 which is the repeating unit of the siloxane structure in the epoxy resin shown by general formula (II), and bifunctional phenols Since the epoxy resin has a weak surface activity and tends to be inferior in foaming property, it is preferable to use it together with a silicone-modified epoxy resin having a long-chain siloxane rather than using it alone.

  In this case, when the silicone-modified epoxy resin having a short-chain siloxane is mixed with the silicone-modified epoxy resin having a long-chain siloxane, or when the silicone-modified epoxy resin having a short-chain siloxane is reacted with a bifunctional phenol, Or reacting with an epoxy resin having The equivalent ratio A / B of the equivalent A of the epoxy resin having a long-chain siloxane and the equivalent B of an epoxy resin having a short-chain siloxane during the reaction is preferably 0.2 to 5, and preferably 0.3 to 3. It is more preferable. If the equivalent ratio is less than 0.2, the foam breaking property and defoaming property tend to be insufficient, and if it exceeds 5, the reactivity of the resulting silicone-modified epoxy resin tends to be lowered.

  These silicone-modified epoxy resins (B-1) may be used alone or in combination of two or more.

Other liquid epoxy resins (B-2)
As the liquid epoxy resin (B), other liquid epoxy resins (B-2) other than the silicone-modified epoxy resin (B-1) can be used in combination. The other liquid epoxy resin (B-2) is not particularly limited as long as it is liquid at normal temperature (5 to 30 ° C.), but preferably has two or more epoxy groups in one molecule. Specific examples thereof include bisphenol A type epoxy resin, bisphenol F type epoxy resin, glycidyl ester type epoxy resin obtained by reaction of polybasic acid such as phthalic acid and dimer acid and epichlorohydrin, diamine diphenylmethane, isocyanuric acid and other polyamines. Glycidylamine type epoxy resin obtained by reaction of epichlorohydrin, linear aliphatic epoxy resin obtained by oxidizing olefin bond with peracid such as peracetic acid, and alicyclic epoxy resin, or phenol, cresol, alkylphenol, allylphenol Glycidyl etherified products of phenols such as bisphenol F and bisphenol A, glycidyl etherified products of phenols, glycidyl etherified products of alcohols, and hydrogenated products thereof It is below. These may be used alone or in combination of two or more.

  When silicone modified epoxy resin (B-1) and other liquid epoxy resin (B-2) are used in combination, the blending ratio of silicone modified epoxy resin (B-1) is based on the total amount of liquid epoxy resin (B). And preferably 30% by mass or more, more preferably 35% by mass or more, still more preferably 40% by mass or more, and particularly preferably 50% by mass or more. When the said mixture ratio is less than 30 mass%, the reduction effect of the elasticity modulus of hardened | cured material is inadequate, and it exists in the tendency for curvature to increase.

  The blending ratio of the liquid epoxy resin (B) is not particularly limited, but is preferably 30 to 83% by mass with respect to the total amount of the component (B), the component (C) and the component (F), 30 -75 mass% is more preferable. If the blending amount of the liquid epoxy resin (B) is less than 30% by mass, the crosslink density is low and sufficient strength may not be obtained after molding. If it exceeds 83% by mass, the warpage of the wafer increases with an increase in curing shrinkage. Tends to increase and the water absorption rate tends to increase.

(C) component: phenol resin In this invention, the sclerosis | hardenability of the liquid resin composition for sealing can be improved, without reducing a mechanical characteristic by mix | blending a phenol resin (C). The phenol resin (C) used in the liquid resin composition for sealing of the present invention is not particularly limited as long as it has two or more phenolic hydroxyl groups in one molecule. For example, phenol, cresol, resorcin, catechol, Phenols such as bisphenol A, bisphenol F, phenylphenol and aminophenol and / or naphthols such as α-naphthol, β-naphthol and dihydroxynaphthalene and a compound having an aldehyde group such as formaldehyde are condensed or co-polymerized in an acidic catalyst. Aralkyl-type phenolic resins such as phenol-aralkyl resins and naphthol-aralkyl resins synthesized from novolak-type phenolic resins obtained by condensation, phenols and / or naphthols and dimethoxyparaxylene or bis (methoxymethyl) biphenyl Fat, dicyclopentadiene modified phenolic resin, cyclopentadiene modified phenolic resin, terpene modified phenolic resin, polycyclic aromatic ring modified phenolic resin, triphenolmethane type phenolic resin, bisphenol A, bisphenol F, bisphenol S, thiodiphenol, naphthalenediol Etc. Furthermore, the above-described phenol resin can be used as an allylated product. These phenol resins may be liquid or solid, but are preferably liquid from the viewpoint of lowering the viscosity of the resin composition, and more preferably allylated phenol novolac resins. Moreover, these phenol resins may be used independently or may use 2 or more types together. Commercially available commercially available phenol resins include MEH-8000H (trade name, manufactured by Meiwa Kasei Co., Ltd.). When using a solid phenol resin, it is preferable to use it by dissolving in advance in an organic solvent (F) described later.

  The blending amount of the phenol resin (C) is not particularly limited, but is preferably 2 to 35% by mass, more preferably based on the total amount of the component (B), the component (C) and the component (F). Is 7 to 30% by mass, and the blending ratio of the phenol resin (C) is preferably 10 to 50% by mass, more preferably 15 to 15%, based on the total amount of the component (C) and the component (F). 40% by mass. When the blending amount of the phenol resin (C) is less than the above range, sufficient curability may not be obtained, and when it exceeds the above range, the curability is improved but the water absorption is increased, and the mechanical properties are increased. May decrease.

Component (D): Elastomer The elastomer (D) used in the sealing liquid resin composition of the present invention is not particularly limited, and examples thereof include silicone elastomers, acrylic elastomers, polyolefin elastomers, styrene elastomers, Examples of the copolymer include a core / shell type polymer containing a core layer composed of one type selected from these elastomers and a shell layer composed of one or more other types, such as a silicone rubber particle or a solid silicone polymer. Core / shell type silicone polymer particles containing a core layer made of the above and a shell layer made of an organic polymer are preferred.

  The silicone rubber particles are more preferably silicone rubber particles formed by crosslinking in a liquid epoxy resin by a hydrosilylation reaction of an alkenyl group-containing organopolysiloxane and a SiH group-containing organohydrogenpolysiloxane. Thereby, since the particle size of the silicone rubber particles becomes fine, silicone rubber particles having good dispersibility in the cured product can be obtained. The above reaction in a liquid bisphenol type epoxy resin as a liquid epoxy resin results in the viscosity of the liquid resin composition for sealing finally obtained, the glass transition temperature of the cured product, the adhesiveness, the strength, and the wafer after molding It is preferable from the viewpoint of balance such as warpage. More preferably, the alkenyl group in the organopolysiloxane is a vinyl group. Furthermore, the silicone rubber particles preferably have a functional group capable of reacting with a phenolic hydroxyl group or an epoxy group. Examples of the functional group include a carboxyl group, a hydroxyl group, an isocyanate group, a thiol group, an epoxy group, and an amino group. Among them, an epoxy group is preferable.

  As a specific example of preparing silicone rubber fine particles to which an epoxy group is imparted in a liquid epoxy resin, for example, as disclosed in US Pat. No. 4,853,434, a liquid bisphenol type epoxy resin containing a vinyl group Organopolysiloxane and SiH group-containing organohydrogenpolysiloxane, epoxidized allyl alcohol having an ethylene oxide chain, and allyl glycidyl ether are mixed with each other in the presence of a platinum-based catalyst such as hexachloroplatinic acid, and then dispersed by a dispersing device. Examples thereof include those obtained by stirring at 110 ° C. for 2 hours and crosslinking by a hydrosilylation reaction to produce silicone rubber particles having an epoxy group. Examples of such commercially available silicone rubber particles include ALBIDUR EP2240 (trade name, manufactured by Hanse Chemie, silicone rubber particle-dispersed bisphenol A epoxy resin). Thus, in this invention, it is preferable to mix | blend a silicone rubber particle as a mixture with a liquid epoxy resin (B).

  The silicone rubber particles are preferably spherical, and the particle size is preferably 0.1 μm or more and 2 μm or less, more preferably 0.1 μm or more and 1 μm or less. By using such silicone rubber particles, the average particle size of the silicone rubber particles in the liquid resin composition for sealing of the present invention is reduced, the dispersibility is improved, and the content of the silicone rubber particles is further increased. It becomes possible.

The core / shell type silicone polymer particles contain a core layer made of a solid silicone polymer and a shell layer made of an organic polymer. The solid silicone polymer serving as the core layer is an organopolysiloxane having [RR′SiO _2/2 ] units, and has a trifunctional siloxane unit [RSiO _3/2 ] and / or a tetrafunctional siloxane unit as a crosslinking component [ It is preferable to have SiO _4/2 ]. Here, R is an alkyl group having 6 or less carbon atoms such as a methyl group, an ethyl group, a propyl group, a butyl group, an isobutyl group, a pentyl group or a hexyl group, an aryl group such as a phenyl group, a xylyl group or a tolyl group, or , A vinyl group, an allyl group, a methacryl group, a methacryloxy group, or a substituent having a carbon double bond at the end, such as an alkyl group having these at the end. R ′ represents the same alkyl group or aryl group having 6 or less carbon atoms as R.

  The trifunctional or tetrafunctional siloxane component is preferably used in an amount of 0.5 to 20 mol%, more preferably 2 to 10 mol%. When the trifunctional or tetrafunctional siloxane component is increased, the hardness and elastic modulus of the silicone polymer serving as the core layer are increased, and the effect of reducing the elastic modulus of the cured product of the target sealing liquid resin composition and the effect of reducing the generated stress are obtained. There is a possibility of becoming smaller. Further, when the trifunctional or tetrafunctional siloxane component is decreased, a polymer having a low elastic modulus can be obtained, but the crosslinking density is decreased, so that the unreacted siloxane component tends to increase.

  Further, the organic polymer to be the shell layer is preferably an organic polymer obtained by vinyl polymerization, and examples thereof include polyvinyl butyral, polyvinyl acetate, polystyrene, acrylic polymer, and among these, An acrylic polymer is more preferable. Examples of the acrylic polymer include polymers of acrylic monomers such as acrylic acid, acrylic acid ester, methacrylic acid, methacrylic acid ester, acrylamide, and acrylonitrile, and acrylic monomers such as styrene and vinyltoluene. Examples thereof include a copolymer with a polymerizable vinyl monomer. Among these, polymethacrylic acid ester is preferable. Since the core / shell type silicone polymer particles have the core / shell structure as described above, it is possible to achieve both excellent dispersibility of the organic polymer in the resin and excellent stress relaxation ability of the solid silicone polymer. It becomes.

  The core / shell type silicone polymer particles can be obtained by synthesizing a silicone polymer to be a core layer by emulsion polymerization, and then adding an acrylic monomer and an initiator to perform the second stage polymerization. And a method of forming a shell layer. In this case, an acrylic polymer is grafted through the double bond by appropriately blending the siloxane compound having a double bond with the organosiloxane monomer or oligomer component used in the first stage polymerization, and the core layer and the shell The layer interface becomes strong.

  The particle size of the core / shell type silicone polymer particles is preferably finer in order to uniformly modify the liquid resin composition for sealing, and the average primary particle size is in the range of 0.05 to 1.0 μm. It is preferable that it is in the range of 0.05 to 0.5 μm. When the particle diameter exceeds 1.0 μm, the effect of low warpage tends to be reduced. The core / shell type silicone polymer particles are preferably blended in advance as a mixture with (A) the liquid epoxy resin. As a method of obtaining a mixture, core / shell type silicone polymer particles are added to (A) liquid epoxy resin heated to about 80 to 120 ° C. with stirring, and high-speed shear stirring is performed, or a planetary mixer, homogenizer is used. It can be obtained by mixing and dispersing with a kneader such as a mixer or three rolls.

  The blending amount of the elastomer (D) is not particularly limited, but is preferably 1 to 50 parts by mass, preferably 100 parts by mass with respect to a total of 100 parts by mass of the (B) component, the (C) component and the (F) component. 5 to 40 parts by mass. When the blending amount of the elastomer (D) is less than the above range, the warping tends to be large because the stress reduction is insufficient, and when it exceeds the above range, the strength and moisture resistance of the cured product tend to decrease. .

(E) component: organic solvent Although the organic solvent (E) used for the liquid resin composition for sealing of this invention is not specifically limited, By increase of the compounding quantity of the silicone modified epoxy resin which is (B-1) component. Without causing a decrease in the mechanical strength of the cured product, it gives an optimum viscosity and thixotropic index for the print moldability of the sealing liquid resin composition, and a solid dihydrobenzoxazine ring as a component (F) It is a component for dissolving them when using the compound which has it, or when using a solid phenol resin as (C) component.

  As the organic solvent (E), those having a boiling point of 170 ° C. or higher are preferable from the viewpoint of avoiding void formation due to rapid volatilization at the time of heat curing or suppressing solvent volatilization during printing work, and the boiling point is 200 ° C. The above is more preferable. Moreover, when forming a coating film by vacuum printing, since the sealing liquid resin composition is always handled under vacuum, there exists a possibility that a solvent may volatilize gradually and a viscosity change may arise. In this case, the boiling point of the organic solvent is preferably in the range of 240 ° C to 300 ° C. Specifically, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, triethylene glycol monobutyl ether, tetraethylene glycol monobutyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, ethylene glycol Monohexyl ether, diethylene glycol monohexyl ether, ethylene glycol phenyl ether, ethylene glycol mono-2-ethylhexyl ether, diethylene glycol mono-2-ethylhexyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol Monoethyl ether, dipropylene glycol monobutyl ether, dipropylene glycol propyl ether, tripropylene glycol monomethyl ether, propylene glycol mono n-butyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, 3-methyl-3-methoxybutyl acetate, Examples thereof include butyl carbitol acetate, 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate, 2,2,4-trimethyl-1,3-pentanediol diisobutyrate, and γ-butyrolactone. These may be used alone or in combination of two or more.

  The compounding amount of the organic solvent (E) is not particularly limited, but is preferably 1 to 10% by mass, more preferably 3 to 8% by mass, based on the total amount of the components (A) to (F). It is. When the blending amount of the organic solvent (E) is less than 1% by mass, the effect of reducing the viscosity is insufficient, and the printing workability is not easily lowered or unfilled, and when it exceeds 10% by mass, the viscosity is decreased. Since the fluidity may be increased too much, there is a concern that after printing, the resin composition may flow around to the back side of the wafer, or may cause defects such as voids or significant film loss after curing.

Component (F): Compound having dihydrobenzoxazine ring The compound (F) having a dihydrobenzoxazine ring used in the liquid resin composition for sealing of the present invention is a dihydrobenzoxazine represented by the following formula (a). There is no particular limitation as long as it contains one or more rings in the molecule.

Specific examples of the compound (F) having a dihydrobenzoxazine ring include monofunctional compounds containing one dihydrobenzoxazine ring represented by the following general formulas (III) to (IX), general formulas (X) to (XVI And a polyfunctional compound containing a plurality of dihydrobenzoxazine rings.

  As a commercially available product of a compound having a dihydrobenzoxazine ring, there is RLV100 (trade name, manufactured by Air Water Chemical Co., Ltd.).

  The compound (F) having a dihydrobenzoxazine ring has one or more phenolic hydroxyl groups in one molecule, and at least one ortho-position to the hydroxyl group is not substituted, monocyclic or condensed polycyclic phenols, It can be synthesized by a known method from primary amines having one formaldehyde and one amino group in one molecule. For example, a method in which phenols are dissolved in a solvent such as dioxane, toluene, methanol, ethylene glycol dimethyl ether, methyl ethyl ketone, and primary amines and formaldehyde are added thereto can be used. Usually, the reaction is allowed to proceed without a catalyst, but alkali metal, alkaline earth metal hydroxides, tertiary amines and the like can also be used as catalysts. The raw material charging ratio is usually phenolic hydroxyl group / amino group / aldehyde group = 1/1/2 (molar ratio), and the reaction is carried out at a reaction temperature of 60 to 120 ° C. for 2 to 24 hours. After the elapse of a predetermined time, the target compound having a dihydrobenzoxazine ring can be obtained by removing the organic layer as a reaction product and the condensed water generated by the reaction by distillation or the like.

  The compound (F) having a dihydrobenzoxazine ring obtained by the above reaction contains, as impurities, unreacted phenols in which the phenolic hydroxyl group in the raw material remains without being converted to oxazine. The purity of the compound having a dihydrobenzoxazine ring can be easily calculated from the peak area ratio by gel permeation chromatography. The purity of the compound having a dihydrobenzoxazine ring is preferably 50% or more, more preferably 55% or more, and particularly preferably 60% or more. When the purity of the compound having a dihydrobenzoxazine ring is less than 50%, the storage stability of the encapsulating liquid resin composition is lowered and the warpage of the wafer after molding tends to increase.

  In addition, the compound (F) having a dihydrobenzoxazine ring may be liquid or solid. However, when a compound having a solid dihydrobenzoxazine ring is used, it is preliminarily added to the organic solvent (E) described later. It is preferable to use by dissolving. Moreover, the compound which has a dihydrobenzoxazine ring may be used independently, or may use 2 or more types together.

  Although the compounding quantity of the compound (F) which has a dihydrobenzoxazine ring is not specifically limited, It is 8.5-63 with respect to the total amount of (B) component, (C) component, and (F) component. % By mass is preferable, and 10 to 50% by mass is more preferable. When the compounding amount of the compound (F) having a dihydrobenzoxazine ring is less than 8.5% by mass, the glass transition temperature and the temperature cycle resistance are likely to be significantly lowered. There is a tendency for the strength of the to decrease.

  The encapsulating liquid resin composition of the present invention contains the components (A) to (F). The blending ratio of the component (A) is preferably 64 to 87% by weight, more preferably 73 to 86% by weight, and the blending ratio of the component (B) with respect to the total amount of the components (A) to (F). Is preferably 1.5 to 10% by mass, more preferably 2 to 9% by mass, and the blending ratio of the component (C) is preferably 0.1 to 4% by mass, more preferably 0.15 to 3%. The blending ratio of the component (D) is preferably 0.1 to 10% by weight, more preferably 0.9 to 5% by weight, and the blending ratio of the component (E) is preferably 1 to 10% by weight. It is 10 mass%, More preferably, it is 3-8 mass%, The compounding ratio of (F) component becomes like this. Preferably it is 0.5-8 mass%, More preferably, it is 0.7-6 mass%. When the blending ratio of the component (A) is in the range of 64 to 87% by mass, the warpage is easily reduced. When the blending ratio of the component (B) is in the range of 1.5 to 10% by mass, sufficient strength and glass transition temperature can be easily obtained. When the blending ratio of the component (C) is in the range of 0.1 to 4% by mass, the curing becomes sufficient and the cured product is easily made to absorb moisture. When the blending ratio of the component (D) is in the range of 0.1 to 40% by mass, it becomes easy to reduce warpage after curing. When the blending ratio of the component (E) is in the range of 1 to 10% by mass, the viscosity of the liquid sealing material can be easily maintained in an appropriate range. When the blending ratio of the component (F) is in the range of 0.5 to 8% by mass, sufficient strength and glass transition temperature can be easily obtained.

(Curing accelerator)
Moreover, in order to accelerate | stimulate reaction of an epoxy resin and a phenol resin, the hardening accelerator can be added to the liquid resin composition for sealing of this invention. Any curing accelerator may be used as long as it accelerates the reaction between an epoxy group and a phenolic hydroxyl group. For example, 1,8-diazabicyclo [5,4,0] undecene-7,1,5-diazabicyclo Cycloamidine compounds such as [4,3,0] nonene-5,5,6-dibutylamino-1,8-diazabicyclo [5,4,0] undecene-7, derivatives of the cycloamidine compounds, triethylamine, triethylenediamine , Tertiary amines such as benzyldimethylamine, triethanolamine, dimethylaminoethanol, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl Imidazoles such as 2-methylimidazole, tributylphosphine , Organic diphosphines such as methyldiphenylphosphine, triphenylphosphine, diphenylphosphine, phenylphosphine, tetraphenylphosphonium / tetraphenylborate, triphenylphosphinetetraphenylborate, 2-ethyl-4-methylimidazole / tetraphenylborate, N -Tetraphenylboron salts such as methylmorpholine and tetraphenylborate. These may be used alone or in combination of two or more. Although the compounding quantity of a hardening accelerator is not specifically limited, 0.1-10 mass parts is preferable with respect to 100 mass parts of liquid epoxy resins (B). When the blending amount of the curing accelerator is less than 0.1 parts by mass, the reaction promoting effect tends to be low, and when it exceeds 10 parts by mass, the storage stability tends to decrease.

(Coupling agent)
The liquid resin composition for sealing according to the present invention improves the dispersibility by increasing the affinity between the resin component and the inorganic filler (A-1) containing porous silica whose surface is coated with an inorganic compound. In addition, a coupling agent can be used as necessary. Examples of this coupling agent include known couplings such as various silane compounds such as epoxy silane, mercapto silane, amino silane, alkyl silane, ureido silane, and vinyl silane, titanium compounds, aluminum chelates, and aluminum / zirconium compounds. It is preferable to add an agent. Illustrative examples are vinyltrichlorosilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-acryloxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, vinyltriacetoxysilane, γ-mercaptopropyltrimethoxysilane, γ- Aminopropyltriethoxysilane, γ-anilinopropyltrimethoxysilane, γ-anilinopropylmethyldimethoxysilane, γ- [bis (β-hydroxyethyl)] aminopropyltriethoxysilane, N-β- (Aminoethyl) -γ-aminopropyltrimethoxysilane, γ- (β-aminoethyl) aminopropyldimethoxymethylsilane, N- (trimethoxysilylpropyl) ethylenediamine, N- (dimethoxymethylsilylisopropyl) ethylenediamine, methyltrimethoxy Silane, dimethyldimethoxysilane, methyltriethoxysilane, N-β- (N-vinylbenzylaminoethyl) -γ-aminopropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, hexamethyldisilane, vinyltrimethoxysilane, γ -Silane coupling agents such as mercaptopropylmethyldimethoxysilane, isopropyl triisostearoyl titanate, isopropyl tris (dioctyl pyrophosphate) titanate, isopropyl tri N-aminoethyl-aminoethyl) titanate, tetraoctyl bis (ditridecyl phosphite) titanate, tetra (2,2-diallyloxymethyl-1-butyl) bis (ditridecyl) phosphite titanate, bis (dioctyl pyrophosphate) oxy Acetate titanate, bis (dioctylpyrophosphate) ethylene titanate, isopropyl trioctanoyl titanate, isopropyl dimethacrylisostearoyl titanate, isopropyl tridodecylbenzenesulfonyl titanate, isopropyl isostearoyl diacryl titanate, isopropyl tri (dioctyl phosphate) titanate, isopropyl tricumyl Phenyl titanate, tetraisopropyl bis (dioctyl phosphite) titanate And titanate coupling agents such as These may be used alone or in combination of two or more.

  The blending ratio of the coupling agent is preferably 0.05 to 5% by mass, more preferably 0.1 to 2.5% by mass with respect to the inorganic filler (A). If the blending ratio of the coupling agent is less than 0.05% by mass, the effect of improving the dispersibility of the filler tends not to be obtained, and if it exceeds 5% by mass, voids tend to occur in the cured product.

(Ion trap agent)
Furthermore, an ion trap agent can be used in the liquid resin composition for sealing according to the present invention as needed from the viewpoint of improving the moisture resistance and heat resistance of a semiconductor element such as an IC. The ion trapping agent is not particularly limited and conventionally known ones can be used, for example, hydrotalcites, hydrous oxides of elements such as magnesium, aluminum, titanium, zirconium, bismuth, etc. These may be used alone or in combination of two or more.

  The mixing ratio of the ion trapping agent is not particularly limited as long as it is a sufficient amount capable of capturing anions such as halogen ions and cations such as sodium, but is preferably 1 to 10 mass with respect to the liquid epoxy resin (B). %.

(Other additives)
Furthermore, the liquid resin composition for sealing of the present invention includes a dye; a pigment; a colorant such as carbon black; a phosphate ester, a melamine, a melamine derivative, a compound having a triazine ring, a cyanuric acid derivative, and an isocyanuric acid derivative. Nitrogen-containing compounds, phosphorous nitrogen-containing compounds such as cyclophosphazene, metal compounds such as zinc oxide, iron oxide, molybdenum oxide, and ferrocene, antimony oxides such as antimony trioxide, antimony tetraoxide, and antimony pentoxide, brominated epoxy resins, etc. A conventionally well-known flame retardant; etc. can be mix | blended as needed.

(Preparation of liquid resin composition for sealing)
The liquid resin composition for sealing of the present invention can be prepared by any method as long as the various components can be uniformly dispersed and mixed. As a general method, there can be mentioned a method in which components having a predetermined blending amount are weighed and dispersed and kneaded by a three roll, a crusher, a planetary mixer, a homomixer or the like. Also, use a master batch in which compounding components such as an appropriate amount of liquid epoxy resin, a compound having a dihydrobenzoxazine ring, a phenol resin, silicone rubber particles, an inorganic filler, a coupling agent, and an organic solvent are predispersed and preheated. The method is preferable from the viewpoint of uniform dispersibility and fluidity.

  The liquid resin composition for sealing of the present invention preferably has a viscosity at 25 ° C. of 10 Pa · s to 100 Pa · s, and more preferably 20 Pa · s to 70 Pa · s. If the viscosity is less than 10 Pa · s, the resin composition tends to flow to the wafer edge or the back surface after printing, and if it exceeds 100 Pa · s, the spreadability and fillability tend to decrease.

  What is necessary is just to adjust with the compounding ratio of an organic solvent etc., so that the viscosity of the liquid resin composition for sealing may be 10 Pa.s-100 Pa.s.

  In the liquid resin composition for sealing of the present invention, the throttling index is preferably 1.5 or less, and more preferably 1.3 or less. When the change index exceeds 1.5, the spreadability and defoaming property of the liquid resin composition for sealing tend to decrease.

  What is necessary is just to adjust with a dispersing agent, a rheology control agent, etc., in order to make the change index of the liquid resin composition for sealing become 1.5 or less.

Here, the viscosity can be obtained from Equation (1) using an E-type viscometer (using a 3 ° cone), measuring at 25 rpm and 5 rpm, and using the value at 5 rpm.
Viscosity (Pa · s) = Value at 5 rpm × f1 (1)
(In Formula (1), f1 is a correction coefficient of 5 rpm.)
Further, the fluctuation index can be obtained as a ratio of viscosity at a rotational speed of 1 rpm / viscosity at a rotational speed of 5 rpm.

  In the sealing liquid resin composition of the present invention, the glass transition temperature by dynamic viscoelasticity measurement of the cured product is preferably 50 ° C or higher, more preferably 60 to 165, and more preferably 100 ° C or higher. Is more preferable. When the glass transition temperature is less than 50 ° C., mechanical strength and moisture resistance reliability tend to be lowered. In order for the glass transition temperature of the cured product to be 50 ° C. or higher, it can be adjusted by the compounding amount of the compound having a dihydrohenoxazine ring, the selection of an epoxy resin, a compound having a dihydrobenzoxazine ring, and a phenol resin. Good.

  Here, the glass transition temperature is a temperature indicating a maximum value of the loss tangent when measured using a dynamic viscoelasticity measuring apparatus (frequency: 10 Hz).

  The encapsulating liquid resin composition of the present invention is suitable for encapsulating various elements such as active elements such as semiconductor chips, transistors, diodes, thyristors, and passive elements such as capacitors, resistors, resistor arrays, coils, and switches. Although it can be used, it can be used particularly effectively for sealing an element of a wafer level chip size package that requires low warpage and high reliability.

(Electronic component equipment)
The electronic component device of the present invention comprises an element encapsulated with the encapsulating liquid resin composition of the present invention. Electronic component devices include, for example, lead frames, wired tape carriers, wiring boards, glass, silicon wafers, and other supporting members, active elements such as semiconductor chips, transistors, diodes, thyristors, capacitors, resistors, resistor arrays An electronic component device obtained by mounting an element such as a passive element such as a coil or a switch and sealing a necessary portion with the liquid resin composition for sealing of the present invention. Especially, the liquid resin composition for sealing of the present invention is effective for an electronic component device that requires low warpage and high reliability, and is particularly suitable for a wafer level chip size package.

  Examples of a method for sealing an element using the sealing liquid resin composition of the present invention include a dispensing method, a casting method, a printing method, and the like, and a printing method is particularly preferable.

  Examples of a method for sealing an element formed on a wafer using the sealing liquid resin composition of the present invention include a dispensing method, a casting method, a printing method, and the like, and a printing method is particularly preferable. .

  EXAMPLES Next, although an Example demonstrates this invention, the scope of the present invention is not limited to these Examples.

(Production Example 1: Silicone-modified epoxy resin)
“KF-105” (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.) as an epoxy resin having a siloxane structure in a 1-liter flask equipped with a nitrogen introduction tube, a thermometer, a cooling tube and a mechanical stirrer, an epoxy having a siloxane structure “TSL 9906” (trade name, manufactured by GE Toshiba Silicone Co., Ltd.) 74.8 g as resin, 67 g of terpene diphenol “YP-90” (trade name, manufactured by Yasuhara Chemical Co., Ltd.), and 1,8-diazabicyclo (5, 4, 0 as catalyst) ) Undecene-7 (trade name “DBU” manufactured by San Apro Co., Ltd.) (2.8 g) was added and reacted at 150 ° C. for 5 hours in a nitrogen atmosphere to obtain an epoxy equivalent of 830 g / eq. A liquid silicone-modified epoxy resin 1 was obtained.

(Production Example 2: Production of Compound 1 having a Dihydrobenzoxazine Ring)
Bisphenol F 1.0 kg (equivalent to 5 mol) and 0.93 kg of aniline (equivalent to 10 mol) were mixed in 0.5 kg of methyl ethyl ketone and stirred at 80 ° C. for 5 hours to prepare a uniform mixed solution. Into a 5 liter flask, 1.62 kg of formalin was charged and heated to 90 ° C., and a mixed solution of bisphenol F / aniline / methyl ethyl ketone was added little by little over 30 minutes. After completion of the addition, the reflux temperature was maintained for 30 minutes. After that, the condensed water was removed by reducing the pressure to 6666.1 Pa or less at 100 ° C. for 2 hours, and 75% of the reactive phenolic hydroxyl group was oxazineated. Compound 1 having a dihydrobenzoxazine ring represented by general formula (X) was obtained. The reaction rate was calculated from the ratio of the number of moles of condensed water removed to the number of moles of phenolic hydroxyl groups that can react.

[Preparation of liquid resin composition for sealing]
(Examples 1-8 and Comparative Examples 1-7)
The following components are blended in parts by mass shown in Tables 1 to 4 and kneaded with three rolls under conditions of a roll pressure of 10 to 30 kgf, and then a crusher under conditions of a kneading temperature of 25 ° C and a kneading time of 30 minutes. After kneading and dispersing in, vacuum degassing was carried out to produce sealing liquid resin compositions of Examples 1 to 8 and Comparative Examples 1 to 7.

  The ratio in Table 1 to Table 4 is mass%, and the number of blended parts is mass parts.

  In Tables 1-4, (E) Examples 1, 2, and 7, and Comparative Examples 1 to 5 using a liquid epoxy resin 2 / silicone rubber mixture as an elastomer, the liquid epoxy resin 2 / Include in the column of silicone rubber mixture. Since the liquid epoxy resin 2 / silicone rubber mixture is a mixture comprising 60% by mass of liquid epoxy resin 2 and 40% by mass of silicone rubber fine particles, the liquid used in Examples 1, 2, 7 and Comparative Examples 1-5. Table 4 shows the number of blended liquid epoxy resin 2 and silicone rubber fine particles in the epoxy resin 2 / silicone rubber mixture. For example, the liquid epoxy resin 2 / silicone rubber mixture used in Example 1 is a mixture of 30 parts by mass of liquid epoxy resin 2 and 20 parts by mass of silicone rubber fine particles, and the liquid epoxy resin 2 / silicone used in Example 2 is used. The rubber mixture is a mixture of 21 parts by mass of liquid epoxy resin 2 and 41 parts by mass of silicone rubber fine particles.

(A) Inorganic filler Fused silica 1: Spherical fused silica having an average particle size of 0.5 μm Fused silica 2: Spherical fused silica having an average particle size of 4 μm Porous silica 1: Average particle size of 10 μm, specific surface area of 1.1 m ² / g , Porous silica whose surface has a compressive strength of 519.8 MPa and coated with silicon dioxide (Catalyst Kasei Kogyo Co., Ltd., product name “HOLLOWY N-15”)
Porous silica 2: porous silica having an average particle size of 5 μm, a specific surface area of 838 m ² / g, and a compressive strength of 40 MPa (Asahi Glass S-Tech Co., Ltd., product name “Sunsphere H-51”)
(B) Liquid epoxy resin Liquid epoxy resin 1: Bisphenol F type epoxy resin (trade name “YDF8170C” manufactured by Tohto Kasei Co., Ltd.)
Silicone-modified poxy resin 1: Liquid silicone-modified poxy resin 1 obtained in Production Example 1
Silicone-modified epoxy resin 2: Liquid silicone-modified epoxy resin having an epoxy equivalent of 804 g / eq (trade name “ALBIFEX 296” manufactured by Hanse Chemie)
(C) Phenol resin Phenol resin 1: An allylated phenol novolak resin (trade name “MEH-8000H” manufactured by Meiwa Kasei Co., Ltd.) having a hydroxyl group equivalent of 140 and a viscosity of 1.7 Pa · s (25 ° C.).
(C ′) Acid anhydride curing agent Acid anhydride curing agent: trade name “MHAC-HR” manufactured by Hitachi Chemical Co., Ltd.
(D) Elastomer Liquid Epoxy Resin 2 / Silicone Rubber Mixture: Silicone fine rubber particles having epoxy groups crosslinked by hydrosilylation reaction of alkenyl group-containing organopolysiloxane and SiH group-containing organohydrogenpolysiloxane are liquid bisphenol-type epoxy resins. (Liquid epoxy resin 2: bisphenol A type epoxy resin (trade name “Epomic R140P” manufactured by Mitsui Chemicals, Inc.) dispersed in a silicone rubber fine particle-containing liquid bisphenol A type epoxy resin (silicone rubber fine particle content 40% by mass, Silicone rubber fine particle diameter of 0.1 to 1.0 μm, trade name “ALBIDUR EP2240” manufactured by Hanse Chemie)
Core-shell silicone polymer particles: a dimethyl type solid silicone polymer in which the core layer contains 3 mol% of methyltrimethoxysilane and 2 mol% of methacryloxypropyltrimethoxysilane as a trifunctional siloxane component, and the shell layer is composed of polymethylmethacrylate, Core / shell type silicone polymer particles having a core layer / shell layer mass ratio of 2/1 and an average primary particle size of 0.12 μm (E) Organic solvent Compound having diethylene glycol monoethyl ether acetate (F) dihydrobenzoxazine ring Compound 1 having dihydrobenzoxazine ring 1: Compound 1 having dihydrobenzoxazine ring obtained in Production Example 2
(Curing accelerator)
Curing accelerator 1: Triphenylphosphine (Reagent manufactured by Wako Pure Chemical Industries, Ltd.)
Curing accelerator 2: 2-ethyl-4-methylimidazole (Shikoku Kasei Kogyo Co., Ltd. product name “CURESOL 2E4MZ”)
(Coupling agent)
Coupling agent: γ-glycidoxypropyltrimethoxysilane (trade name “KBM403” manufactured by Shin-Etsu Chemical Co., Ltd.)
(Coloring agent)
Carbon black (ion trapping agent)
Ion trap agent: Bismuth-based anion trap agent (trade name “IXE500”, Toagosei Co., Ltd.)
[Characteristic evaluation of liquid resin composition for sealing]
The characteristics of the sealing liquid resin compositions produced in Examples 1 to 8 and Comparative Examples 1 to 7 were evaluated by the tests shown in (1) to (7) below. The evaluation results are shown in Tables 1 to 4.

  In addition, the heat curing of the liquid resin composition for sealing in various trials is performed at 130 ° C. for 1 hour and then at 180 ° C. for 3 hours in Examples 1 to 8 and Comparative Examples 1 to 6, and in Comparative Example 7 at 100 ° C. 1 hour, then at 150 ° C. for 2 hours.

(1) Viscosity and Fluctuation Index The viscosity at 25 ° C. of the liquid resin composition for sealing was measured using an E-type viscometer (manufactured by Tokyo Keiki Co., Ltd., cone angle 3 °, rotation speed 5 rpm). The change index was calculated as the ratio of the viscosity measured at 1 rpm to the viscosity measured at 5 rpm (viscosity at 1 rpm / 5 viscosity at 5 rpm).

(2) Warpage On a 8-inch silicon wafer (thickness: about 730 μm), using a metal mask with an opening of 197 mmφ and a thickness of 300 μm, a liquid resin composition for sealing is applied by a printing molding method and cured by heating to a resin thickness of about A 200 μm wafer with resin was prepared. Both surfaces of this resin-coated wafer were ground to a resin thickness of 70 μm and a wafer thickness of 230 μm. The ground wafer was reflowed at 260 ° C. The warpage of the wafer was measured by measuring the maximum height after 15 hours had elapsed from the curing, after grinding and after reflowing, by fixing one end of the wafer on the surface plate.

(3) Glass transition temperature and elastic modulus The liquid resin composition for sealing was heat-cured into a sheet having a thickness of about 290 μm, and this sheet was cut into 4 mm × 34 mm to prepare test pieces. And using a dynamic viscoelasticity measuring device DVE type (manufactured by Rheology Co., Ltd.), continuous vibration with a sine wave with a chuck distance of 25 mm and a frequency of 10 Hz, a strain amount of 5 μm, an automatic static load, a heating rate of 3 ° C./min. The glass transition temperature was measured at a temperature range of 20 to 250 ° C. and the temperature showing the maximum value of the loss tangent. Moreover, the storage elastic modulus of 25 degreeC was read.

(4) Dicing blade wearability A resin-coated wafer having a resin thickness of about 200 μm was produced in the same manner as in (2) above. This wafer with resin was diced into 1 mm squares using an automatch dicing saw DAD341 (manufactured by Disco), and the amount of blade wear after dicing was measured. As a dicing blade, NBC-ZH-2050-SE27HEDG manufactured by Disco Corporation was used, and the amount of blade wear was measured at a rotational speed of 35,000 rpm and a feed rate of 50 mm / s.

(5) Reflow resistance A liquid resin composition for sealing is applied to an 8-inch silicon wafer (thickness: about 730 μm) coated with polyimide using a metal mask with an opening of 197 mmφ and a thickness of 250 μm by a printing molding method under reduced pressure. Then, it was heat-cured to produce a wafer with resin having a resin thickness of about 160 μm. The wafer with resin was diced into 5 mm square using an automatch dicing saw DAD341 (manufactured by Disco Corporation) to prepare a test piece. The test piece was subjected to 260 ° C. reflow treatment 20 times after saturated moisture absorption under the condition of 85 ° C./85% RH. Then, the appearance of the test piece and the wafer cross-section were observed, and the evaluation was made based on the number of the test pieces in which the appearance defect (hanging, cracks, etc.) or peeling occurred / the number of measurement test pieces (30).

(6) Temperature cycle resistance A 5 mm square test piece was produced in the same manner as in (5) above. This test piece was repeated 1000 cycles with a heat cycle of 15 minutes at −50 ° C. and then 15 minutes at 150 ° C., the appearance of the test piece and the wafer cross-section were observed, and the appearance was poor (deposition, cracks, etc.) or peeling Was evaluated by the number of test pieces in which the number of occurrences / the number of measurement test pieces (30).

(7) Moisture resistance reliability A test element group (TEG) in which an electroplated Cu film was formed in a comb-like electrode shape with a line / space of 15 μm / 25 μm and a thickness of 5 μm on a polyimide-coated silicon wafer was produced. Next, the comb electrode part was heat-cured with a sealing liquid resin composition to a thickness of about 90 μm, and the sealed TEG was subjected to a continuity test for 300 hours under an environment of 135 ° C. and 85% RH with 7.5 V applied. The number of defective packages / the number of measurement packages (10) was evaluated.

  The sealing liquid resin compositions obtained in Examples 1 to 8 exhibited good characteristics in any evaluation.

  On the other hand, both Comparative Example 1 using fused silica 2 instead of porous silica 1 of Example 1 and Comparative Example 5 using fused silica 2 instead of porous silica 1 of Example 2 were both dicing. There was a lot of blade wear. In Comparative Example 2 not containing porous silica 1, the cured product had a low elastic modulus of 5 GPa and a large amount of dicing blade wear. In Comparative Example 3, porous silica 1 was used in place of fused silica 2 of Comparative Example 2, but the cured product elastic modulus was as low as 5 GPa, and the amount of wear of the dicing blade was large, and could not be improved. In Comparative Example 4 in which porous silica 2 having a large specific surface area was used instead of porous silica 1 in Example 1, the viscosity was remarkably increased although the blending ratio of the organic solvent was increased to 10% by mass. The sample could not be prepared. The comparative example 6 which did not mix | blend an elastomer had large curvature, and its temperature cycle resistance was also low. Moreover, the comparative example 7 which used the acid anhydride type hardening | curing agent instead of the phenol resin as a hardening | curing agent had large curvature, and reflow resistance and moisture-proof reliability were inadequate.

  According to the encapsulating liquid resin composition of the present invention, even when applied to an electronic component device that requires low warpage such as a wafer level chip size package, the warpage is suppressed to a small level, and the strength, thermal shock resistance, and moisture resistance are reduced. A liquid resin composition for sealing excellent in reliability such as reliability and processability, and an electronic component device and a wafer level chip size package comprising an element sealed with the liquid resin composition for sealing be able to.

Claims (16)

  A liquid resin composition for sealing containing an inorganic filler (A) containing porous silica particles whose surface is coated with an inorganic compound, which is 25 ° C. of the cured product of the liquid resin composition for sealing. The liquid resin composition for sealing whose elastic modulus in is 6-15GPa. The liquid resin composition for sealing according to claim 1, wherein the specific surface area of the porous silica particles whose surfaces are coated with an inorganic compound is 0.5 to 10.0 m ² / g.   The liquid resin composition for sealing according to claim 1 or 2, wherein the compressive strength of the porous silica particles whose surface is coated with an inorganic compound is 30 to 1500 MPa.   Furthermore, it contains a liquid epoxy resin (B), a phenol resin (C), an elastomer (D) and an organic solvent (E), and the liquid epoxy resin (B) contains at least 30% by mass of a silicone-modified epoxy resin. The liquid resin composition for sealing as described in any one of Claims 1-3 characterized by the above-mentioned.   Furthermore, the compound (F) which has a dihydrobenzoxazine ring is contained, The liquid resin composition for sealing of Claim 4 characterized by the above-mentioned. The liquid resin composition for sealing according to claim 4 or 5, wherein the silicone-modified epoxy resin is an epoxy resin having a siloxane structure represented by the following general formula (I).

(R ¹ and R ² in the general formula (I) represent an alkyl group or an aryl group, and may be the same or different, and n is an integer of 1 or more.)   The blending ratio of the liquid epoxy resin (B) is 30 to 83% by mass and the blending ratio of the compound (F) having a dihydrobenzoxazine ring with respect to the total amount of the component (B), the component (C) and the component (F). Is 8.5 to 63 mass%, the blending ratio of the phenol resin (C) is 2 to 35 mass%, and the total amount of the (C) component and the (F) component is that of the phenol resin (C). The liquid resin composition for sealing according to claim 5 or 6, wherein the blending ratio is 10 to 50% by mass.   The elastomer (D) is a silicone rubber particle formed by crosslinking in a liquid epoxy resin by a hydrosilylation reaction of an alkenyl group-containing organopolysiloxane and a SiH group-containing organohydrogenpolysiloxane. The liquid resin composition for sealing according to item.   The liquid resin composition for sealing according to claim 8, wherein the silicone rubber particles have an average particle size of 0.1 to 2 μm.   The said elastomer (D) is a core / shell type silicone polymer particle containing the core layer which consists of a solid silicone polymer, and the shell layer which consists of an organic polymer, As described in any one of Claims 4-7. Liquid resin composition for sealing. The core / shell type silicone polymer particles have units consisting of [RSiO _3/2 ] and / or [SiO _4/2 ], wherein [RR′SiO _2/2 ] units (where R is a carbon number of 6 A core layer made of a silicone polymer containing the following alkyl group, aryl group, or substituent having a carbon double bond at the end, and R ′ represents an alkyl group or aryl group having 6 or less carbon atoms): The liquid resin composition for sealing according to claim 10, comprising a shell layer made of an organic polymer obtained by vinyl polymerization.   The liquid resin composition for sealing according to claim 10 or 11, wherein the organic polymer is an acrylic polymer.   The compounding quantity of the said elastomer (D) is 1-50 mass parts with respect to a total of 100 mass parts of (B) component, (C) component, and (F) component, It is any one of Claims 4-12 The liquid resin composition for sealing as described.   The electronic component apparatus provided with the element sealed with the liquid resin composition for sealing as described in any one of Claims 1-13.   The liquid resin composition for sealing according to any one of claims 1 to 13, which is used for sealing a wafer level chip size package.   A wafer level chip size package comprising an element encapsulated with the encapsulating liquid resin composition according to claim 1.