Thermosetting resin composition and semiconductor device

Abstract

An object of the present invention is to provide a thermosetting resin composition having excellent adhesion to metals. 【Means for solving the problem】 (A) Thermosetting resin (B) A silane coupling agent represented by the following formula (I) JPEG2026074727000038.jpg27170(In the formula (I), R 1 are each independently an alkyl group having 1 to 8 carbon atoms, m is an integer of 1 to 3, n is an integer of 0 to 10, Q is a single bond or an amide bond (-NHCO-), and A is a nitrogen-containing heterocyclic group containing at least two nitrogen atoms, and one of the nitrogen atoms is -(CH2) n - or bonded to the carbon atom of -NHCO-) (C) A curing accelerator, and (D) An inorganic filler A thermosetting resin composition containing the above components.

Description

[Technical Field]

[0001] The present invention relates to a thermosetting resin composition and a semiconductor device having a cured product thereof. [Background technology]

[0002] With the recent trend towards miniaturization and weight reduction of electronic devices, high-density mounting of electronic components onto circuit boards is required. Compared to conventional pin-insertion type packages, surface-mount type packages can be mounted without using much circuit board area, thus enabling miniaturization and weight reduction.

[0003] In surface mount packages, the entire package is exposed to high temperatures during the reflow oven process when soldering to the circuit board. If the package has absorbed moisture, the rapid expansion of the moisture can cause delamination between the insert (such as the component or lead frame) and the encapsulant, resulting in package cracks. Therefore, the encapsulant must be able to absorb moisture and maintain good adhesion to the insert after reflow.

[0004] Patent Document 1 investigates epoxy group-containing silane coupling agents, amino group-containing silane coupling agents, and thiol group-containing silane coupling agents, but their adhesion to nickel and nickel / palladium / gold was insufficient. [Prior art documents] [Patent Documents]

[0005] [Patent Document 1] Japanese Patent Publication No. 2007-063549 [Overview of the Initiative] [Problems that the invention aims to solve]

[0006] Therefore, the present invention aims to provide a thermosetting resin composition that exhibits excellent adhesion to metals. [Means for solving the problem]

[0007] As a result of intensive studies to solve the above problems, the present inventors have found that a thermosetting resin composition containing a specific silane coupling agent shown below can achieve the above object, and have completed the present invention. That is, the present invention provides the following thermosetting resin composition and a semiconductor device having a cured product of the composition.

[0008] That is, the present invention [1] provides a thermosetting resin composition containing the following components (A) to (D). (A) A thermosetting resin (B) A silane coupling agent represented by the following formula (I) [Chemical formula] (In formula (I), R 1 are each independently an alkyl group having 1 to 8 carbon atoms, m is an integer of 1 to 3, n is an integer of 0 to 10, Q is a single bond or an amide bond (-NHCO-), and A is a nitrogen-containing heterocyclic group containing at least two nitrogen atoms, and one of the nitrogen atoms is -(CH2) n - or -NHCO- is bonded to the carbon atom of) (C) A curing accelerator, and (D) An inorganic filler A thermosetting resin composition containing.

[0009] Furthermore, the present invention provides a thermosetting resin composition having at least one configuration shown in the following [2] to [9]. [2] The thermosetting resin composition according to [1] above, wherein the (B) silane coupling agent is one or more selected from compounds represented by any of the following (1) to (4). [Chemical formula] [Chemical formula] [Chemical formula] [Chemical formula] (In equations (1) to (4), R 1 X, Y, and Z are each independently an alkyl group having 1 to 8 carbon atoms, and X, Y, and Z are each independently a carbon atom or a nitrogen atom, with 1 or 2 of X, Y, and Z being nitrogen atoms, and R 2 ~R 6 (Each element is independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a phenyl group; m is an integer from 1 to 3; n is an integer from 0 to 10; a, b, and c are 0 or 1; if X is a carbon atom, a is 1; if X is a nitrogen atom, a is 0; if Y is a carbon atom, b is 1; if Y is a nitrogen atom, b is 0; if Z is a carbon atom, c is 1; if Z is a nitrogen atom, c is 0; and d is an integer from 0 to 4). [3] The thermosetting resin composition according to [1] or [2] above, wherein the thermosetting resin composition contains an optional curing agent, and the amount of component (B) is 0.1 to 10 parts by mass, the amount of component (C) is 0.2 to 8 parts by mass, and the amount of component (D) is 50 to 1,500 parts by mass, based on 100 parts by mass of the total of component (A) and the optional curing agent. [4] The thermosetting resin composition according to any one of [1] to [3] above, wherein the amount of component (D) is 30 to 97% by mass of the total mass of the thermosetting resin composition. [5] The thermosetting resin composition according to any one of [1] to [4] above, wherein the (A) thermosetting resin is one or more selected from epoxy resins, phenolic resins, maleimide resins, bismaleimide resins, citraconimide resins, cyclic imide compounds, cyanate ester compounds, styrene resins, cyclopentadiene compounds and / or their oligomers, oxetane resins, (meth)acrylate resins, terminal (meth)acrylic group-modified polyphenylene ether resins, unsaturated polyester resins and diallyl phthalate resins. [6] The thermosetting resin composition according to any one of [1] to [5] above, wherein the (A) thermosetting resin is an epoxy resin. [7] The thermosetting resin composition according to [6] above, further comprising a curing agent. [8] The thermosetting resin composition according to [6] or [7] above, wherein the epoxy resin is one or more selected from the group consisting of phenol novolac type epoxy resin, orthocresol novolac type epoxy resin, biphenyl type epoxy resin, bisphenol type epoxy resin, triphenolmethane type epoxy resin, alkyl-modified triphenolmethane type epoxy resin, phenol aralkyl type epoxy resin, biphenyl aralkyl type epoxy resin, and dicyclopentadiene-modified phenol type epoxy resin. [9] The thermosetting resin composition according to any one of [6] to [9] above, wherein the curing agent is one or more selected from the group consisting of phenol novolac resin, orthocresol novolac resin, triphenolmethane resin, alkyl-modified triphenolmethane resin, phenol aralkyl resin, biphenyl aralkyl resin, and dicyclopentadiene-modified phenol resin.

[10] The thermosetting resin composition according to any one of [1] to [9] above, wherein Q is a single bond in formula (I). Furthermore, the present invention provides a semiconductor device having a cured product of the above-mentioned thermosetting resin composition. [Effects of the Invention]

[0010] The thermosetting resin composition of the present invention exhibits excellent adhesion to metals even after moisture absorption and reflow soldering. Therefore, the thermosetting resin composition of the present invention is useful as a encapsulant for surface mount type packages. [Modes for carrying out the invention]

[0011] The present invention will be described in more detail below.

[0012] [(A) Thermosetting resin] The thermosetting resin composition of the present invention contains (A) a thermosetting resin. The thermosetting resin can be, for example, one or more resins selected from epoxy resins, phenolic resins, maleimide resins, bismaleimide resins, citraconimide resins, cyclic imide compounds, cyanate ester compounds, styrene resins, cyclopentadiene compounds and / or their oligomers, oxetane resins, (meth)acrylate resins, terminal (meth)acrylic group-modified polyphenylene ether resins, unsaturated polyester resins, and diallyl phthalate resins. Among these, epoxy resins are preferred. The blending ratio of (A) thermosetting resin in the thermosetting resin composition of the present invention is 3 to 60% by mass of the thermosetting resin relative to the total composition, preferably 5 to 50% by mass.

[0013] The epoxy resin is not particularly limited, but examples include epoxy resins conventionally used in the field of epoxy resin compositions for semiconductor encapsulation. Such epoxy resins include crystalline epoxy resins such as phenol novolac type epoxy resins, orthocresol novolac type epoxy resins, naphthol novolac type epoxy resins, biphenyl type epoxy resins, bisphenol type epoxy resins, stilbene type epoxy resins, and dihydroanthracenediol type epoxy resins; polyfunctional epoxy resins such as triphenolmethane type epoxy resins and alkyl-modified triphenolmethane type epoxy resins; phenol aralkyl type epoxy resins having a phenylene skeleton; biphenyl aralkyl type epoxy resins having a biphenylene skeleton; and phenylene skeleton-containing epoxy resins. Examples of epoxy resins include aralkyl epoxy resins such as phthol aralkyl epoxy resins and naphthol biphenylaralkyl epoxy resins having a biphenylene skeleton; naphthol epoxy resins such as dihydroxynaphthalene epoxy resins and epoxy resins obtained by glycidyl etherification of dihydroxynaphthalene dimers; triazine nucleus-containing epoxy resins such as triglycidyl isocyanurate and monoallyl diglycidyl isocyanurate; and cyclic hydrocarbon compound-modified phenol epoxy resins such as dicyclopentadiene-modified phenol epoxy resins. These may be used individually or in combination of two or more. Among these, phenol novolac epoxy resins, orthocresol novolac epoxy resins, biphenyl epoxy resins, bisphenol epoxy resins, triphenolmethane epoxy resins, alkyl-modified triphenolmethane epoxy resins, phenol aralkyl epoxy resins, biphenyl aralkyl epoxy resins, and dicyclopentadiene-modified phenol epoxy resins are preferred due to their excellent moldability and cured properties.

[0014] Epoxy resins can be used in combination with a curing agent. Suitable curing agents include phenolic resins, acid anhydrides, amines, and activated esters. Among these, phenolic resins are preferred due to their heat resistance and moisture resistance.

[0015] Examples of phenolic resins include phenol novolac resin, orthocresol novolac resin, triphenolmethane resin, alkyl-modified triphenolmethane resin, phenol aralkyl resin, biphenyl aralkyl resin, dicyclopentadiene-modified phenolic resin, naphthalene ring-containing phenolic resin, biphenyl-type phenolic resin, alicyclic phenolic resin, heterocyclic phenolic resin, naphthalene ring-containing phenolic resin, bisphenol A-type phenolic resin, bisphenol F-type phenolic resin, etc. These may be used individually or in combination of two or more. Among these, phenol novolac resin, orthocresol novolac resin, triphenolmethane resin, alkyl-modified triphenolmethane resin, phenol aralkyl resin, biphenyl aralkyl resin, and dicyclopentadiene-modified phenolic resin are preferred due to their excellent moldability and cured properties.

[0016] The mixing ratio of epoxy resin and curing agent can be adjusted as appropriate according to conventionally known formulations. For example, if the curing agent is a phenolic resin, the amount of (epoxy group / phenolic hydroxyl group) is preferably 0.5 to 1.5 in equivalent ratio, and more preferably 0.8 to 1.2. Within this range of mixing ratio, the amount of curing agent is appropriate and insufficient curing will not occur.

[0017] [(B) Silane coupling agent] The thermosetting resin composition of the present invention is characterized by containing (B) a silane coupling agent having a nitrogen-containing heterocyclic group. The silane coupling agent exhibits adhesion by coordinating with the metal to be adhered. The silane coupling agent can be represented by the following formula (I). [ka] In formula (1), R 1 The elements are, independently of each other, alkyl groups having 1 to 8 carbon atoms, m is an integer from 1 to 3, n is an integer from 0 to 10, Q is a single bond or an amide bond (-NHCO-), and A is a nitrogen-containing heterocyclic group containing at least two nitrogen atoms, one of which is -(CH2) n- Or - is bonded to the carbon atom of -NHCO-. Preferably, A is a heterocyclic group having a five-membered ring containing at least two nitrogen atoms. Among them, a group having one structure selected from an imidazole structure, a pyrazole structure, a 1,2,3-triazole structure, a 1,2,4-triazole structure, a benzimidazole structure, a benzopyrazole structure, and a 1,2,3-benzotriazole structure is preferable. Q is preferably a single bond.

[0018] (Component (B) is more preferably one or more silane coupling agents selected from the compounds represented by any of the following formulas (1) to (4). The silane coupling agent may be used alone or in combination of two or more.

Chemical formula

Chemical formula

Chemical formula

Chemical formula

[0019] In the above formulas, R 1 are each independently an alkyl group having 1 to 8 carbon atoms, X, Y, and Z are each independently a carbon atom or a nitrogen atom, one or two of X, Y, and Z are nitrogen atoms, and R 2 ~R 6 are each independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a phenyl group, m is an integer of 1 to 3, n is an integer of 0 to 10, a, b, and c are 0 or 1, when X is a carbon atom, a is 1, when X is a nitrogen atom, a is 0, when Y is a carbon atom, b is 1, when Y is a nitrogen atom, b is 0, when Z is a carbon atom, c is 1, when Z is a nitrogen atom, c is 0, and d is an integer of 0 to 4.

[0020] In the above formulas, R 1The alkyl group having 1 to 8 carbon atoms, represented by , may be linear, branched, or cyclic. Examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, neopentyl, n-hexyl, cyclohexyl, n-heptyl, and n-octyl groups. Among these, alkyl groups having 1 to 3 carbon atoms are preferred, with methyl and ethyl groups being more preferred.

[0021] In each of the above formulas, R 2 ~R 6 These are, independently of each other, a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a phenyl group. Examples of alkyl groups having 1 to 8 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, neopentyl, n-hexyl, cyclohexyl, n-heptyl, and n-octyl groups, among which alkyl groups having 1 to 3 carbon atoms are preferred. More preferably, R 2 ~R 6 is a hydrogen atom, and more preferably R 2 ~R 6 All of them are hydrogen atoms.

[0022] In the above formulas, m is an integer between 1 and 3, preferably 3. n is an integer between 0 and 10, preferably 2 and 7. d is an integer between 0 and 4, preferably 0.

[0023] X, Y, and Z are independently carbon atoms or nitrogen atoms, with at least one of X, Y, and Z being a nitrogen atom, and more preferably one or two of X, Y, and Z being nitrogen atoms. In each of the above formulas, if X is a carbon atom, a is 1, and if X is a nitrogen atom, a is 0. If Y is a carbon atom, b is 1, and if Y is a nitrogen atom, b is 0. If Z is a carbon atom, c is 1, and if Z is a nitrogen atom, c is 0.

[0024] Component (B) is not particularly limited as long as it satisfies the above structure, but preferably the nitrogen-containing heterocyclic group indicated in A above has an imidazole, pyrazole, 1,2,3-triazole, 1,2,4-triazole, benzimidazole, benzopyrazole, or 1,2,3-benzotriazole structure.

[0025] Particularly preferred is that component (B) is a compound represented by any of the following formulas (5) to (18). [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] In the above equations (5) to (18), R 1 ~R 5 , m, n are as described above, R 6 Each of the elements independently represents a hydrogen atom, an alkyl group, or a phenyl group, and d is an integer from 0 to 4, preferably 0.

[0026] In the above equations (5) to (18), R 2 ~R 6 A hydrogen atom is preferred, R 2 ~R 6 It is preferable that all of them are hydrogen atoms.

[0027] The amount of component (B) is preferably 0.1 to 10 parts by mass, more preferably 0.2 to 8 parts by mass, and even more preferably 0.3 to 6 parts by mass, per 100 parts by mass of the total of the thermosetting resin (A) and the optional curing agent. Within this range, good adhesion to metal can be achieved.

[0028] [(C) Curing accelerator] The thermosetting resin composition of the present invention contains (C) a curing accelerator. The curing accelerator is not particularly limited as long as it promotes the reaction between components (A) or between components (A) and other components. For example, imidazoles such as 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-methyl-4-ethylimidazole, 2-phenylimidazole, and 2-methyl-4-methylimidazole; tertiary amines such as 1,8-diazabicyclo[5.4.0]undecene-7, triethylenediamine, and benzyldimethylamine; organic phosphines such as triphenylphosphine, tributylphosphine, and tetraphenylphosphonium-tetraphenylborate, etc., and microencapsulated versions thereof, N,N,N',N'-tetramethylurea, N'-phenyl-N,N-dimethylurea, N,N-diethylurea, N' Compounds having a urea structure such as -[3-[[[(dimethylamino)carbonyl]amino]methyl]-3,5,5-trimethylcyclohexyl]-N,N-dimethylurea, N,N''-(4-methyl-1,3-phenylene)bis(N',N'-dimethylurea); organic peroxides such as dicumyl peroxide, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, tert-butylcumyl peroxide, di-tert-butyl peroxide, 1,1,3,3-tetramethylbutyl hydroperoxide, and cumene hydroperoxide can be used individually or in combination of two or more.

[0029] The amount of component (C) is preferably 0.2 to 8.0 parts by mass, and more preferably 0.4 to 6.0 parts by mass, relative to 100 parts by mass of the total of component (A) and any optional curing agent. Within this range, the thermosetting resin reacts quickly, and a cured product can be easily obtained.

[0030] [(D) Inorganic filler] The thermosetting resin composition of the present invention contains (D) an inorganic filler. The inorganic filler is added to reduce the thermal expansion coefficient and improve the mechanical properties of the cured product of the thermosetting resin composition of the present invention. Examples of inorganic fillers include silicas such as spherical silica, fused silica, crystalline silica, and cristobalite, as well as alumina, silicon nitride, aluminum nitride, boron nitride, titanium oxide, glass fiber, and magnesium oxide. The average particle size and shape of these inorganic fillers can be selected according to the application.

[0031] The top cut diameter of component (D) is preferably 5 to 120 μm, and more preferably 10 to 75 μm, in the wet sieving method. The top cut diameter referred to here is the mesh opening of the sieve used in the wet sieving method for classifying the manufactured inorganic filler, and is the value at which the proportion of particles larger than the mesh opening is 2 volume% or less in the volume particle size distribution measurement value measured by laser diffraction.

[0032] The amount of component (D) is preferably 50 to 1,500 parts by mass, and more preferably 150 to 1,200 parts by mass, based on 100 parts by mass of the total of component (A) and any optional curing agent. The amount of inorganic filler in the composition is preferably 30 to 97% by mass, more preferably 40 to 95% by mass, and even more preferably 50 to 92% by mass, based on 100% by mass of the entire composition.

[0033] Component (D) may be pre-surface-treated with a coupling agent such as a silane coupling agent or titanate coupling agent to strengthen the bond between the resin component and the inorganic filler. Examples of such coupling agents include epoxysilanes such as 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane; aminosilanes such as N-2(aminoethyl)-3-aminopropyltrimethoxysilane, a reaction product of imidazole and 3-glycidoxypropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, and N-phenyl-3-aminopropyltrimethoxysilane; and 3-mercaptopropyltrimethoxysilane and 3-episulf Examples of silane coupling agents containing epoxy groups, amino groups, mercapto groups, vinyl groups, styryl groups, or methacrylic groups include mercaptosilanes such as idoxypropyltrimethoxysilane; vinylsilanes such as vinyltrimethoxysilane and vinyltriethoxysilane; styrylsilanes such as p-styryltrimethoxysilane; and methacrylicsilanes such as 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, and 3-methacryloxypropyltriethoxysilane. Silane coupling agents having amino groups are particularly preferred from the viewpoint of improving strength. There are no particular restrictions on the amount of coupling agent used in surface treatment or the surface treatment method.

[0034] The thermosetting resin composition of the present invention may contain silane coupling agents other than component (B). The silane coupling agent plays a role in assisting the adhesion of component (B) to metal and is not particularly limited, but epoxysilanes such as 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane; aminosilanes such as N-2(aminoethyl)-3-aminopropyltrimethoxysilane, a reaction product of imidazole and 3-glycidoxypropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, and N-phenyl-3-aminopropyltrimethoxysilane; and mercaptosilanes such as 3-mercaptopropyltrimethoxysilane and 3-episulfidoxypropyltrimethoxysilane are preferred, with 3-glycidoxypropyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, and 3-mercaptopropyltrimethoxysilane being particularly preferred.

[0035] The amount of silane coupling agent other than component (B) is preferably 0.1 to 10 parts by mass, more preferably 0.2 to 8 parts by mass, and even more preferably 0.3 to 6 parts by mass, based on 100 parts by mass of the total of component (A) and optional curing agents.

[0036] <Other additives> The thermosetting resin composition of the present invention may further contain, as necessary, other additives such as flame retardants, ion trapping agents, flexibility imparters, colorants, and mold release agents.

[0037] Examples of flame retardants include halogenated epoxy resins, phosphazene compounds, silicone compounds, zinc molybdate-supported talc, zinc molybdate-supported zinc oxide, aluminum hydroxide, aluminum hydroxide oxide, magnesium hydroxide, molybdenum oxide, and antimony trioxide. These flame retardants may be used individually or in combination of two or more, but from the viewpoint of environmental impact and ensuring fluidity, phosphazene compounds, zinc molybdate-supported zinc oxide, molybdenum oxide, and aluminum hydroxide are preferably used.

[0038] Examples of ion trapping agents include hydrotalcite compounds, bismuth compounds, and zirconium compounds, which may be used individually or in combination of two or more.

[0039] Examples of flexibility-imparting agents include silicone compounds such as silicone oil, silicone resin, silicone-modified epoxy resin, and silicone-modified phenolic resin, as well as thermoplastic elastomers such as styrene resin and acrylic resin. These may be used individually or in combination of two or more types.

[0040] Examples of colorants include carbon black, titanium black, and titanium dioxide, which may be used individually or in combination of two or more.

[0041] Examples of release agents include waxes such as carnauba wax, rice wax, polyethylene, polyethylene oxide, montanic acid, ester compounds of montanic acid with saturated alcohol, 2-(2-hydroxyethylamino)-ethanol, ethylene glycol, glycerin, etc.; stearic acid, stearic acid esters, stearic acid amide, ethylenebisstearic acid amide, copolymers of ethylene and vinyl acetate, etc., which may be used individually or in combination of two or more.

[0042] The content of other additives in the epoxy resin composition can be appropriately determined within a range that allows each additive to perform its function well, but for example, it is in the range of 0.1 parts by mass or more and 20 parts by mass or less per 100 parts by mass of the total of component (A) and any curing agent.

[0043] Furthermore, the thermosetting resin composition of the present invention may also contain a laser direct structuring additive. If the laser direct structuring additive is included, the amount can be, for example, 20 to 100 parts by mass, or 30 to 80 parts by mass, per 100 parts by mass of (A) thermosetting resin. Alternatively, the amount of the laser direct structuring additive can be less than 20 parts by mass, or 10 parts by mass or less, per 100 parts by mass of (A) thermosetting resin. In a more preferred embodiment, the thermosetting resin assembly of the present invention does not contain a laser direct structuring additive. A laser direct structuring additive is a material that is added to a thermosetting resin, and when the cured product is activated by an active energy ray such as a laser, it is possible to form a plating layer (metal layer) only in the irradiated area. The laser direct structuring additive is, for example, a metal oxide having a spinel structure, represented by the average composition formula: AB2O4 (wherein A is one or more metal elements selected from iron, copper, nickel, cobalt, zinc, magnesium, and manganese, and B is iron, chromium, or tungsten, provided that A and B are not both iron). Alternatively, the laser direct structuring additive may be one that has not undergone surface treatment.

[0044] <Method for producing thermosetting resin composition> The thermosetting resin composition of the present invention can be manufactured, for example, as follows: (A) thermosetting resin, (B) silane coupling agent, (C) curing accelerator, (D) inorganic filler, and other materials are each blended in predetermined amounts, thoroughly mixed uniformly using a mixer or the like, then subjected to a melt-mixing treatment using a hot roll, kneader, extruder, etc., followed by cooling and solidification, and then crushed to an appropriate size. The resulting composition can be used as a molding material. It can also be compressed into tablets for use in tablet form.

[0045] Since component (B) reacts well with thermosetting resin (A), there is a risk of reaction during the melt-mixing process. Therefore, it is preferable to pre-melt-mix the materials other than component (B) at 100-130°C, then cool and solidify them, crush them to an appropriate size, then add component (B), mix thoroughly and uniformly using a mixer or the like, and then perform the melt-mixing process at 70-100°C. Alternatively, a predetermined amount of component (B) may be added while the materials other than component (B) are being melt-mixed.

[0046] <Applications of thermosetting resin compositions> The present invention provides a semiconductor device having a cured product of the above-described thermosetting resin composition. In the present invention, a semiconductor device includes a semiconductor device and a substrate having a semiconductor device. More specifically, the present invention provides a semiconductor device and a substrate encapsulated with a cured product of the above-described thermosetting resin composition. The thermosetting resin composition of the present invention is particularly effective as an encapsulating resin for surface-mount semiconductor elements such as SOP type, SON type, QFP type, QFN type, and ball grid array type. The method for encapsulating semiconductor elements with the thermosetting resin composition of the present invention is not particularly limited, and conventional molding methods such as transfer molding, injection molding, compression molding, and casting methods may be used.

[0047] <Cured product of thermosetting resin composition> The molding (curing) conditions for the thermosetting resin composition of the present invention are not particularly restricted, but 120-190°C for 90-300 seconds is preferred. Furthermore, post-curing at 170-250°C for 2-16 hours is preferred. The cured product of the resin composition of the present invention exhibits particularly excellent adhesion to nickel and nickel / palladium / gold. The resin composition of the present invention is suitable as a encapsulant for surface mount type packages. [Examples]

[0048] The present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited to the following examples. The components used in the examples and comparative examples are listed below. In the following description, the amount of each component refers to parts by mass.

[0049] (A) Thermosetting resin • Epoxy resin 1: Orthocresol novolac type epoxy resin: DIC Corporation's "Epiclon N665EXP-S" (epoxy equivalent: 202) • Epoxy resin 2: Biphenyl aralkyl type epoxy resin: Nippon Kayaku Co., Ltd. "NC-3000" (epoxy equivalent: 273) • Epoxy resin 3: Dicyclopentadiene-modified phenol-type epoxy resin: DIC Corporation "HP-7200" (epoxy equivalent: 259)

[0050] (B) Silane coupling agent • Silane coupling agent 1: Represented by the following formula (5'), R 1 This is a silane coupling agent containing a methyl group and an imidazole group with m=3 and n=2: manufactured by Shin-Etsu Chemical Co., Ltd. [ka] • Silane coupling agent 2: Represented by the following formula (7'), R 1 This is a silane coupling agent containing a methyl group and a 1,2,4-triazole group with m=3 and n=2: manufactured by Shin-Etsu Chemical Co., Ltd. [ka] • Silane coupling agent 3: Represented by the following formula (9'), R 1 This is a silane coupling agent containing a methyl group and a benzimidazole group with m=3 and n=2: manufactured by Shin-Etsu Chemical Co., Ltd. [ka] • Silane coupling agent 4: Represented by the following formula (9'), R 1 This is a silane coupling agent containing a methyl group and a benzimidazole group with m=3 and n=7: manufactured by Shin-Etsu Chemical Co., Ltd. [ka] • Silane coupling agent 5: Represented by the following formula (11'), R 1This is a silane coupling agent containing a methyl group and a 1,2,3-benzotriazole group with m=3 and n=2: manufactured by Shin-Etsu Chemical Co., Ltd. [ka] • Silane coupling agent 6: Represented by the following formula (18'), R 1 This is a silane coupling agent containing a methyl group and a 1,2,3-benzotriazole group with m=3 and n=2: manufactured by Shin-Etsu Chemical Co., Ltd. [ka] • Silane coupling agent for comparative example: 7:3-Glycidoxypropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd. "KBM-403")

[0051] (C) Curing accelerator • Curing accelerator 1: 2-phenylimidazole: Shikoku Chemicals "2PZ" (D) Inorganic filler • Silica powder 1: Silica powder dry-surface-treated with 0.3 parts by mass of N-phenyl-3-aminopropyltrimethoxysilane (product name: KBM-573, manufactured by Shin-Etsu Chemical Co., Ltd.) per 100 parts by mass of molten spherical silica manufactured by Ryusen Co., Ltd. (average particle size 13 μm, top cut diameter 75 μm).

[0052] The following ingredients were added as needed. (E) Hardener • Phenolic resin 1: Novolac-type phenolic resin: DIC Corporation's "TD-2093Y" (phenol equivalent: 110) • Phenolic resin 2: Biphenyl aralkyl resin: "MEHC-7851SS" manufactured by Meiwa Kasei Co., Ltd. (Phenol equivalent: 203) (F) Coloring agent • Coloring agent 1: Mitsubishi Chemical Corporation's "Mitsubishi Carbon #3230B" (G) Release agent • Release agent 1: "TOWAX-131" manufactured by Toa Chemical Co., Ltd.

[0053] [Examples 1-10, Comparative Examples 1-3] The components were melted and mixed according to the proportions (parts by mass) shown in Table 1, then cooled and pulverized to obtain resin compositions. Each composition was evaluated according to the method described below, and the results are shown in Table 1 or 2.

[0054] <Nickel-to-nickel adhesion after post-curing> A frustoconical specimen with a top diameter of 3 mm, a bottom diameter of 3.568 mm, and a height of 3 mm was molded on a nickel-plated copper substrate under the following conditions: molding temperature of 175°C, molding pressure of 6.9 MPa, and molding time of 120 seconds. After post-curing the obtained specimen at 180°C for 4 hours, the shear bond strength at room temperature (25°C) was measured using a Bond Tester DAGE-SERIES-4000PXY (manufactured by DAGE).

[0055] <Nickel-to-nickel adhesion after reflow soldering> A frustoconical specimen with a top diameter of 3 mm, a bottom diameter of 3.568 mm, and a height of 3 mm was molded on a nickel-plated copper substrate under the following conditions: molding temperature 175°C, molding pressure 6.9 MPa, and molding time 120 seconds. The resulting specimen was post-cured at 180°C for 4 hours, stored for 168 hours under 85°C / 85%RH conditions, and then reflowed three times at 260°C. Subsequently, the shear bond strength at room temperature (25°C) was measured using a DAGE-SERIES-4000PXY bond tester (manufactured by DAGE). The reduction rate of the bond strength was also calculated using the following formula. {(Nickel-to-nickel adhesion after post-curing - Nickel-to-nickel adhesion after reflow resistance) / Nickel-to-nickel adhesion after post-curing} × 100

[0056] <Post-curing adhesion strength to nickel / palladium / gold (hereinafter, NiPdAu)> A frustoconical specimen with a top diameter of 3 mm, a bottom diameter of 3.568 mm, and a height of 3 mm was molded on a copper substrate with a NiPdAu plated surface under the following conditions: molding temperature of 175°C, molding pressure of 6.9 MPa, and molding time of 120 seconds. After post-curing the obtained specimen at 180°C for 4 hours, the shear bond strength at room temperature (25°C) was measured using a Bond Tester DAGE-SERIES-4000PXY (manufactured by DAGE).

[0057] <Adhesion strength to NiPdAu after reflow resistance> A frustoconical specimen with a top diameter of 3 mm, a bottom diameter of 3.568 mm, and a height of 3 mm was molded on a copper substrate with a NiPdAu plated surface under the following conditions: molding temperature 175°C, molding pressure 6.9 MPa, and molding time 120 seconds. The resulting specimen was post-cured at 180°C for 4 hours, stored for 168 hours under 85°C / 85%RH conditions, and then subjected to three reflow cycles at 260°C. Subsequently, the shear bond strength at room temperature (25°C) was measured using a bond tester DAGE-SERIES-4000PXY (manufactured by DAGE). The reduction rate of the bond strength was also calculated using the following formula. {(Adhesion to NiPdAu after post-curing - Adhesion to NiPdAu after reflow resistance) / Adhesion to NiPdAu after post-curing} × 100

[0058] [Table 1]

[0059] [Table 2]

[0060] As shown in Tables 1 and 2, the cured product of the resin composition of the present invention exhibits particularly excellent adhesion to nickel and nickel / palladium / gold. Therefore, the resin composition of the present invention is suitable as a encapsulant for surface mount type packages.

Claims

1. (A) Thermosetting resin (B) Silane coupling agent represented by the following formula (I) 【Chemistry 1】 (In formula (I), R １ The elements are, independently of each other, alkyl groups having 1 to 8 carbon atoms, m is an integer from 1 to 3, n is an integer from 0 to 10, Q is a single bond or an amide bond (-NHCO-), and A is a nitrogen-containing heterocyclic group containing at least two nitrogen atoms, one of which is -(CH₂). ２ ) ｎ (Bonded to a carbon atom of - or -NHCO-) (C) Curing accelerator, and (D) Inorganic filler A thermosetting resin composition containing [a specific substance].

2. The thermosetting resin composition according to claim 1, wherein the (B) silane coupling agent is one or more compounds selected from any of the compounds represented by (1) to (4) below. 【Chemistry 2】 【Transformation 3】 【Chemistry 4】 【Transformation 5】 (In equations (1) to (4), R １ X, Y, and Z are each independently an alkyl group having 1 to 8 carbon atoms, and X, Y, and Z are each independently a carbon atom or a nitrogen atom, with 1 or 2 of X, Y, and Z being nitrogen atoms, and R ２ ~R ６ (Each element is independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a phenyl group; m is an integer from 1 to 3; n is an integer from 0 to 10; a, b, and c are 0 or 1; if X is a carbon atom, a is 1; if X is a nitrogen atom, a is 0; if Y is a carbon atom, b is 1; if Y is a nitrogen atom, b is 0; if Z is a carbon atom, c is 1; if Z is a nitrogen atom, c is 0; and d is an integer from 0 to 4.)

3. The thermosetting resin composition according to claim 1, wherein the thermosetting resin composition contains an optional curing agent, and the amount of component (B) is 0.1 to 10 parts by mass, the amount of component (C) is 0.2 to 8 parts by mass, and the amount of component (D) is 50 to 1,500 parts by mass, based on 100 parts by mass of the total of component (A) and the optional curing agent.

4. The thermosetting resin composition according to claim 1, wherein the amount of component (D) is 30 to 97% by mass of the total mass of the thermosetting resin composition.

5. The thermosetting resin composition according to claim 1, wherein the (A) thermosetting resin is one or more selected from epoxy resins, phenolic resins, maleimide resins, bismaleimide resins, citraconimide resins, cyclic imide compounds, cyanate ester compounds, styrene resins, cyclopentadiene compounds and / or their oligomers, oxetane resins, (meth)acrylate resins, terminal (meth)acrylic group-modified polyphenylene ether resins, unsaturated polyester resins, and diallyl phthalate resins.

6. The thermosetting resin composition according to claim 1, wherein the thermosetting resin (A) is an epoxy resin.

7. The thermosetting resin composition according to claim 6, further comprising a curing agent.

8. The thermosetting resin composition according to claim 6, wherein the epoxy resin is one or more selected from the group consisting of phenol novolac type epoxy resin, orthocresol novolac type epoxy resin, biphenyl type epoxy resin, bisphenol type epoxy resin, triphenolmethane type epoxy resin, alkyl-modified triphenolmethane type epoxy resin, phenol aralkyl type epoxy resin, biphenyl aralkyl type epoxy resin, and dicyclopentadiene-modified phenol type epoxy resin.

9. The thermosetting resin composition according to claim 7, wherein the curing agent is one or more selected from the group consisting of phenol novolac resin, orthocresol novolac resin, triphenolmethane resin, alkyl-modified triphenolmethane resin, phenol aralkyl resin, biphenyl aralkyl resin, and dicyclopentadiene-modified phenol resin.

10. The thermosetting resin composition according to claim 1, wherein Q is a single bond in formula (I).

11. A semiconductor device having a cured product of a thermosetting resin composition according to any one of claims 1 to 10.

Images