JP6555042B2 - Granular resin composition - Google Patents

Description

  The present invention relates to a granular resin composition suitable as a sealing material for semiconductor encapsulation, particularly a wafer level chip size package.

  A sealing material used for a semiconductor package such as a wafer level chip size package is required to have a low elastic modulus in order to suppress warpage of the substrate (package substrate). For example, Patent Document 1 discloses a thermosetting resin composition containing a specific linear modified polyimide resin and a thermosetting resin as a low elastic modulus thermosetting resin composition. However, when sealing is performed using a film of such a thermosetting resin composition, it is particularly difficult to form a thick film (for example, 200 μm or more), and it is necessary to stack a plurality of films. However, if a plurality of films are formed and stacked, air bubbles are likely to enter between the films, which causes foaming and delamination (that is, delamination) after reflow. On the other hand, when sealing is performed using a liquid material of such a thermosetting resin composition, the liquid resin composition has a high viscosity, and when the resin composition is dispensed, the liquid does not run out easily, and on the wafer. It takes a very long time to uniformly disperse the resin composition, and as a result, an underfill property is insufficient under the chip. Further, a flow mark is generated to spread the liquid resin composition, and the flow mark causes a defective appearance of the product and a decrease in package reliability.

JP 2006-37083 A

  The present invention has been made paying attention to the above-described circumstances, and its purpose is to suppress warpage, delamination and flow marks of a substrate (package substrate) when used as a sealing material for a semiconductor package. It is in providing the resin composition which can be performed. In particular, it is to provide a resin composition that can suppress warpage of a substrate (package substrate), delamination and flow marks at the interface with a semiconductor chip, and enables mold underfill exhibiting good underfill properties. .

  In order to solve the above-mentioned problems, the present inventor has intensively studied, and as a result, a curable resin composition containing a polymer resin having a specific polymer structure and a specific number average molecular weight, an epoxy resin, and an inorganic filler. The present inventors have found that the above-mentioned problems can be solved by making the particles of a specific average particle diameter into a granular shape. That is, the present invention is as follows.

[1] (A) a polymer resin having a number average molecular weight of 5000 to 25000 and having one or more structures selected from a polybutadiene structure, a polyisoprene structure, a polycarbonate structure, a (meth) acrylate structure, and a polysiloxane structure;
(B) inorganic filler,
(C) An epoxy resin, and (D) a granular resin composition containing a curing accelerator,
A granular resin composition having an average particle size of 60 μm or more.
[2] The granular resin composition according to the above [1], wherein the average particle size is 60 μm or more and 300 μm or less.
[3] The granular resin composition according to the above [1] or [2], wherein the angle of repose is 30 ° to 60 °.
[4] The polymer resin as the component (A) is a polyimide resin having one or more structures selected from a polybutadiene structure, a polyisoprene structure, a polycarbonate structure, a (meth) acrylate structure, and a polysiloxane structure. The granular resin composition according to any one of [1] to [3].
[5] The structure represented by the formula (1-a) and the structure represented by the formula (1-b) of the polymer resin as the component (A):

[Wherein R1 represents a divalent organic group having a polybutadiene structure, a divalent organic group having a polyisoprene structure, or a divalent organic group having a polycarbonate structure, and R2 represents a tetravalent organic group. R3 represents a divalent organic group. ]
The granular resin composition according to any one of [1] to [4] above, which is a polyimide resin having
[6] The granular resin composition according to any one of [1] to [5], wherein (C) the epoxy resin includes (C1) an epoxy resin that is solid at 25 ° C.
[7] The above [1] to [6], wherein the (C) epoxy resin includes (C1) an epoxy resin that is solid at 25 ° C, and (C2) an epoxy resin that is liquid at 25 ° C. Granular resin composition.
[8] The content of the polymer resin as the component (A) is 6 to 40% by mass with respect to the entire nonvolatile components of the resin composition, and the content of the inorganic filler as the component (B) is nonvolatile in the resin composition. The granular resin composition according to any one of the above [1] to [7], which is 50 to 92% by mass based on the total components.
[9] The granular resin composition according to any one of [1] to [8], which is used for a sealing material for a semiconductor package.
[10] The granular resin composition according to any one of [1] to [8], which is for mold underfill.

According to the granular resin composition of the present invention, it is possible to provide a semiconductor package sealing material capable of suppressing warpage, delamination and flow mark of a substrate (package substrate).
According to the granular resin composition of the present invention, it is possible to provide a mold underfill material that can suppress warpage of a substrate (package substrate) and delamination at an interface with a chip and is excellent in underfill properties.

<(A) Polymer resin having a number average molecular weight of 5000 to 25000>
The granular resin composition of the present invention (hereinafter also simply referred to as “resin composition”) contains a polymer resin having a number average molecular weight of 5000 to 25000 as the component (A). The polymer resin which is a component (A) can use 1 type (s) or 2 or more types.

  Since the polymer resin as the component (A) has a number average molecular weight of 5,000 to 25,000, sufficient heat resistance is imparted to the resin composition. The number average molecular weight of the polymer resin is preferably 7,000 to 22,000, more preferably 9,000 to 20,000. Here, the number average molecular weight of the polymer resin is a value measured by a gel permeation chromatography (GPC) method (polystyrene conversion). Specifically, the number average molecular weight determined by the GPC method is LC-9A / RID-6A manufactured by Shimadzu Corporation as a measuring device, and Shodex K-800P / K-804L / K- manufactured by Showa Denko KK as a column. 804 L can be measured using chloroform as a mobile phase at a column temperature of 40 ° C. and calculated using a standard polystyrene calibration curve.

  From the viewpoint of imparting sufficient flexibility to the cured product of the resin composition, the glass transition temperature of the polymer resin as the component (A) is preferably 30 ° C. or lower, more preferably −15 ° C. to 29 ° C., and further Preferably it is -10 degreeC-20 degreeC. Here, the glass transition temperature of the polymer resin can be read from a tan δ peak temperature obtained by dynamic viscoelasticity measurement or thermomechanical analysis by a tensile load method using a thermomechanical analyzer.

  The content of the polymer resin as the component (A) is preferably 10 to 80% by mass, based on the entire nonvolatile component in the resin composition, from the viewpoint of securing the adhesion between the resin composition and the adherend. More preferably, it is 12-75 mass%, More preferably, it is 13-70 mass%.

  The polymer resin as component (A) is preferably a resin having one or more structures selected from a polybutadiene structure, a polyisoprene structure, a polycarbonate structure, a (meth) acrylate structure, and a polysiloxane structure. Both the polybutadiene structure and the polyisoprene structure may be hydrogenated. The polymer resin is more preferably a polyimide resin having one or more structures selected from a polybutadiene structure, a polyisoprene structure, a polycarbonate structure, a (meth) acrylate structure, and a polysiloxane structure, and more preferably a polybutadiene structure, A polyimide resin having an isoprene structure or a polycarbonate structure, particularly preferably a polyimide resin having a polybutadiene structure or a polycarbonate structure.

  When a polyimide resin is used as the component (A), the acid value is preferably 3 to 30 mgKOH / g, more preferably 5 to 20 mKOH / g.

  Examples of the polybutadiene structure include a polybutadiene structure represented by the formula (ia) or the formula (ib), or a hydrogenated polybutadiene structure represented by the formula (ic) or the formula (id). Can be mentioned.

[In the formulas (ia) to (id), n1 represents an integer of 5 to 30 (preferably an integer of 10 to 20). ]

  Examples of the polyisoprene structure include a polyisoprene structure represented by the formula (ii-a) or a hydrogenated polyisoprene structure represented by the formula (ii-b).

[In the formulas (ii-a) and (ii-b), n2 represents an integer of 5 to 30 (preferably an integer of 10 to 20). ]

  Examples of the polycarbonate structure include those represented by the formula (iii).

[In Formula (iii), R4 and R5 each independently represent an alkylene group having 1 to 20 carbon atoms (preferably 1 to 10 carbon atoms), and n3 is an integer of 5 to 30 (preferably 10 to 20). Integer). ]

  Examples of the (meth) acrylate structure include those represented by the formula (iv).

[In Formula (iv), R6 represents a hydrogen atom or a methyl group, and R7 represents an alkyl group having 1 to 20 carbon atoms or a hydroxyalkyl group having 1 to 20 carbon atoms. ]

  Examples of the polysiloxane structure include those represented by the formula (v).

(In the formula, R8 and R9 each independently represent an alkylene group having 1 to 5 carbon atoms, a phenylene group or an oxyalkylene group having 1 to 5 carbon atoms, and R10 to R14 each independently represent a carbon number. An alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or a phenoxy group, a, b and c each independently represent an integer of 0 or more, and b + c ≧ 1 and a + b + c ≧ 60 In the formula, a hydrogen atom on the benzene ring may be substituted with a halogen atom, an alkyl group having 1 to 8 carbon atoms, or the like.)

  Specific examples of the resin having a polysiloxane structure include those described in International Publication No. 2010/053185.

  Examples of the polyimide resin having a polybutadiene structure, a polyisoprene structure, or a polycarbonate structure include a structure represented by the formula (1-a) and a structure represented by the formula (1-b):

[Wherein R1 represents a divalent organic group having a polybutadiene structure, a divalent organic group having a polyisoprene structure, or a divalent organic group having a polycarbonate structure (preferably a divalent organic group having a polybutadiene structure). Group or a divalent organic group having a polycarbonate structure), R2 represents a tetravalent organic group, and R3 represents a divalent organic group. ]
(Hereinafter sometimes abbreviated as “polyimide resin (1-a) (1-b)”).

  Among the polyimide resins (1-a) (1-b), a structure represented by the formula (abc):

[In formula, R1-R3 is synonymous with the above, and n and m show an integer. ]
A polyimide resin (hereinafter sometimes abbreviated as “polyimide resin (abc)”) is preferred. n is an integer of, for example, 1 to 100, preferably an integer of 1 to 10, and m is an integer of, for example, 1 to 100, preferably an integer of 1 to 10. Hereinafter, the polyimide resin (1-a) (1-b) and the polyimide resin (abc) may be collectively referred to as “polyimide resin (A)”.

  The divalent organic group having a polybutadiene structure is, for example, a residue excluding the hydroxy group of a bifunctional hydroxy group-terminated polybutadiene used as a raw material. Examples of such groups include the following.

[In the formulas (ia) to (id), n1 represents an integer of 5 to 30 (preferably an integer of 10 to 20). ]

  The divalent organic group having a polyisoprene structure is, for example, a residue excluding the hydroxy group of a bifunctional hydroxy group-terminated polyisoprene used as a raw material. Examples of such groups include the following.

[In the formulas (ii-a) and (ii-b), n2 represents an integer of 5 to 30 (preferably an integer of 10 to 20). ]

  The divalent organic group having a polycarbonate structure is, for example, a residue excluding the hydroxy group of polycarbonate diol used as a raw material. Examples of such groups include the following.

[In Formula (iii), R4 and R5 each independently represent an alkylene group having 1 to 20 carbon atoms (preferably 1 to 10 carbon atoms), and n3 is an integer of 5 to 30 (preferably 10 to 20). Integer). ]

  The tetravalent organic group is, for example, a residue excluding a carboxy group or an acid anhydride group of a polybasic acid or its anhydride used as a raw material. Examples of such tetravalent organic groups include the following groups.

[Wherein, A is an oxygen atom, a sulfur atom, CO, SO, SO ₂ , CH ₂ , CH (CH ₃ ), C (CH ₃ ) ₂ , C (CF ₃ ) ₂ , or C (CCl ₃ ) ₂ Represents. In the formula, a hydrogen atom on the aromatic ring may be substituted with a halogen atom, an alkyl group having 1 to 8 carbon atoms, or the like. ]

  The divalent organic group which is R3 is, for example, a residue excluding the isocyanate group of the diisocyanate compound. Examples of the diisocyanate compound include aromatic diisocyanates such as toluene-2,4-diisocyanate, toluene-2,6-diisocyanate, xylylene diisocyanate, and diphenylmethane diisocyanate; aliphatic diisocyanates such as hexamethylene diisocyanate; fats such as isophorone diisocyanate. And cyclic diisocyanates. Among these, aromatic diisocyanates and alicyclic diisocyanates are preferable, and toluene-2,4-diisocyanate and isophorone diisocyanate are more preferable.

  A polyimide resin having a polybutadiene structure, a polyisoprene structure or a polycarbonate structure can be produced, for example, as follows. First, a bifunctional hydroxy group-terminated polybutadiene, a bifunctional hydroxy group-terminated polyisoprene or a polycarbonate diol, and a diisocyanate compound are converted into a bifunctional hydroxy group-terminated polybutadiene, a bifunctional hydroxy group-terminated polyisoprene, or a hydroxy group 1 of a polycarbonate diol. The amount of the isocyanate group of the diisocyanate compound with respect to mol is reacted at a ratio exceeding 1 mol, and the formula (ab):

[Wherein R 1, R 3 and n are as defined above. ]
The diisocyanate reaction product represented by the formula (hereinafter sometimes abbreviated as “diisocyanate reaction product (ab)”) is produced.

  The number average molecular weight of the bifunctional hydroxy group-terminated polybutadiene used as a raw material is preferably 800 to 10,000, more preferably 1,000 to 6,000, from the viewpoint of good compatibility with other raw materials. It is. The method for measuring the number average molecular weight of the bifunctional hydroxy group-terminated polybutadiene is the same as the method for measuring the number average molecular weight of the polymer resin (GPC method). The preferred number average molecular weight of the residue excluding the hydroxy group of the bifunctional hydroxy group-terminated polybutadiene as R1 is the same as described above.

  Commercially available products can be used as the bifunctional hydroxy group-terminated polybutadiene. Examples of such commercial products include G-3000, G-1000, GI-3000, GI-1000 manufactured by Nippon Soda Co., Ltd., R-45EPI manufactured by Idemitsu Petrochemical Co., Ltd., and the like.

  The number average molecular weight of the bifunctional hydroxy group-terminated polyisoprene used as a raw material is preferably 800 to 10,000, more preferably 1,000 to 6, from the viewpoint of good compatibility with other raw materials. 000. The method for measuring the number average molecular weight of the bifunctional hydroxy group-terminated polyisoprene is the same as the method for measuring the number average molecular weight of the polymer resin (GPC method). The preferred number average molecular weight of the residue excluding the hydroxy group of the bifunctional hydroxy group-terminated polyisoprene as R1 is the same as described above.

  Commercially available products can be used as the bifunctional hydroxy group-terminated polyisoprene.

  The number average molecular weight of the polycarbonate diol used as the raw material is preferably 500 to 5,000, more preferably 1,000 to 3,000, from the viewpoint of good compatibility with other raw materials. In addition, the measuring method of the number average molecular weight of polycarbonate diol is the same as the measuring method (GPC method) of the above-mentioned polymer resin. Moreover, the preferable number average molecular weight of the residue except the hydroxyl group of polycarbonate diol which is said R1 is also the same as the above.

  A commercially available product can be used as the polycarbonate diol. Examples of such commercially available products include C-1015N and C-2015N manufactured by Kuraray Co., Ltd., T-6002, T-4672, T-5562 manufactured by Asahi Kasei Chemicals Corporation, and CD205 manufactured by Daicel Corporation. CD205PL, CD205HL, CD210, CD210PL, Nippon Polyurethane Industry Co., Ltd. Nippon Run 981, 980R, and the like.

  Examples of the diisocyanate compound used as a raw material include aromatic diisocyanates such as toluene-2,4-diisocyanate, toluene-2,6-diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate; aliphatic diisocyanates such as hexamethylene diisocyanate; isophorone diisocyanate. And alicyclic diisocyanates such as Among these, aromatic diisocyanates and alicyclic diisocyanates are preferable, and toluene-2,4-diisocyanate and isophorone diisocyanate are more preferable.

  Bifunctional hydroxy group-terminated polybutadiene, difunctional hydroxy group-terminated polyisoprene or polycarbonate diol, in an amount such that the molar ratio of hydroxy group: isocyanate group of diisocyanate compound is 1: 1.5 to 1: 2.5. It is preferable to react.

  The reaction between the bifunctional hydroxy group-terminated polybutadiene and the difunctional hydroxy group-terminated polyisoprene or polycarbonate diol and the diisocyanate compound is usually carried out in an organic solvent at a temperature of 80 ° C. or lower for 1 to 8 hours. In this reaction, a catalyst may be used if necessary.

  Examples of the organic solvent include N, N′-dimethylformamide, N, N′-diethylformamide, N, N′-dimethylacetamide, N, N′-diethylacetamide, dimethyl sulfoxide, diethyl sulfoxide, N-methyl- Examples include polar solvents such as 2-pyrrolidone, tetramethylurea, γ-butyrolactone, cyclohexanone, diglyme, triglyme, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate. These polar solvents may use only 1 type and may use 2 or more types together. Further, if necessary, nonpolar solvents such as aromatic hydrocarbons may be appropriately mixed and used.

  Examples of the catalyst include organometallic catalysts such as dibutyltin dilaurate, dimethyltin dichloride, cobalt naphthenate, and zinc naphthenate.

  Next, a polybasic acid or an anhydride thereof is reacted with the obtained diisocyanate reactant (ab).

  Examples of the polybasic acid or its anhydride used as a raw material include pyromellitic acid, benzophenone tetracarboxylic acid, biphenyl tetracarboxylic acid, naphthalene tetracarboxylic acid, 5- (2,5-dioxotetrahydrofuryl) -3- Tetrabasic acids such as methyl-cyclohexene-1,2-dicarboxylic acid, 3,3′-4,4′-diphenylsulfonetetracarboxylic acid and their anhydrides, tribasic acids such as trimellitic acid, cyclohexanetricarboxylic acid, and the like; These anhydrides, 1,3,3a, 4,5,9b-hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphth (1,2-C) furan-1,3-dione Etc. Among these, tetrabasic acid anhydrides are preferable, tetrabasic acid dianhydrides are more preferable, and benzophenone tetracarboxylic dianhydride is more preferable.

In order not to leave the isocyanate group in the polyimide resin (A) as much as possible, the molar amount of the isocyanate group contained in the diisocyanate compound is X, difunctional hydroxy group-terminated polybutadiene, bifunctional hydroxy group-terminated polyisoprene or polycarbonate diol. When the molar amount of the hydroxy group contained in W is W, the molar amount of the carboxy group contained in the polybasic acid or anhydride thereof is Y _1, and the molar amount of the acid anhydride group is Y ₂ , 0.5Y ₁ + Y ₂ > It is preferable to carry out the reaction in an amount satisfying the relationship of X−W ≧ (0.5Y ₁ + Y ₂ ) / 5.

  The reaction between the diisocyanate reactant (ab) and the polybasic acid or anhydride thereof is usually performed at a temperature of 120 to 180 ° C. for 2 to 24 hours. In this reaction, a catalyst may be used if necessary. Further, the reaction may be carried out after further adding the above-mentioned organic solvent.

  Examples of the catalyst include amines such as tetramethylbutanediamine, benzyldimethylamine, triethanolamine, triethylamine, N, N′-dimethylpiperidine, α-methylbenzyldimethylamine, N-methylmorpholine, and triethylenediamine. It is done. Of these, triethylenediamine is preferred.

  In the reaction described above, it is preferable to confirm the disappearance of the isocyanate group by FT-IR or the like so as not to leave the isocyanate group (—NCO) in the polyimide resin (A) as much as possible. The end of the polyimide resin (A) thus obtained is represented by formula (1-c) or formula (1-d):

[In each formula, R2 is as defined above. ]
Can be expressed as

In the production of the polyimide resin (A), after reacting the diisocyanate reactant (ab) with the polybasic acid or its anhydride, the resulting reactant is further reacted with a diisocyanate compound to obtain a higher molecular weight. The polyimide resin can be manufactured. In this case, the reaction ratio of the isocyanate compound is not particularly limited, but the molar amount of the isocyanate group contained in the diisocyanate compound is X, the hydroxy group contained in the bifunctional hydroxy group-terminated polybutadiene, difunctional hydroxy group-terminated polyisoprene or polycarbonate diol. the molar amount of isocyanate group contained a molar amount of base is W, the molar amount of carboxyl groups contained in the polybasic acids or anhydrides thereof on the molar amount of Y ₁ and acid anhydride groups in Y _2, a diisocyanate compound is further reacted Is Z, it is preferable to carry out the reaction in an amount satisfying the relationship of (0.5Y ₁ + Y ₂ ) − (X−W)> Z ≧ 0.

  The above reaction with a further diisocyanate compound is usually carried out at a temperature of 120 to 180 ° C. for 2 to 24 hours.

  When the polyisocyanate or the anhydride thereof is reacted with the diisocyanate reactant (ab), a modifier such as a polyfunctional phenol compound can be added as appropriate.

<(B) Inorganic filler>
The resin composition of the present invention contains an inorganic filler as component (B). Examples of the inorganic filler include silica, alumina, barium sulfate, talc, clay, mica powder, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum borate, barium titanate, Examples include strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, barium zirconate, and calcium zirconate. Among them, amorphous silica, pulverized silica, fused silica, crystalline silica, synthetic silica, hollow silica, spherical silica, and the like are preferable, and fused silica and spherical silica are more preferable from the viewpoint of enhancing the filling property, and spherical fused silica is more preferable. preferable. Examples of commercially available spherical fused silica include “SO-C2” and “SO-C1” manufactured by Admatechs.

  The average particle diameter of the inorganic filler is not particularly limited, but is preferably 5 μm or less, more preferably 3 μm or less, further preferably 2 μm or less, and more preferably 1 μm or less from the viewpoint of imparting good underfill performance to the resin composition. Even more preferred is 0.8 μm or less, particularly preferred is 0.6 μm or less. On the other hand, from the viewpoint of preventing the viscosity of the resin composition from increasing and handling properties from decreasing, the average particle size is preferably 0.01 μm or more, more preferably 0.03 μm or more, and 0.05 μm or more. More preferably, 0.07 μm or more is even more preferable, and 0.1 μm or more is even more preferable. The average particle diameter of the inorganic filler can be measured by a laser diffraction / scattering method based on Mie scattering theory. Specifically, the particle size distribution of the inorganic filler can be created on a volume basis with a laser diffraction / scattering particle size distribution measuring apparatus, and the median diameter can be measured as the average particle diameter. As the measurement sample, an inorganic filler dispersed in water by ultrasonic waves can be preferably used. As a laser diffraction scattering type particle size distribution measuring apparatus, LA-950 manufactured by Horiba, Ltd. or the like can be used.

  As the inorganic filler, it is preferable to use an inorganic filler surface-treated with one or more surface treatment agents. Examples of the surface treatment agent include amino silane coupling agents, epoxy silane coupling agents, mercapto silane coupling agents, styryl silane coupling agents, acrylate silane coupling agents, isocyanate silane coupling agents, and sulfides. Examples include silane coupling agents, vinyl silane coupling agents, silane coupling agents, organosilazane compounds, and titanate coupling agents. By the surface treatment, the dispersibility and moisture resistance of the inorganic filler can be improved.

  Specific surface treatment agents include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyldiethoxymethylsilane, N-phenyl-3-aminopropyltrimethoxysilane, and N-methylamino. Aminosilane coupling agents such as propyltrimethoxysilane, N-2 (-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyldimethoxymethylsilane; 3-glycidyloxy Propyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, 3-glycidyloxypropylmethyldiethoxysilane, 3-glycidyloxypropyl (dimethoxy) methylsilane, glycidylbutyltrimethoxysilane, 2- (3,4-epoxy (Cyclohexyl) Epoxysilane coupling agents such as ethyltrimethoxysilane; mercapto such as 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 11-mercaptoundecyltrimethoxysilane Silane coupling agents; styrylsilane coupling agents such as p-styryltrimethoxysilane; 3-acryloxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyldimethoxysilane, 3-methacryl Acrylate silane coupling agents such as oxypropyltriethoxysilane and 3-methacryloxypropyldiethoxysilane; 3-isocyanatopropyltrimethoxy Isocyanate silane coupling agents such as run; sulfide silane coupling agents such as bis (triethoxysilylpropyl) disulfide and bis (triethoxysilylpropyl) tetrasulfide; methyltrimethoxysilane, octadecyltrimethoxysilane, phenyltrimethoxy Silane coupling agents such as silane, methacryloxypropyltrimethoxysilane, imidazolesilane, triazinesilane, t-butyltrimethoxysilane; hexamethyldisilazane, 1,3-divinyl-1,1,3,3-tetramethyl Disilazane, hexaphenyldisilazane, trisilazane, cyclotrisilazane, octamethylcyclotetrasilazane, hexabutyldisilazane, hexaoctyldisilazane, 1,3-diethyltetramethyldisilazane 1,3-di-n-octyltetramethyldisilazane, 1,3-diphenyltetramethyldisilazane, 1,3-dimethyltetraphenyldisilazane, 1,3-diethyltetramethyldisilazane, 1,1,3 Organosilazane compounds such as 1,3-tetraphenyl-1,3-dimethyldisilazane, 1,3-dipropyltetramethyldisilazane, hexamethylcyclotrisilazane, dimethylaminotrimethylsilazane, tetramethyldisilazane; tetra-n- Butyl titanate dimer, titanium-i-propoxyoctylene glycolate, tetra-n-butyl titanate, titanium octylene glycolate, diisopropoxytitanium bis (triethanolaminate), dihydroxytitanium bislactate, dihydroxybis (ammonium lactate) G) Titanium, bis (dioctyl pyrophosphate) ethylene titanate, bis (dioctyl pyrophosphate) oxyacetate titanate, tri-n-butoxytitanium monostearate, tetra-n-butyl titanate, tetra (2-ethylhexyl) titanate, tetraisopropyl Bis (dioctyl phosphite) titanate, tetraoctyl bis (ditridecyl phosphite) titanate, tetra (2,2-diallyloxymethyl-1-butyl) bis (ditridecyl) phosphite titanate, isopropyl trioctanoyl titanate, isopropyl tricumyl Phenyl titanate, isopropyl triisostearoyl titanate, isopropyl isostearoyl diacryl titanate, isopropyl dimethacryliso And titanate coupling agents such as theaeroyl titanate, isopropyl tri (dioctyl phosphate) titanate, isopropyl tridodecylbenzenesulfonyl titanate, isopropyl tris (dioctyl pyrophosphate) titanate, isopropyl tri (N-amidoethyl / aminoethyl) titanate . Of these, aminosilane coupling agents, epoxysilane coupling agents, mercaptosilane coupling agents, and organosilazane compounds are preferred, and aminosilane coupling agents are more preferred. Commercially available products include “KBM403” (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., “KBM803” (3-mercaptopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., Shin-Etsu Chemical Co., Ltd. "KBE903" (3-aminopropyltriethoxysilane) manufactured by Co., Ltd., "KBM573" (N-phenyl-3-aminopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "SZ" manufactured by Shin-Etsu Chemical Co., Ltd. -31 "(hexamethyldisilazane) and the like.

  The surface treatment method of the inorganic filler with the surface treatment agent is not particularly limited, and examples thereof include a dry method and a wet method. As a dry method, for example, an inorganic filler is charged in a rotary mixer, and a solution or alcohol solution of a surface treatment agent is dropped or sprayed while stirring, followed by further stirring, classification with a sieve, and then surface treatment by heating. And a method of dehydrating and condensing the agent and the inorganic filler. As a wet method, for example, a surface treatment agent is added while stirring a slurry of an inorganic filler and an organic solvent, and after stirring, classification is performed by filtration, drying and sieving, and then the surface treatment agent and the inorganic solvent are heated. The method of dehydrating and condensing with a filler is mentioned.

  The content of the inorganic filler in the resin composition is preferably 40 to 95 mass%, more preferably 50 to 90 mass% in the resin composition from the viewpoint of realizing low warpage of the substrate.

<(C) Epoxy resin>
The resin composition of the present invention contains an epoxy resin as the component (C). The epoxy resin is preferably an epoxy resin having two or more epoxy groups in one molecule and having an epoxy equivalent of 80 g / eq or more and less than 8,000 g / eq. The epoxy equivalent of the epoxy resin is more preferably 80 to 500 g / eq, further preferably 100 to 400 g / eq, and particularly preferably 150 to 300 g / eq. Here, the epoxy equivalent is the number of grams (g / eq) of a resin containing 1 gram equivalent of an epoxy group, and is measured according to the method defined in JIS K 7236. The number average molecular weight of the epoxy resin is preferably 100 to 5,000, more preferably 200 to 3,000.

  The content of the epoxy resin as component (C) is preferably 1 to 70% by mass, more preferably 3 to 60% in the resin composition from the viewpoint of imparting chemical resistance to the resin composition after thermosetting. It is 5 mass%, More preferably, it is 5-55 mass%.

  Examples of the epoxy resin include biphenyl type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin, phenol novolac type epoxy resin, and tert-butyl-catechol type epoxy resin. , Naphthalene type epoxy resins, naphthylene ether type epoxy resins, glycidyl amine type epoxy resins, glycidyl ester type epoxy resins, cresol novolac type epoxy resins, anthracene type epoxy resins, linear aliphatic epoxy resins, epoxy resins having a polybutadiene structure, Alicyclic epoxy resin, heterocyclic epoxy resin, spiro ring-containing epoxy resin, cyclohexanedimethanol type epoxy resin, trimethylol type epoxy resin, halogen Epoxy resins. One or more epoxy resins can be used. The epoxy resin is preferably one or more selected from a biphenyl type epoxy resin, a bisphenol A type epoxy resin, and a naphthalene type epoxy resin.

  In the present invention, the epoxy resin as component (C) includes at least a solid epoxy resin at 25 ° C. from the viewpoint of imparting sufficient heat resistance to the resin composition and making the resin composition have an appropriate viscosity. That is, when the total amount of the epoxy resin as component (C) is a liquid epoxy resin at 25 ° C., the heat resistance of the resin composition is not sufficient, and the viscosity tends to be too low. By including a solid epoxy resin at 25 ° C., a resin composition having sufficient heat resistance and optimum viscosity for mold underfill can be provided. The “viscosity of the resin composition” as used in the present invention refers to the melt viscosity at 90 to 160 ° C. (preferably 100 to 130 ° C.) which is the heating temperature (mold temperature) in the compression mold (compression molding). In the temperature range, the melt viscosity is preferably 10 poise or more and 20000 poise or less, the lower limit value is more preferably 500 poise or more, still more preferably 2500 poise or more, and the upper limit value is not particularly limited, but more preferably. Is 18000 poise or less.

  Examples of the epoxy resin solid at 25 ° C. include biphenyl type epoxy resin, naphthalene type epoxy resin, dicyclopentadiene type epoxy resin, fluorene type epoxy resin, triazine skeleton type epoxy resin, polyphenylene ether type epoxy resin, adamantane type epoxy resin, fat Cyclic epoxy resins, anthracene epoxy resins and the like are preferable, biphenyl epoxy resins and naphthalene epoxy resins are more preferable, and biphenyl epoxy resins are particularly preferable. Specific examples of the epoxy resin solid at 25 ° C. include “YX-4000HK” (biphenyl type epoxy resin, epoxy equivalent: about 185 g / eq) manufactured by Mitsubishi Chemical Corporation, “NC” manufactured by Nippon Kayaku Co., Ltd. -3000H "(biphenyl type epoxy resin, epoxy equivalent: 288 g / eq). One or two or more epoxy resins that are solid at 25 ° C. can be used.

  The epoxy resin as component (C) preferably contains both an epoxy resin that is solid at 25 ° C. and an epoxy resin that is liquid at 25 ° C. from the viewpoint of optimum heat resistance and viscosity in the resin composition. Examples of epoxy resins that are liquid at 25 ° C. include bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol AF type epoxy resins, naphthalene type epoxy resins, glycidyl ester type epoxy resins, phenol novolac type epoxy resins, and fats having ester skeletons. Cyclic epoxy resins and epoxy resins having a butadiene structure are preferred, and bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol AF type epoxy resins and naphthalene type epoxy resins are more preferred. Specific examples of the liquid epoxy resin include “HP4032”, “HP4032D”, “HP4032SS” (naphthalene type epoxy resin) manufactured by DIC Corporation, “828US”, “jER828EL” (bisphenol A) manufactured by Mitsubishi Chemical Corporation. Type epoxy resin), “jER807” (bisphenol F type epoxy resin), “jER152” (phenol novolac type epoxy resin), “YL7760” (bisphenol AF type epoxy resin), “ZX1059” manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. ( Bisphenol A type epoxy resin and bisphenol F type epoxy resin mixture), “EX-721” (glycidyl ester type epoxy resin) manufactured by Nagase ChemteX Corporation, “Celoxide 2021P” (ester structure) manufactured by Daicel Corporation Alicyclic Epoxy with Resin), "PB-3600" (epoxy resin having a butadiene structure) and the like. One or two or more epoxy resins which are liquid at 25 ° C. can be used.

  When the epoxy resin as the component (C) includes both an epoxy resin that is solid at 25 ° C. and an epoxy resin that is liquid at 25 ° C., the quantitative ratio is the mass ratio (epoxy resin that is solid at 25 ° C .: 25 ° C. 15:85 to 30:70, and more preferably 20:80 to 25:75.

  In addition, you may use an epoxy hardening | curing agent (component (E)) with the epoxy resin which is a component (C). The epoxy curing agent is not particularly limited as long as it has a function of curing the epoxy resin. For example, an amine curing agent, a guanidine curing agent, an imidazole curing agent, a phenol curing agent (for example, a phenol novolac resin), and naphthol. Examples thereof include a series curing agent, a benzoxazine-based curing agent, a carbodiimide-based curing agent, a cyanate ester-based curing agent, an acid anhydride-based curing agent, or an epoxy adduct or a microencapsulated one thereof. Only one type of epoxy curing agent may be used, or two or more types may be used in combination.

  As the phenol-based curing agent and the naphthol-based curing agent, a phenol-based curing agent having a novolak structure or a naphthol-based curing agent having a novolak structure is preferable from the viewpoint of heat resistance and water resistance. Further, from the viewpoint of obtaining an insulating layer having excellent adhesion to the conductor layer, a nitrogen-containing phenol-based curing agent and a nitrogen-containing naphthol-based curing agent are preferable, and a triazine skeleton-containing phenol-based curing agent and a triazine skeleton-containing naphthol-based curing agent are more preferable. preferable. Of these, a triazine skeleton-containing phenol novolak resin and a triazine skeleton-containing naphthol novolak resin are preferred from the viewpoint of highly satisfying heat resistance, water resistance, and adhesion to the conductor layer. Specific examples of the phenol-based curing agent and the naphthol-based curing agent include, for example, “MEH-7700”, “MEH-7810”, “MEH-7785” manufactured by Meiwa Kasei Co., Ltd., and Nippon Kayaku Co., Ltd. “NHN”, “CBN”, “GPH”, “SN-170”, “SN-180”, “SN-190”, “SN-475”, “SN-485” manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. "SN-495", "SN-375", "SN-395", "LA-7052," "LA-7054," "LA-3018," "LA-1356," "TD2090" manufactured by DIC Corporation Or the like.

  Although it does not specifically limit as a cyanate ester type hardening | curing agent, For example, novolak type (phenol novolak type, alkylphenol novolak type, etc.) cyanate ester type hardening agent, dicyclopentadiene type cyanate ester type hardening agent, bisphenol type (bisphenol A type, Bisphenol F type, bisphenol S type, etc.) cyanate ester-based curing agents, and prepolymers in which these are partially triazines. Specific examples include bisphenol A dicyanate, polyphenol cyanate, oligo (3-methylene-1,5-phenylene cyanate), 4,4′-methylenebis (2,6-dimethylphenyl cyanate), 4,4′-ethylidene diphenyl diester. Cyanate, hexafluorobisphenol A dicyanate, 2,2-bis (4-cyanate) phenylpropane, 1,1-bis (4-cyanatephenylmethane), bis (4-cyanate-3,5-dimethylphenyl) methane, , 3-bis (4-cyanatephenyl-1- (methylethylidene)) benzene, bis (4-cyanatephenyl) thioether, and bifunctional cyanate resins such as bis (4-cyanatephenyl) ether, phenol novolac and cresol novolac From Guide is the polyfunctional cyanate resin, these cyanate resins prepolymers and the like obtained by partly triazine of. These may be used alone or in combination of two or more. Examples of commercially available cyanate ester curing agents include dicyclopentadiene structure-containing cyanate ester resins (manufactured by Lonza Japan Co., Ltd., DT-4000, DT-7000), “primerset ( “Primaset BA200” (manufactured by Lonza), “Primaset BA230S” (manufactured by Lonza), “Primaset LECY” (Lonza), which is a bisphenol H-type cyanate ester resin. ), “Arocy L10” (manufactured by Bantico), “Primaset PT30” (manufactured by Lonza), “Arocy XU371” (Bante), a novolac-type cyanate ester resin Manufactured by co Ltd.), a dicyclopentadiene type cyanate ester resin "Aroshi (Arocy) XP71787.02L" (Vantico Inc.), and the like. Only one type of cyanate ester curing agent may be used, or two or more types may be used in combination.

  Specific examples of the benzoxazine-based curing agent include “HFB2006M” manufactured by Showa Polymer Co., Ltd., “Pd” and “Fa” manufactured by Shikoku Kasei Kogyo Co., Ltd.

  Specific examples of the carbodiimide curing agent include “V-03” and “V-07” manufactured by Nisshinbo Chemical Co., Ltd.

<(D) Curing accelerator>
The resin composition of the present invention contains a curing accelerator as component (D). The polymer resin of component (A) reacts with the epoxy group of the epoxy resin of component (C) by heating to cure the epoxy resin of component (C). The epoxy resin of component (C) can be efficiently cured by the curing accelerator. Although it does not specifically limit as a hardening accelerator, An imidazole type hardening accelerator, an amine type hardening accelerator, a guanidine type hardening accelerator, a phosphonium type hardening accelerator etc. are mentioned. Of these, imidazole curing accelerators are preferred. A hardening accelerator can use 1 type (s) or 2 or more types.

  Examples of the imidazole curing accelerator include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl- 2 Phenylimidazolium trimellitate, 2,4-diamino-6- [2'-methylimidazolyl- (1 ')]-ethyl-s-triazine, 2,4-diamino-6- [2'-undecylimidazolyl- (1 ′)]-ethyl-s-triazine, 2,4-diamino-6- [2′-ethyl-4′-methylimidazolyl- (1 ′)]-ethyl-s-triazine, 2,4-diamino- 6- [2′-Methylimidazolyl- (1 ′)]-ethyl-s-triazine isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl- 4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo [1,2-a] benzimidazole, 1-dodecyl-2-methyl 3-benzyl-imidazolium chloride, 2-methyl-imidazoline, 2-phenyl-imidazo imidazole compounds such as phosphorus and imidazole compounds and adducts such as with epoxy resin. A commercial item may be used for an imidazole series hardening accelerator. Examples of commercially available imidazole curing accelerators include “2P4MZ” manufactured by Shikoku Kasei Co., Ltd.

  Examples of amine curing accelerators include trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6, -tris (dimethylaminomethyl) phenol, 1,8-diazabicyclo. And amine compounds such as [5.4.0] -undecene (hereinafter abbreviated as DBU).

  Examples of the guanidine curing accelerator include dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1- (o-tolyl) guanidine, dimethylguanidine, diphenylguanidine, trimethylguanidine, Tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo [4.4.0] dec-5-ene, 7-methyl-1,5,7-triazabicyclo [4.4.0] Deca-5-ene, 1-methyl biguanide, 1-ethyl biguanide, 1-n-butyl biguanide, 1-n-octadecyl biguanide, 1,1-dimethyl biguanide, 1,1-diethyl biguanide, 1-cyclohexyl biguanide, 1 -Allyl biguanide, 1-phenyl biguanide, 1- ( - tolyl) biguanide, and the like.

  Examples of the phosphonium curing accelerator include triphenylphosphine, phosphonium borate compound, tetraphenylphosphonium tetraphenylborate, n-butylphosphonium tetraphenylborate, tetrabutylphosphonium decanoate, (4-methylphenyl) triphenylphosphonium thiocyanate. , Tetraphenylphosphonium thiocyanate, butyltriphenylphosphonium thiocyanate, and the like.

  Preferably content of a hardening accelerator is 0.5-5 mass parts with respect to 100 mass parts of epoxy resins which are a component (C), More preferably, it is 1-3 mass parts.

<Other ingredients>
In addition to the components (A) to (E), the resin composition of the present invention includes bismaleimide resin, bisallyl nadiimide resin, vinyl benzyl ether resin, benzoxazine resin, and a polymer of bismaleimide and diamine. The resin which can react with the polymer resin which is a component (A) with a heat | fever can be included.

  Examples of the bismaleimide resin include “BMI-S” (Mitsui Chemical Co., Ltd.), which is 4,4′-phenylmethane bismaleimide, and “BMI-M-20” (Mitsui Chemicals, Inc.), which is polyphenylmethane maleimide. Etc.). Bismaleimide resin may use only 1 type and may use 2 or more types together.

  Examples of the bisallylnadiimide resin include “BANI-M” (manufactured by Maruzen Petrochemical Co., Ltd.), which is diphenylmethane-4,4′-bisallylnadicimide. A bisallyl nadiimide resin may use only 1 type and may use 2 or more types together.

  Examples of the vinyl benzyl ether resin include V-1000X (manufactured by Showa Polymer Co., Ltd.), US Pat. No. 4,116,936, US Pat. No. 4,170,711, US Pat. No. 4,278,708, and JP-A-9-31006. No. 1, JP-A No. 2001-181383, JP-A No. 2001-253992, JP-A No. 2003-277440, JP-A No. 2003-283076, WO 02/083610, and the like. . Only 1 type may be used for a vinyl benzyl ether resin, and it may use 2 or more types together.

  Examples of the benzoxazine resin include “Ba type benzoxazine” and “Bm type benzoxazine” manufactured by Shikoku Kasei Co., Ltd. Only one type of benzoxazine resin may be used, or two or more types may be used in combination.

  Examples of the polymer of the bismaleimide compound and the diamine compound which are thermosetting resins include “Techmite E2020” manufactured by Printec Co., Ltd. As the polymer of the bismaleimide compound and the diamine compound, only one type may be used, or two or more types may be used in combination.

  The resin composition of the present invention can contain a thermoplastic resin (component (F)). The weight average molecular weight in terms of polystyrene of the thermoplastic resin is preferably in the range of 8,000 to 70,000, more preferably in the range of 10,000 to 60,000, and still more preferably in the range of 20,000 to 60,000. The weight average molecular weight in terms of polystyrene of the thermoplastic resin is measured by a gel permeation chromatography (GPC) method. Specifically, the polystyrene-reduced weight average molecular weight of the thermoplastic resin is LC-9A / RID-6A manufactured by Shimadzu Corporation as a measuring device, and Shodex K-800P / K- manufactured by Showa Denko KK as a column. 804L / K-804L can be calculated using a standard polystyrene calibration curve by measuring the column temperature at 40 ° C. using chloroform or the like as a mobile phase.

  A phenoxy resin is preferable as the thermoplastic resin. For example, bisphenol A skeleton, bisphenol F skeleton, bisphenol S skeleton, bisphenol acetophenone skeleton, novolak skeleton, biphenyl skeleton, fluorene skeleton, dicyclopentadiene skeleton, norbornene skeleton, naphthalene skeleton, anthracene skeleton, adamantane skeleton, terpene skeleton, and trimethylcyclohexane Examples thereof include phenoxy resins having one or more skeletons selected from the group consisting of skeletons. The terminal of the phenoxy resin may be any functional group such as a phenolic hydroxyl group or an epoxy group. A phenoxy resin may be used individually by 1 type, and may be used in combination of 2 or more type. Specific examples of the phenoxy resin include “1256” and “4250” (both bisphenol A skeleton-containing phenoxy resin) and “YX8 phenol acetophenone skeleton-containing phenoxy resin” manufactured by Mitsubishi Chemical Corporation. “FX280” and “FX293” manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., “YL6954BH30”, “YX7553”, “YL6794”, “YL7213”, “YL7290” and “YL7482” manufactured by Mitsubishi Chemical Corporation .

  The phenoxy resin may have an epoxy group similarly to the epoxy resin. However, in the present invention, when these are distinguished by the epoxy equivalent, the epoxy equivalent of the epoxy resin as the component (C) is 80 g / eq or more 8 The epoxy equivalent of the phenoxy resin is 8000 g / eq or more.

  The resin composition of the present invention further comprises organic fillers such as silicone powder, nylon powder, fluorine powder, rubber particles; thickeners such as Orben and Benton; silicone-based, fluorine-based, polymer-based antifoaming agents or Leveling agents; adhesion-imparting agents such as thiazole-based silane coupling agents and triazole-based silane coupling agents; coloring agents such as phthalocyanine blue, phthalocyanine green, iodin green, disazo yellow, and carbon black; organophosphorous flame retardants , Organic nitrogen-containing phosphorus compounds, nitrogen compounds, silicone flame retardants, flame retardants such as metal hydroxides, and the like.

<Average particle size>
One of the main characteristics of the resin composition of the present invention is that the resin composition is prepared in the form of granules having an average particle size of 60 μm or more. The average particle size is preferably 80 μm or more, more preferably 100 μm or more, still more preferably 120 μm or more, and particularly preferably 140 μm or more. Moreover, 300 micrometers or less are preferable and 280 micrometers or more are more preferable. The average particle diameter can be measured by a laser diffraction / scattering method based on the Mie scattering theory. Specifically, it can be measured by creating a particle size distribution on a volume basis with a laser diffraction / scattering particle size distribution measuring apparatus and setting the median diameter as the average particle diameter. As the measurement sample, a granular resin composition dispersed in water by ultrasonic waves can be preferably used. As a laser diffraction scattering type particle size distribution measuring device, SALD2200 manufactured by Horiba Ltd. can be used.

  As will be apparent from the comparison between Examples and Comparative Examples described later, the resin composition containing the components (A) to (D) in the granular resin composition of the present invention has an average particle diameter of 60 μm or more. Therefore, mold underfill that exhibits excellent underfill performance can be performed in a compression mold.

  The granular resin composition of the present invention preferably has an angle of repose of 30 ° to 60 °, and more preferably an angle of repose of 45 ° to 55 °. The angle of repose is a physical property value that is measured by the following method and serves as an index of the fluidity of the granular resin composition. The smaller the angle of repose, the better the fluidity.

(Measurement method of repose angle)
The angle of repose is measured in accordance with “JIS R 9301-2-2 Alumina powder—Part 2: Physical property measurement method-2: Angle of repose” obtained by vacuum drying a granular resin composition at 40 ° C. for 5 hours.

  Since the granular resin composition having an angle of repose within the above preferred range has appropriate fluidity, a base material (for example, a semiconductor substrate (wafer, etc.), a glass epoxy substrate, a metal plate, a glass plate, etc.) It will have excellent sprayability to the top and will be better in terms of spray uniformity. The angle of repose of the granular resin composition can be adjusted, for example, by changing the particle size distribution of the granular resin composition.

  The method for preparing the resin composition into the granular resin composition having the above average particle diameter and angle of repose is not particularly limited. For example, the above components are mixed as appropriate, and if necessary, a solid obtained by kneading or mixing by a kneading means such as a three roll, ball mill, bead mill, sand mill, or a stirring means such as a super mixer or a planetary mixer. Examples include a method of pulverizing and classifying an object using a knife mill, a hammer mill, a pulverizer, or the like. Further, a varnish in which the above components are dissolved or dispersed in an organic solvent is prepared, the varnish is applied to a release-treated support layer, and the organic solvent is dried by heating, hot air blowing, etc. Then, the resin composition layer is formed on the support layer, and the resin composition layer is peeled off from the support layer to obtain a resin composition film. The film is pulverized and classified using a knife mill, a hammer mill, a pulverizer, or the like. A method is mentioned. The classification is performed, for example, by a known classifier such as a wet classifier or a dry classifier. In addition, as an organic solvent used for the preparation of the varnish used for the film formation of the resin composition, for example, ketones such as acetone, methyl ethyl ketone, cyclohexanone, ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, Examples include acetates such as carbitol acetate, carbitols such as cellosolve and butyl carbitol, aromatic hydrocarbons such as toluene and xylene, amide solvents such as dimethylformamide, dimethylacetamide, and N-methylpyrrolidone. These can be used alone or in combination of two or more. Further, as the support layer, polyolefin films such as polyethylene, polypropylene, polyvinyl chloride, polyethylene terephthalate (hereinafter sometimes abbreviated as “PET”), polyester films such as polyethylene naphthalate, polycarbonate films, Various types of plastic film such as polyimide film, release paper, metal foil such as copper foil and aluminum foil, or metal with a metal vapor-deposited layer (for example, copper vapor-deposited layer) formed on a releasable plastic film that has been subjected to a mold release treatment A vapor deposition film is mentioned. The thickness of the resin composition layer (film) is preferably about 30 to 1000 μm from the viewpoint of easy handling of the resin composition layer (film).

  The molding conditions in the compression mold using the granular resin composition of the present invention are not particularly limited. However, in the production of a semiconductor package, the mold temperature is usually 80 to 160 ° C. (preferably 100 to 140 ° C.), the pressure : 2-15 MPa (preferably 3-12 MPa), cure time: 2-20 min (preferably 3-12 min).

  The granular resin composition of the present invention may be expressed as a granular composition by those skilled in the art.

  Hereinafter, the present invention will be described more specifically with reference to synthesis examples, examples and comparative examples. However, the present invention is not limited by the following synthesis examples and the like, and can be adapted to the above and the following purposes. It is of course possible to carry out the invention with appropriate modifications, and these are all included in the technical scope of the present invention. Note that “%” and “parts” described below mean “% by mass” and “parts by mass” unless otherwise specified.

  The “equivalent” described below means the number of grams (g / eq) of a compound containing 1 gram equivalent of a functional group. In other words, the “equivalent” described below means a value obtained by dividing the molecular weight of a compound having a functional group that is the target of equivalent by the number of functional groups that the compound has, that is, the molecular weight per functional group. To do. For example, the acid anhydride equivalent is a value obtained by dividing the molecular weight of a compound having an acid anhydride group (carbonyloxycarbonyl group) by the number of acid anhydride groups of the compound contained in one molecule, ie, acid anhydride. It means the molecular weight per substance group.

Synthesis Example 1 Production of Polymer Resin A1 Varnish Bifunctional hydroxy group-terminated polybutadiene (number average molecular weight: 5,047 (GPC method), hydroxyl equivalent: 1798 g / eq, solid content: 100%, Nippon Soda ( "G-3000" 50 g, aromatic hydrocarbon-based mixed solvent (boiling point: 184-205 ° C, "Ipsol 150" manufactured by Idemitsu Petrochemical Co., Ltd.), and 0.005 g of dibutyltin laurate Were mixed and dissolved uniformly. When the mixture became uniform, the temperature was raised to 50 ° C., and while further stirring, 4.8 g of toluene-2,4-diisocyanate (isocyanate group equivalent: 87.08 g / eq) was added, and the reaction was carried out for about 3 hours. It was. The reaction was then allowed to cool to room temperature, after which 8.96 g of benzophenonetetracarboxylic dianhydride (acid anhydride equivalent: 161.1 g / eq), 0.07 g of triethylenediamine, diethylene glycol monoethyl ether 40.4 g of acetate (boiling point: 217 ° C., “Ethyl diglycol acetate” manufactured by Daicel Corporation) was added, the temperature was raised to 130 ° C. with stirring, and the reaction was carried out for about 4 hours. The disappearance of the NCO peak at 2250 cm ⁻¹ was confirmed by FT-IR. After confirming the disappearance of the NCO peak, it was regarded as the end point of the reaction, and the reaction product was cooled to room temperature, filtered through a filter cloth having an opening of 100 μm, and polymer resin A1 having an imide structure, a urethane structure, and a polybutadiene structure. A varnish was obtained.
Viscosity of polymer resin A1 varnish: 7.5 Pa · s (25 ° C., E-type viscometer)
Polymer resin A1 varnish solid content: 50%
Acid value of the polymer resin A1: 16.9 mgKOH / g
Number average molecular weight of polymer resin A1: 13,723
Glass transition temperature of polymer resin A1: −10 ° C.
Content of polybutadiene structure of polymer resin A1: 50 / (50 + 4.8 + 8.96) × 100 = 78.4%

Synthesis Example 2: Production of polymer resin A2 varnish Polycarbonate diol (number average molecular weight: about 2,000, hydroxyl group equivalent: 1000 g / eq, solid content: 100%, “C-2015N” manufactured by Kuraray Co., Ltd.) in a reaction vessel 80 g and 0.01 g of dibutyltin dilaurate were uniformly dissolved in 37.6 g of diethylene glycol monoethyl ether acetate (boiling point: 217 ° C., “Ethyl diglycol acetate” manufactured by Daicel Corporation). Next, the temperature of the mixture was raised to 50 ° C., 13.9 g of toluene-2,4-diisocyanate (isocyanate group equivalent: 87.08 g / eq) was added with further stirring, and the reaction was performed for about 3 hours. The reaction was then cooled to room temperature before it was added 14.3 g benzophenone tetracarboxylic dianhydride (acid anhydride equivalent: 161.1 g / eq), 0.11 g triethylenediamine, and diethylene glycol monoethyl ether acetate. (Boiling point: 217 ° C., “Ethyl Diglycol Acetate” manufactured by Daicel Corporation) 70.5 g was added, the temperature was raised to 130 ° C. with stirring, and the reaction was performed for about 4 hours. The disappearance of the NCO peak at 2250 cm ⁻¹ was confirmed by FT-IR. After confirming the disappearance of the NCO peak, it was regarded as the end point of the reaction, and after the reaction product was cooled to room temperature, it was filtered through a filter cloth having an opening of 100 μm, and the polymer resin A2 having an imide structure, a urethane structure and a polycarbonate structure A varnish was obtained.
Viscosity of polymer resin A2 varnish: 6 Pa · s (25 ° C., E-type viscometer)
Solid content of polymer resin A2 varnish: 50%
Acid value of polymer resin A2: 15.6 mgKOH / g
Number average molecular weight of polymer resin A2: 11,500
Glass transition temperature of polymer resin A2: −10 ° C.
Content of polycarbonate structure of polymer resin A2: 80 / (80 + 13.9 + 14.3) × 100 = 73.9%

Synthesis Example 3 Production of Polymer Resin A3 Varnish Bifunctional hydroxy group-terminated polybutadiene (number average molecular weight: 5,047 (GPC method), hydroxyl equivalent: 1500 g / eq, solid content: 100%, Nippon Soda ( "GI-3000") 50g, aromatic hydrocarbon-based mixed solvent (boiling point: 184-205 ° C, "Ipsol 150" manufactured by Idemitsu Petrochemical Co., Ltd.), and dibutyltin laurate 0.005g Were mixed and dissolved uniformly. When the mixture became uniform, the temperature was raised to 50 ° C., and while further stirring, 4.8 g of toluene-2,4-diisocyanate (isocyanate group equivalent: 87.08 g / eq) was added, and the reaction was carried out for about 3 hours. It was. The reaction was then allowed to cool to room temperature, after which 8.96 g of benzophenonetetracarboxylic dianhydride (acid anhydride equivalent: 161.1 g / eq), 0.07 g of triethylenediamine, diethylene glycol monoethyl ether 40.4 g of acetate (boiling point: 217 ° C., “Ethyl Diglycol Acetate” manufactured by Daicel Corporation) was added, the temperature was raised to 130 ° C. with stirring, and the reaction was performed for about 4 hours. The disappearance of the NCO peak at 2250 cm ⁻¹ was confirmed by FT-IR. After confirming the disappearance of the NCO peak, it was regarded as the end point of the reaction, the reaction product was cooled to room temperature, filtered through a filter cloth having an opening of 100 μm, and the polymer resin A3 having an imide structure, a urethane structure, and a polybutadiene structure. A varnish was obtained.
Viscosity of polymer resin A3 varnish: 8.4 Pa · s (25 ° C., E-type viscometer)
Solid content of polymer resin A3 varnish: 50%
Acid value of the polymer resin A3: 17.2 mgKOH / g
Number average molecular weight of polymer resin A3: 14540
Glass transition temperature of polymer resin A3: −23 ° C.
Content ratio of polybutadiene structure of polymer resin A3: 50 / (50 + 4.8 + 8.96) × 100 = 78.4%

Example 1
35 parts of liquid bisphenol A type epoxy resin (epoxy equivalent: 180 g / eq, “jER828EL” manufactured by Mitsubishi Chemical Corporation), biphenyl type epoxy resin (epoxy equivalent: 288 g / eq, “NC-3000H manufactured by Nippon Kayaku Co., Ltd.) )) 6 parts, biphenyl type epoxy resin (epoxy equivalent: about 185 g / eq, "YX-4000HK" manufactured by Mitsubishi Chemical Corporation), curing accelerator (imidazole derivative, "2P4MZ" manufactured by Shikoku Kasei Co., Ltd.) 1 part, 300 parts of polymer resin A1 varnish, 20 parts of liquid naphthalene type epoxy resin (epoxy equivalent: 151 g / eq, “HP-4032” manufactured by DIC Corporation), phenol novolac resin (phenolic hydroxyl group equivalent: 105 g / eq) DIC Corporation "TD-2090" 10 parts, phenylaminosilane coupling agent (Shin 920 parts of spherical silica (“SO-C2” manufactured by Admatechs Co., Ltd., average particle size: 0.5 μm) surface-treated with “KBM573” manufactured by Chemical Industry Co., Ltd. is mixed and uniformly mixed with a high-speed rotary mixer. Dispersing to prepare a resin composition varnish having a solid content of about 89%. Next, this varnish was applied on a polyethylene terephthalate film (thickness 38 μm, hereinafter abbreviated as “PET film”) with a die coater so that the thickness of the resin composition layer after drying was 40 μm. And dried at 80 to 120 ° C. (average 100 ° C.) for 10 minutes to obtain a resin composition film with a support. The resin composition film is peeled off from the support (PET film) to form a resin composition film alone, which is then pulverized by a pulverizer, and has a mean particle size of 270 μm, an angle of repose of 53 °, and a melt viscosity of 950 poise at 100 ° C. A composition was obtained.

Example 2
35 parts of liquid bisphenol A type epoxy resin (epoxy equivalent: 180 g / eq, “jER828EL” manufactured by Mitsubishi Chemical Corporation), biphenyl type epoxy resin (epoxy equivalent: 288 g / eq, “NC-3000H manufactured by Nippon Kayaku Co., Ltd.) "" 6 parts, 9 parts of biphenyl type epoxy resin (epoxy equivalent: about 185 g / eq, "YX4000HK" manufactured by Mitsubishi Chemical Corporation), 1 part of curing accelerator (imidazole derivative, "2P4MZ" manufactured by Shikoku Kasei Co., Ltd.) 246 parts of polymer resin A2 varnish, 20 parts of liquid naphthalene type epoxy resin (epoxy equivalent: 151 g / eq, “HP4032” manufactured by DIC Corporation), phenol novolac resin (phenolic hydroxyl group equivalent: 105 g / eq, DIC Corporation) ) "TD2090") 10 parts, phenylaminosilane coupling agent (Shin-Etsu Chemical) 920 parts of spherical silica (“SO-C2” manufactured by Admatechs Co., Ltd., average particle size: 0.5 μm) surface-treated with “KBM573” manufactured by Kogyo Co., Ltd. is mixed and dispersed uniformly with a high-speed rotary mixer A resin composition varnish having a solid content of about 92% was prepared. Next, this varnish was applied on a polyethylene terephthalate film (thickness 38 μm, hereinafter abbreviated as “PET film”) with a die coater so that the thickness of the resin composition layer after drying was 40 μm. And dried at 80 to 120 ° C. (average 100 ° C.) for 10 minutes to obtain a resin composition film with a support. The resin composition film is peeled off from the support (PET film) to form a resin composition film alone, which is then pulverized by a pulverizer, and has an average particle diameter of 246 μm, an angle of repose of 48 °, and a melt viscosity of 6800 poise at 100 ° C. A composition was obtained.

Example 3
35 parts of liquid bisphenol A type epoxy resin (epoxy equivalent: 180 g / eq, “jER828EL” manufactured by Mitsubishi Chemical Corporation), biphenyl type epoxy resin (epoxy equivalent: 288 g / eq, “NC-3000H manufactured by Nippon Kayaku Co., Ltd.) "" 6 parts, 9 parts of biphenyl type epoxy resin (epoxy equivalent: about 185 g / eq, "YX4000HK" manufactured by Mitsubishi Chemical Corporation), 1 part of curing accelerator (imidazole derivative, "2P4MZ" manufactured by Shikoku Kasei Co., Ltd.) 200 parts of polymer resin A3 varnish, 20 parts of liquid naphthalene type epoxy resin (epoxy equivalent: 151 g / eq, “HP4032” manufactured by DIC Corporation), phenol novolac resin (phenolic hydroxyl group equivalent: 105 g / eq, DIC Corporation) ) "TD2090") 10 parts, phenylaminosilane coupling agent (Shin-Etsu Chemical) 920 parts of spherical silica (“SO-C2” manufactured by Admatechs Co., Ltd., average particle size: 0.5 μm) surface-treated with “KBM573” manufactured by Kogyo Co., Ltd. is mixed and dispersed uniformly with a high-speed rotary mixer Thus, a resin composition varnish having a solid content of about 96% was prepared. Next, this varnish was applied on a polyethylene terephthalate film (thickness 38 μm, hereinafter abbreviated as “PET film”) with a die coater so that the thickness of the resin composition layer after drying was 40 μm. And dried at 80 to 120 ° C. (average 100 ° C.) for 10 minutes to obtain a resin composition film with a support. The resin composition film is peeled off from the support (PET film) to form a resin composition film alone, which is then subjected to a pulverizer and pulverized. A composition was obtained.

Comparative Example 1
40 parts of liquid bisphenol A type epoxy resin (epoxy equivalent: 180, "jER828EL" manufactured by Mitsubishi Chemical Corporation), 22 parts of naphthalene type tetrafunctional epoxy resin (epoxy equivalent: 163, "HP-4710" manufactured by DIC Corporation) , 1 part of curing accelerator (imidazole derivative, “2P4MZ” manufactured by Shikoku Kasei Co., Ltd.), phenoxy resin solution (“YX-6554” manufactured by Mitsubishi Chemical Co., Ltd.), mixed solution of MEK and cyclohexanone, nonvolatile content: 30% ) 20 parts, 30 parts of MEK solution (non-volatile content: 50%) of naphthol-based curing agent (hydroxyl equivalent: 215, “SN-485” manufactured by Nippon Steel & Sumikin Co., Ltd.), 30 parts of MEK, and inorganic filler {phenyl Spherical silica surface-treated with an aminosilane coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd., “KBM573”) (manufactured by Admatechs Co., Ltd.) "SO-C2", average particle diameter 0.5 [mu] m)} 300 parts were mixed, and uniformly dispersed in a high-speed rotary mixer to prepare a solid content of about 87% of the resin composition varnish. Next, this varnish was applied on a polyethylene terephthalate film (thickness 38 μm, hereinafter abbreviated as “PET film”) with a die coater so that the thickness of the resin composition layer after drying was 40 μm. And dried at 80 to 120 ° C. (average 100 ° C.) for 10 minutes to obtain a resin composition film with a support. The resin composition film is peeled off from the support (PET film) to form a resin composition film alone, which is then pulverized by use of a pulverizer, and has an average particle size of 56 μm, an angle of repose of 63 °, and a melt viscosity of 2000 poise at 100 ° C. A resin composition was obtained.

Comparative Example 2
35 parts of liquid bisphenol A type epoxy resin (epoxy equivalent 180, “jER828EL” manufactured by Mitsubishi Chemical Corporation), 6 parts biphenyl type epoxy resin (epoxy equivalent 288, manufactured by Nippon Kayaku Co., Ltd., “NC-3000H”), 9 parts of biphenyl type epoxy resin (epoxy equivalent: about 185, “YX4000HK” manufactured by Mitsubishi Chemical Corporation), 1 part of imidazole derivative (“2P4MZ” manufactured by Shikoku Kasei Co., Ltd.), 300 parts of polyimide resin A1 varnish, liquid naphthalene type Epoxy resin (epoxy equivalent 151, DIC Corporation, "HP4032" 20 parts, phenol novolak resin (phenolic hydroxyl equivalent 105, DIC Corporation, "TD2090"), phenylaminosilane coupling agent (Shin-Etsu) Spherical paper surface-treated by Chemical Industry Co., Ltd. (“KBM573”) 920 parts of KA (manufactured by Admatechs Co., Ltd., “SO-C2”, average particle size 0.5 μm) are mixed and uniformly dispersed with a high-speed rotary mixer to prepare a resin composition varnish having a solid content of about 88% Next, the varnish was formed on a polyethylene terephthalate film (thickness 38 μm, hereinafter abbreviated as “PET film”) with a die coater so that the thickness of the resin composition layer after drying was 40 μm. It was applied and dried at 80 to 120 ° C. (average 100 ° C.) for 10 minutes to obtain a resin composition film with a support, and the resin composition film was peeled off from the support (PET film) to separate the resin composition film alone. Obtained.

Comparative Example 3
35 parts of liquid bisphenol A type epoxy resin (epoxy equivalent 180, “jER828EL” manufactured by Mitsubishi Chemical Corporation), 6 parts biphenyl type epoxy resin (epoxy equivalent 288, manufactured by Nippon Kayaku Co., Ltd., “NC-3000H”), 9 parts of biphenyl type epoxy resin (epoxy equivalent: about 185, “YX4000HK” manufactured by Mitsubishi Chemical Corporation), 1 part of imidazole derivative (“2P4MZ” manufactured by Shikoku Kasei Co., Ltd.), 300 parts of polyimide resin A1 varnish, liquid naphthalene type Epoxy resin (epoxy equivalent 151, DIC Corporation, "HP4032" 20 parts, phenol novolak resin (phenolic hydroxyl equivalent 105, DIC Corporation, "TD2090"), phenylaminosilane coupling agent (Shin-Etsu) Spherical paper surface-treated by Chemical Industry Co., Ltd. (“KBM573”) 920 parts of KA (manufactured by Admatechs Co., Ltd., “SO-C2”, average particle size 0.5 μm) are mixed and uniformly dispersed with a high-speed rotary mixer to prepare a resin composition varnish having a solid content of about 88% Next, the varnish was formed on a polyethylene terephthalate film (thickness 38 μm, hereinafter abbreviated as “PET film”) with a die coater so that the thickness of the resin composition layer after drying was 40 μm. The resultant was applied and dried at 80 to 120 ° C. (average 100 ° C.) for 10 minutes to obtain a resin composition film with a support, and the resin composition film was peeled off from the support (PET film). After that, the mixture was pulverized by a pulverizer and classified to obtain a granular resin composition having an average minor axis of 45 μm, an angle of repose of 65 °, and a melt viscosity of 950 poise at 100 ° C.

  The said Example and the comparative example were used for the following evaluation tests. In the following evaluation tests, the resin compositions of Examples 1 to 3 and the resin compositions of Comparative Examples 1 and 3 were used in a granular state, and the resin composition of Comparative Example 2 was used in a film state.

(1) Warpage evaluation Both sides of glass cloth base epoxy resin double-sided copper-clad laminate (copper foil thickness 18 μm, substrate thickness 0.3 mm, size 30 cm × 30 cm, R5715ES manufactured by Matsushita Electric Works Co., Ltd.) ) After immersing in CZ8100 manufactured to roughen the copper surface, using the resin compositions obtained in Examples 1 to 3 and Comparative Examples 1 to 3, using a compression mold apparatus, mold temperature: After forming a resin layer by compression molding under the conditions of 130 ° C., pressure: 8 Mpa, and curing time: 10 min, a post-cure 160 ° C. for 30 minutes was performed to obtain a laminate with resin. The obtained laminated board with resin was placed, and the amount of warpage of the portion with the largest warpage was measured.
The amount of warpage was 0 mm or more and less than 6 mm was evaluated as good (◯), 6 mm or more and less than 15 mm was acceptable (Δ), and 15 mm or more was evaluated as unacceptable (x).

(2) Mold underfill evaluation A 1 cm square silicon chip on which bumps (height 50 μm, pitch 50 μm, size 40 μm) are mounted on a 12-inch silicon wafer, and Examples 1-3 and Comparative Examples 1- Using the resin composition of No. 3, mold underfill was performed with a compression molding apparatus. The compression mold conditions were a mold temperature: 130 ° C., a pressure: 8 MPa, and a cure time: 10 min. Thereafter, it was confirmed with an ultrasonic imaging device (SAT) whether or not the resin composition was filled in the portion under the silicon chip. The filled one was evaluated as good (◯), the unfilled portion having an area of less than 1 square millimeter was acceptable (Δ), and the unfilled portion having an area of 1 square millimeter or more was evaluated as unacceptable (x).

(3) Delamination Evaluation A 1 cm square silicon chip on which bumps (height 50 μm, pitch 50 μm, size 40 μm) are mounted on a 12-inch silicon wafer, and Examples 1 to 3 and Comparative Examples 1 to 3 are arranged thereon. Was molded by a compression molding apparatus (compression molding condition = mold temperature: 130 ° C., pressure: 8 MPa, cure time: 10 min). The sample was processed with a reflow apparatus set to have a surface peak temperature of 260 ° C., and the presence / absence of delamination at the chip / resin composition interface was confirmed with an ultrasonic imaging apparatus (SAT). The case where delamination did not occur was evaluated as good (◯), and the case where it was generated was evaluated as impossible (×).

(4) Flow Mark Evaluation A 1 cm square silicon chip on which bumps (height 50 μm, pitch 50 μm, size 40 μm) are mounted on a 12-inch silicon wafer, and Examples 1 to 3 and Comparative Examples 1 to 3 are arranged thereon. Using the resin composition, mold underfill was performed with a compression molding apparatus. The compression mold conditions were a mold temperature: 130 ° C., a pressure: 8 MPa, and a cure time: 10 min. Thereafter, the presence / absence of a flow mark at the chip / resin composition interface was confirmed by an ultrasonic imaging device (SAT). The case where no flow mark was generated was evaluated as good (◯), and the case where it was generated was evaluated as unacceptable (×).

  Table 1 below shows the composition of the resin compositions of Examples 1 to 3 and Comparative Examples 1 to 3, the form of the composition, and the evaluation results. In addition, all the compounding quantities of the constituent material of a resin composition are solid content conversion values.

Claims (9)

(A) a polyimide resin having a number average molecular weight of 5000 to 25000 and having one or more structures selected from a polybutadiene structure, a polyisoprene structure, a polycarbonate structure, a (meth) acrylate structure, and a polysiloxane structure;
(B) inorganic filler,
(C) An epoxy resin, and (D) a granular resin composition containing a curing accelerator,
A granular resin composition having an average particle size of 60 μm or more.   The granular resin composition of Claim 1 whose average particle diameter is 60 micrometers or more and 300 micrometers or less.   The granular resin composition of Claim 1 or 2 whose angle of repose is 30 degrees-60 degrees. The polyimide resin as the component (A) has a structure represented by the formula (1-a) and a structure represented by the formula (1-b):

[Wherein R1 represents a divalent organic group having a polybutadiene structure, a divalent organic group having a polyisoprene structure, or a divalent organic group having a polycarbonate structure, and R2 represents a tetravalent organic group. R3 represents a divalent organic group. ]
The granular resin composition of any one of Claims 1-3 which is a polyimide resin which has this. The granular resin composition according to any one of claims 1 to 4 , wherein the (C) epoxy resin comprises (C1) an epoxy resin that is solid at 25 ° C. The granular resin composition according to any one of claims 1 to 5 , wherein the (C) epoxy resin comprises (C1) an epoxy resin that is solid at 25 ° C, and (C2) an epoxy resin that is liquid at 25 ° C. The content of the polyimide resin as the component (A) is 6 to 40% by mass based on the entire nonvolatile components of the resin composition, and the content of the inorganic filler as the component (B) is based on the entire nonvolatile components of the resin composition. 50-92% by mass, the granular resin composition according to any one of claims 1-6. The granular resin composition according to any one of claims 1 to 7 , which is used for a sealing material for a semiconductor package. The granular resin composition according to any one of claims 1 to 7 , which is used for mold underfill.