JP6922158B2 - Thermosetting resin compositions, resin-sealed substrates, and electronic devices - Google Patents

Description

The present invention relates to thermosetting resin compositions, resin-sealed substrates, and electronic devices.

So far, various developments have been made on sealing epoxy resin compositions used for transfer molding. Examples of this type of technology include the technology described in Patent Document 1. According to the same document, it is described that the transfer moldability can be improved by increasing the fluidity of the epoxy resin composition for sealing molded into a tablet shape.

Japanese Unexamined Patent Publication No. 5-152363

However, in recent years, from the viewpoint of improving the productivity of the semiconductor package manufacturing process, the area of the mold used has been increasing more and more.
As a result of examination by the present inventor based on such a development environment, after molding the epoxy resin composition for sealing described in the above document in the cavity of the mold, the mold is opened and the obtained molded product is obtained. It was found that when a part of the molded product was taken out from the mold, a part of the molded product stuck to the inside of the mold and remained.
That is, in the epoxy resin composition for sealing described in the above document, there is room for improvement in terms of mold sticking during mold molding.

From the viewpoint of mold sticking, the present inventor has come to pay attention to the adhesion of a molded product made of a cured product of a thermosetting resin composition to a mold having a large area. As a result of deepening the study based on this point of view, it was found that the wettability on the surface of the molded product is related to the mold adhesion.
As a result of further studies by the present inventor, it was found that the surface energy of the cured plate obtained by curing the thermosetting resin composition at 175 ° C. is appropriate as an index for evaluating the mold adhesion.
As a result of further diligent research based on such findings, it was found that by setting the surface energy to a predetermined value or less, the mold adhesion can be appropriately controlled and the mold sticking during mold molding can be suppressed. The invention was completed.

（ただし、上記一般式（１）において、Ｒ_１は炭素数１ないし１２のアルキル基、アリール基、アラルキル基から選択される有機基であり、互いに同一であっても異なっていてもよい。Ｒ_２は炭素数１ないし９のアルキレン基を示す。Ｒ_３は水素原子又は炭素数１ないし９のアルキル基である。Ａは、エポキシ基、水酸基、アミノ基、ウレイド基、およびアリール基から選択される官能基である。Ｒ_４は炭素数１ないし１２のアルキル基、アリール基、アラルキル基から選択される有機基、又は炭素、窒素、酸素、硫黄、水素から選択される原子から構成される基であり、互いに同一であっても異なっていてもよい。また、平均値であるｌ、ｍ、ｎ、ａ、及びｂについては以下の関係にある。
ｌ≧０、ｍ≧０、ｎ≧１、ｌ＋ｍ＋ｎ≧５、
０．０２≦ｎ／（ｌ＋ｍ＋ｎ）≦０．８、
ａ≧０、ｂ≧０、ａ＋ｂ≧１）
According to the present invention
A thermosetting resin composition used for forming a resin-sealed substrate.
It contains an epoxy resin and a silicone oil represented by the general formula (1).
The content of the silicone oil is 0.05% by mass or more and 1.0% by mass or less with respect to the entire thermosetting resin composition.
The surface energy of the cured plate obtained by curing the thermosetting resin composition at 175 ° C. is 22 mN / m or more and 30 mN / m or less.
A thermosetting resin composition having a gel time of 50 seconds or more at 175 ° C. is provided.

(However, in the above general formula (1), R ₁ is an organic group selected from an alkyl group having 1 to 12 carbon atoms, an aryl group, and an aralkyl group, and may be the same as or different from each other. ₂ represents an alkylene group _{having 1 to 9 carbon atoms. R 3} is a hydrogen atom or an alkyl group having 1 to 9 carbon atoms. A is selected from an epoxy group, a hydroxyl group, an amino group, a ureido group, and an aryl group. that is a functional group .R ₄ is alkyl of 1 to 12 carbon atoms, an aryl group, an organic group selected from aralkyl group, or a carbon, nitrogen, oxygen, sulfur, group composed of atoms selected from hydrogen It may be the same as or different from each other, and the average values l, m, n, a, and b have the following relationship.
l ≧ 0, m ≧ 0, n ≧ 1, l + m + n ≧ 5,
0.02 ≤ n / (l + m + n) ≤ 0.8,
a ≧ 0, b ≧ 0, a + b ≧ 1)

Further, according to the present invention, there is provided a resin-sealed substrate provided with a cured product of the thermosetting resin composition.

Further, according to the present invention.
With the above resin-sealed substrate,
An electronic device including an electronic component mounted on the resin-sealed substrate is provided.

According to the present invention, there is provided a thermosetting resin composition, a resin-sealed substrate using the same, and an electronic device capable of suppressing mold sticking during mold molding.

It is sectional drawing which shows an example of the structure of the electronic device which concerns on this embodiment. It is a process sectional view which shows an example of the manufacturing process of the electronic device which concerns on this embodiment. It is a top view which shows the structure of the resin sealing substrate which concerns on this embodiment. It is the schematic which showed the measuring method of the angle of repose (φ) and the collapse angle (θ). It is the schematic of an example which shows the method of obtaining the granular thermosetting resin composition.

Hereinafter, embodiments of the present invention will be described with reference to the drawings. In all drawings, similar components are designated by the same reference numerals, and description thereof will be omitted as appropriate.

The thermosetting resin composition of the present embodiment is a thermosetting resin composition used for forming a resin-sealed substrate (Molded Substrate). In the present embodiment, the surface energy of the cured plate obtained by curing the thermosetting resin composition at 175 ° C. can be 30 mN / m or less.

As a result of examining the sticking of the mold, the present inventor has come to pay attention to the relationship between the molded product made of the cured product of the thermosetting resin composition and the adhesion to the mold having a large area. As a result of examination based on this point of view, it was found that the wettability on the surface of the molded product has a correlation with the mold adhesion.
As a result of further studies by the present inventor, it was found that the surface energy of the cured plate obtained by curing the thermosetting resin composition at 175 ° C. is appropriate as an index for evaluating the mold adhesion.
As a result of further diligent research based on such findings, it was found that by setting the surface energy to 30 mN / m or less, the mold adhesion can be appropriately controlled and the mold sticking during mold molding can be suppressed. The present invention has been completed.

According to the thermosetting resin composition of the present embodiment, it is possible to suppress the sticking of the molded body of the thermosetting resin composition to the mold at the time of molding with a large area.

Hereinafter, the components of the thermosetting resin composition of the present embodiment will be described.

(Thermosetting resin)
The thermosetting resin composition of the present embodiment can contain a thermosetting resin.
The thermosetting resin is not particularly limited, but may contain, for example, an epoxy resin.

The epoxy resin is not particularly limited, but for example, a monomer, an oligomer, or a polymer having two or more epoxy groups in one molecule can be used in general.
Specific examples of such an epoxy resin include biphenyl type epoxy resin; bisphenol A type epoxy resin, bisphenol F type epoxy resin, tetramethylbisphenol F type epoxy resin, bisphenol E type epoxy resin, bisphenol S type epoxy resin, and the like. Hydrogenated bisphenol A type epoxy resin, bisphenol M type epoxy resin (4,4'-(1,3-phenylenediisopridiene) bisphenol type epoxy resin), bisphenol P type epoxy resin (4,4'-(1,4'-(1,3' 4-Phenylene diisopridiene) bisphenol type epoxy resin), bisphenol Z type epoxy resin (4,5'-cyclohexidiene bisphenol type epoxy resin) and other bisphenol type epoxy resin; stillben type epoxy resin; phenol novolac type epoxy resin , Novolak type epoxy resin such as brominated phenol novolak type epoxy resin, cresol novolak type epoxy resin, novolak type epoxy resin having fused ring aromatic hydrocarbon structure; trihydroxyphenylmethane type epoxy resin, alkyl modified trihydroxyphenonylmethane Polyfunctional epoxy resin such as type epoxy resin, tetraphenylol ethane type epoxy resin; phenol aralkyl type epoxy resin containing phenylene skeleton, phenol aralkyl type epoxy resin containing biphenylene skeleton; phenol aralkyl type epoxy resin such as dihydroxynaphthalene type epoxy resin, naphthalene Naphthalene skeletons such as bifunctional to tetrafunctional naphthalene dimer epoxy resin, binaphthyl type epoxy resin, naphthol aralkyl type epoxy resin obtained by glycidyl etherification of diol type epoxy resin, hydroxynaphthalene and / or dihydroxynaphthalene dimer. Anthracene type epoxy resin; Phenoxy type epoxy resin; Arihashi cyclic hydrocarbon compound modified phenol type epoxy resin such as dicyclopentadiene modified phenol type epoxy resin; Norbornen type epoxy resin; Adamantane type epoxy resin; Resin, phosphorus-containing epoxy resin, alicyclic epoxy resin, aliphatic chain epoxy resin, bisphenol A novolak type epoxy resin, bixylenol type epoxy resin; heterocyclic epoxy such as triglycidyl isocyanurate and monoallyl diglycidyl isocyanurate. Resin; N, N, N', N'-tetraglycidyl Glycidylamines such as m-xylylenediamine, N, N, N', N'-tetraglycidylbisaminomethylcyclohexane, N, N-diglycidylaniline; compounds having an ethylenically unsaturated double bond with glycidyl (meth) acrylate. Copolymer with; An epoxy resin having a butadiene structure and the like can be mentioned. These may be used alone or in combination of two or more. Among these, a trihydroxyphenylmethane type epoxy resin and a biphenyl type epoxy resin may be used from the viewpoint of low line expansion and high elastic modulus of the semiconductor package. As a result, the reflow resistance of the semiconductor device can be improved, and the warp of the semiconductor package can be suppressed.

In the present embodiment, the lower limit of the content of the thermosetting resin is, for example, preferably 3% by mass or more, and more preferably 5% by mass or more, based on the entire thermosetting resin composition. preferable. Thereby, the fluidity at the time of molding can be improved. Therefore, it is possible to improve the filling property and the molding stability. The upper limit of the content of the thermosetting resin is not particularly limited, but is, for example, preferably 30% by mass or less, and 25% by mass or less, based on the entire thermosetting resin composition. Is more preferable. As a result, the moisture resistance reliability and reflow resistance of the semiconductor device can be improved. Further, by controlling the content of the thermosetting resin within such a range, the warp of the resin-sealed substrate can be suppressed.

(Hardener)
The thermosetting resin composition of the present embodiment may contain a curing agent.
The curing agent is not particularly limited as long as it is a compound that reacts with a thermosetting resin such as an epoxy resin.

Examples of the curing agent include linear aliphatic diamines having 2 to 20 carbon atoms such as ethylenediamine, trimethylenediamine, tetramethylenediamine, and hexamethylenediamine, metaphenylenediamine, paraphenylenediamine, paraxylenediamine, 4,4. '-Diaminodiphenylmethane, 4,4'-diaminodiphenylpropane, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylsulfone, 4,4'-diaminodicyclohexane, bis (4-aminophenyl) phenylmethane, Aminos such as 1,5-diaminonaphthalene, metaxylene diamine, paraxylene diamine, 1,1-bis (4-aminophenyl) cyclohexane, dicyanodiamide; resol-type phenol resins such as aniline-modified resol resin and dimethyl ether resol resin; Novolac-type phenol resins such as phenol novolac resin, cresol novolak resin, tert-butylphenol novolak resin, nonylphenol novolak resin; polyfunctional phenol resins such as trihydroxyphenylmethane-type phenol resin; phenylene skeleton-containing phenol aralkyl resin, biphenylene skeleton-containing phenol Phenol aralkyl resin such as aralkyl resin; Phenol resin having condensed polycyclic structure such as naphthalene skeleton and anthracene skeleton; Polyoxystyrene such as polyparaoxystyrene; Hexahydrophthalic anhydride (HHPA), Methyltetrahydrophthalic anhydride (MTHPA) Such as alicyclic acid anhydrides, acid anhydrides containing aromatic acid anhydrides such as trimellitic anhydride (TMA), pyromellitic anhydride (PMDA), and benzophenol tetracarboxylic acid (BTDA); polysulfide, thioester. , Polymercaptan compounds such as thioethers; isocyanate compounds such as isocyanate prepolymers and blocked isocyanates; organic acids such as carboxylic acid-containing polyester resins and the like. These may be used alone or in combination of two or more.

Among these, as the curing agent, a compound having at least two phenolic hydroxyl groups in one molecule is preferable from the viewpoint of moisture resistance, reliability, etc., and phenol novolac resin, cresol novolac resin, tert-butylphenol novolac resin, nonylphenol. Novolac resin, silicon-modified phenol Novolac resin, etc. Novolac type phenol resin; Resol type phenol resin; Polyoxystyrene such as polyparaoxystyrene; Etc. are exemplified. Among these, a trihydroxyphenylmethane-type phenol resin can be used from the viewpoint of heat resistance of the cured product of the thermosetting resin composition and workability at the time of mold molding.

In the present embodiment, the lower limit of the content of the curing agent is not particularly limited, but for example, it is preferably 1.0% by mass or more, preferably 2.0% by mass, based on the entire thermosetting resin composition. The above is more preferable, and 3.0% by mass or more is particularly preferable. As a result, excellent fluidity can be realized at the time of molding, and the filling property and moldability can be improved. On the other hand, the content of the curing agent is not particularly limited, but is preferably 9% by mass or less, more preferably 8% by mass or less, based on the entire thermosetting resin composition, for example. It is particularly preferable that it is 7% by mass or less. As a result, the moisture resistance reliability and reflow resistance of the semiconductor device can be improved.

(Inorganic filler)
The thermosetting resin composition of the present embodiment can contain an inorganic filler.

Examples of the inorganic filler include silica such as melt crushed silica, melt spherical silica, crystalline silica, and secondary aggregated silica; alumina; titanium white; aluminum hydroxide; talc; clay; mica; glass fiber and the like. Among these, molten spherical silica is particularly preferable. Moreover, it is preferable that the particle shape of silica is infinitely spherical. These may be used alone or in combination of two or more.

From the viewpoint of mold filling property, the upper limit of the average particle size d50 of the inorganic filler is, for example, 5 μm or less, preferably 4.5 μm or less, and more preferably 4 μm or less. Thereby, the filling property in the mold having a large area can be improved. The lower limit of the average particle size d50 of the inorganic filler is not particularly limited, but can be, for example, 0.01 μm or more.
In the present embodiment, the average particle size d50 of the inorganic filler can be measured using, for example, a laser diffraction type particle size distribution measuring device (LA-500, manufactured by HORIBA).

In the present embodiment, the lower limit of the content of the inorganic filler is, for example, 70% by mass or more, preferably 75% by mass or more, and more preferably 80% by mass with respect to the entire thermosetting resin composition. % Or more. Thereby, the low hygroscopicity and low thermal expansion property of the cured product of the thermosetting resin composition can be improved, and the moisture resistance reliability and reflow resistance of the semiconductor device can be more effectively improved. The upper limit of the content of the inorganic filler is not particularly limited, but is preferably 95% by mass or less, preferably 93% by mass or less, based on the entire thermosetting resin composition, for example. It is more preferably 90% by mass or less, and particularly preferably 90% by mass or less. This makes it possible to more effectively improve the fluidity and filling property of the thermosetting resin composition during molding. Further, by setting the content of the inorganic filler within the above range, the warp of the resin-sealed substrate can be suppressed.

The thermosetting resin composition of the present embodiment can contain a silicone oil.

（ただし、上記一般式（１）において、Ｒ１は炭素数１ないし１２のアルキル基、アリール基、アラルキル基から選択される有機基であり、互いに同一であっても異なっていてもよい。Ｒ２は炭素数１ないし９のアルキレン基を示す。Ｒ３は水素原子又は炭素数１ないし９のアルキル基である。Ａは、炭素、窒素、酸素、硫黄、水素から選択される原子から構成される基である。Ｒ４は炭素数１ないし１２のアルキル基、アリール基、アラルキル基から選択される有機基、又は炭素、窒素、酸素、硫黄、水素から選択される原子から構成される基であり、互いに同一であっても異なっていてもよい。また、平均値であるｌ、ｍ、ｎ、ａ、及びｂについては以下の関係にある。
ｌ≧０、ｍ≧０、ｎ≧１、ｌ＋ｍ＋ｎ≧５、
０．０２≦ｎ／（ｌ＋ｍ＋ｎ）≦０．８、
ａ≧０、ｂ≧０、ａ＋ｂ≧１） As the silicone oil, for example, a compound having a polyether group in the molecule is used. As such a silicone oil, a silicone oil represented by the following general formula (1) can be used. These may be used alone or in combination of two or more.

(However, in the above general formula (1), R1 is an organic group selected from an alkyl group having 1 to 12 carbon atoms, an aryl group, and an aralkyl group, and R2 may be the same or different from each other. It represents an alkylene group having 1 to 9 carbon atoms. R3 is a hydrogen atom or an alkyl group having 1 to 9 carbon atoms. A is a group composed of an atom selected from carbon, nitrogen, oxygen, sulfur and hydrogen. R4 is an organic group selected from an alkyl group having 1 to 12 carbon atoms, an aryl group, and an aralkyl group, or a group composed of an atom selected from carbon, nitrogen, oxygen, sulfur, and hydrogen, and is the same as each other. However, the average values l, m, n, a, and b have the following relationships.
l ≧ 0, m ≧ 0, n ≧ 1, l + m + n ≧ 5,
0.02 ≤ n / (l + m + n) ≤ 0.8,
a ≧ 0, b ≧ 0, a + b ≧ 1)

The number of repetitions (n) of the polyether group-containing unit in the silicone oil represented by the general formula (1) is 0.02 with respect to the degree of polymerization (l + m + n) of the silicone oil represented by the general formula (1). As mentioned above, it is preferably in the range of 0.8 or less. When the ratio of the number of repetitions (n) of the unit containing the polyether group is within the above range, the compatibility between the silicone oil and the resin component becomes appropriate, and a surface-active action is exhibited to homogenize the resin component. The effect will be obtained. Further, when the ratio of the number of repetitions (n) of the unit containing a polyether group is within the above range, it is possible to suppress an increase in the amount of moisture absorbed by the resin composition due to the presence of an excessive amount of polyether groups, and the corresponding decrease in solder heat resistance. Can be suppressed.

The silicone oil of the present embodiment has no particular limitation on the average degree of polymerization, and in order to impart compatibility with epoxy resins, phenol resins, and inorganic fillers, C, O, N, in addition to methyl groups and phenyl groups, It may have an organic group containing an S atom or the like.

For example, the silicone oil represented by the above general formula (1) has various groups in the molecule composed of atoms selected from carbon, nitrogen, oxygen, sulfur and hydrogen atoms in addition to the polyether group. You may. Examples of these groups include an epoxy group, a hydroxyl group, an amino group, a ureido group, a functional group having reactivity with an epoxy resin and a curing agent, an aryl group and the like.

In the present embodiment, the lower limit of the content of the silicone oil is not particularly limited, but is, for example, 0.05% by mass or more, preferably 0.08% by mass or more, based on the entire thermosetting resin composition. It is more preferably 0.1% by mass or more. As a result, the silicone oil can bleed to the interface of the cured product of the thermosetting resin composition, and the wettability of the interface can be optimized. The upper limit of the content of the silicone oil is not particularly limited, but is, for example, 1% by mass or less, preferably 0.5% by mass or less, based on the entire thermosetting resin composition. As a result, the amount of bleeding of the silicone oil can be appropriately controlled, so that deterioration of the moldability of the cured product of the thermosetting resin composition can be suppressed.

The thermosetting resin composition of the present embodiment may contain a cyanate resin.
As a result, it is possible to reduce the linear expansion and improve the elastic modulus and rigidity of the cured product of the thermosetting resin composition. In addition, the heat resistance and moisture resistance of the semiconductor device can be improved.
The cyanate resin is, for example, a novolak type cyanate resin; a bisphenol type cyanate resin such as a bisphenol A type cyanate resin, a bisphenol E type cyanate resin, a tetramethylbisphenol F type cyanate resin; a reaction between a naphthol aralkyl type phenol resin and cyanate halide. It can contain one or more selected from the naphthol aralkyl type cyanate resin obtained in the above; dicyclopentadiene type cyanate resin; bisphenol skeleton-containing phenol aralkyl type cyanate resin. Among these, from the viewpoint of low line expansion and improvement of elastic modulus and rigidity, it is more preferable to contain at least one of the novolak type cyanate resin and the naphthol aralkyl type cyanate resin, and the novolak type cyanate resin is contained. Is particularly preferable.

The lower limit of the content of the cyanate resin is, for example, preferably 3% by mass or more, and more preferably 5% by mass or more, based on the entire thermosetting resin composition. As a result, it is possible to achieve low linear expansion and high elastic modulus of the cured product of the thermosetting resin composition. On the other hand, the upper limit of the content of the cyanate resin is, for example, preferably 30% by mass or less, more preferably 20% by mass or less, based on the entire thermosetting resin composition. This makes it possible to improve the heat resistance and moisture resistance of the cured product of the thermosetting resin composition.

(Curing accelerator)
The thermosetting resin composition of the present embodiment may contain a curing accelerator.
The curing accelerator is not particularly limited as long as it accelerates the curing reaction between the epoxy group of the epoxy resin and the curing agent.
Examples of the curing accelerator include phosphorus atom-containing compounds such as organic phosphine, tetra-substituted phosphonium compound, phosphobetaine compound, adduct of phosphine compound and quinone compound, and adduct of phosphonium compound and silane compound; 1,8 -Diazabicyclo [5.4.0] Undecene-7, benzyldimethylamine, 2-methylimidazole and the like are exemplified by amidine and tertiary amine, and are selected from nitrogen atom-containing compounds such as the quaternary salt of amidine and amine. It can include one type or two or more types. Among these, it is more preferable to contain a phosphorus atom-containing compound from the viewpoint of improving curability. Further, from the viewpoint of improving the balance between moldability and curability, it has latent properties such as a tetra-substituted phosphonium compound, a phosphobetaine compound, an adduct of a phosphine compound and a quinone compound, and an adduct of a phosphonium compound and a silane compound. It is more preferable to include one. These may be used alone or in combination of two or more.
Examples of the organic phosphine include a first phosphine such as ethylphosphine and phenylphosphine; a second phosphine such as dimethylphosphine and diphenylphosphine; and a third phosphine such as trimethylphosphine, triethylphosphine, tributylphosphine and triphenylphosphine. Can be mentioned.
More preferable is a curing accelerator having a latent property with less rapid thickening after the thermosetting resin composition is melted.

In addition to the above components, the thermosetting resin composition of the present embodiment has, if necessary, a coupling agent, a leveling agent, a colorant, a mold release agent, a low stress agent, a photosensitizer, a defoaming agent, and an ultraviolet absorber. , Foaming agents, antioxidants, flame retardants, ion scavengers and the like may contain one or more additives.

Examples of the coupling agent include an epoxysilane coupling agent, a cationic silane coupling agent, an aminosilane coupling agent, a γ-glycidoxypropyltrimethoxysilane coupling agent, a phenylaminopropyltrimethoxysilane coupling agent, and a mercapto. Examples thereof include silane coupling agents such as silane coupling agents, titanate-based coupling agents and silicone oil type coupling agents. Examples of the leveling agent include acrylic copolymers and the like. Examples of the colorant include carbon black and the like. Examples of the release agent include natural wax, synthetic wax such as montanic acid ester, higher fatty acid or metal salt thereof, paraffin, polyethylene oxide and the like. Examples of the low stress agent include silicone rubber and the like. Examples of the ion scavenger include hydrotalcite and the like. Examples of the flame retardant include aluminum hydroxide. In the present embodiment, for example, the silicone oil and the mold release agent may be used in combination.

The thermosetting resin composition of the present embodiment may be in the form of granules or in the form of sheets. From the viewpoint of mold filling property, a granular thermosetting resin composition may be used, and from the viewpoint of productivity, a sheet-shaped thermosetting resin composition may be used.

In the present embodiment, as a method for producing a granular thermosetting resin composition, for example, it is melt-kneaded inside a rotor composed of a cylindrical outer peripheral portion having a plurality of small holes and a disk-shaped bottom surface. A method of supplying a thermosetting resin composition and passing the thermosetting resin composition through small holes by a centrifugal force obtained by rotating a rotor (hereinafter, also referred to as "centrifugal milling method". ); After premixing each raw material component of the thermosetting resin composition with a mixer, heat-kneading with a kneader such as a roll, kneader or extruder, cooling and crushing to make a crushed product, using a sieve. A method obtained by removing coarse particles and fine powder (hereinafter, also referred to as "crushed sieving method"); after premixing each raw material component of the thermosetting resin composition with a mixer, a small diameter is formed at the tip of the screw. Using an extruder equipped with multiple dies, heat kneading is performed, and the molten resin extruded in a strand shape from the small holes arranged in the dies is cut with a cutter that slides and rotates substantially parallel to the die surface. (Hereinafter, also referred to as “hot cut method”) and the like.

Further, as a method for producing a sheet-shaped thermosetting resin composition, a method of applying the prepared varnish-like thermosetting resin composition on a base film and drying it to form a sheet-like form and volatilizing the solvent. Can be mentioned. As a result, a resin sheet can be produced. In addition, examples of the coating method include a coating method using a coating machine such as a comma coater or a die coater, a printing method such as stencil printing or gravure printing, and the like. As an example of the method for preparing the varnish-like thermosetting resin composition, for example, the resin composition obtained by kneading each raw material component excluding the non-reactive volatile component is dissolved in an organic solvent or the like. There is a way to disperse. Further, the resin sheet may be formed in the form of a sheet by extruding the thermosetting resin composition. The surface of the resin sheet may be protected and covered with a film. The resin sheet may be in the form of a single sheet or a roll that can be rolled up.

Next, the physical characteristics of the thermosetting resin composition of the present embodiment will be described.

In the present embodiment, the upper limit of the surface energy of the cured plate of the thermosetting resin composition cured at 175 ° C. is, for example, 30 mN / m or less, preferably 28 mN / m or less, and more preferably 26 mN / m. It is less than m. As a result, it is possible to prevent the molded product, which is a cured product of the thermosetting resin composition, from sticking to such a mold when molding a mold having a large area.

The lower limit of the surface energy of the cured plate of the thermosetting resin composition cured at 175 ° C. is not particularly limited, but may be, for example, 22 mN / m or more, or 23 mN / m or more. Thereby, the moldability of the cured product of the thermosetting resin composition can be improved.

In the present embodiment, the surface energy can be calculated from the ethanol fraction in the ethanol-based ink and the degree of ink repelling on the surface of the cured plate of the thermosetting resin composition. Specifically, first, a cured plate of a thermosetting resin composition cured under the conditions of, for example, 175 ° C. and 120 seconds is prepared using a mold. At this time, the surface roughness Ra of the cured plate is, for example, 0.10 μm or less. Subsequently, a line is drawn with ethanol-based ink on the surface of such a cured plate having a small surface roughness. The ethanol fraction in the ethanol-based ink can be gradually increased from, for example, 20%. The ethanol fraction when the drawn line is maintained can be measured, and the corresponding surface energy can be calculated from the ethanol fraction.
For example, the surface energy can be calculated by appropriately changing and adjusting the mixing ratio of the reagents ethanol and water. As an example, when the ethanol fraction is 50% (ethanol / water = 50/50), the surface energy is 28.51 mN / m, and when the ethanol fraction is 100%, the surface energy is 22 mN / m. Can be done. The surface roughness Ra can be measured by JIS B 0601-1982.

As described above, as a result of the examination by the present inventor, the surface energy of the cured product of the thermosetting resin composition of the present embodiment can be calculated and calculated by a simple method using an ethanol-based ink. It was found that the surface energy was suitable as an index for evaluating the mold adhesion.

In the present embodiment, for example, the surface energy is controlled by appropriately selecting the type and blending amount of each component contained in the thermosetting resin composition, the method for preparing the thermosetting resin composition, and the like. Is possible. Among these, for example, adding a low molecular weight component that bleeds to the surface of a cured product such as silicone oil or wax, adjusting the affinity between the silicone oil and the epoxy resin, adjusting the cross-linking density of the cured product, and the like are described above. It can be mentioned as an element for setting the surface energy in the desired numerical range.

In the thermosetting resin composition of the present embodiment, the lower limit of the gel time at 175 ° C. is, for example, 50 seconds or more, preferably 53 seconds or more, and more preferably 55 seconds or more. As a result, it is possible to improve the filling property of the mold having a large area. The upper limit of the gel time at 175 ° C. is not particularly limited, but may be, for example, 120 seconds or less, 100 seconds or less, or 80 seconds or less. This makes it possible to improve productivity.

The lower limit of the glass transition temperature (Tg) of the cured product of the thermosetting resin composition of the present embodiment is, for example, 145 ° C. or higher, preferably 150 ° C. or higher, and more preferably 155 ° C. or higher. Thereby, the thermal decomposition of the cured product of the thermosetting resin composition can be suppressed. In addition, warpage of the resin-sealed substrate can be suppressed. On the other hand, the upper limit of the glass transition temperature (Tg) is not particularly limited, but may be, for example, 250 ° C. or lower.

Further, the upper limit of the collapse angle in the granular thermosetting resin composition is preferably 35 ° or less, more preferably 30 ° or less, and further preferably 25 ° or less. As a result, when the granular thermosetting resin composition is transported using a transport means such as a vibration feeder, it is possible to stably transport the granular thermosetting resin composition without causing sticking or clogging. Therefore, it is possible to improve the filling property of the mold having a large area. On the other hand, the lower the collapse angle is, the less likely it is that sticking or clogging will occur. Therefore, the lower limit value thereof is not particularly limited, but can be, for example, 1 ° or more, or 10 ° or more.

In the present embodiment, as a method for measuring the collapse angle, a granular thermosetting resin composition is dropped and deposited on a horizontal plate having a certain area from a hole in a funnel until it has a certain shape, and a conical granule is formed. To form. Next, by dropping a weight of a certain weight on the same pedestal as the horizontal plate, a certain impact is given to the granules, and a partially granular thermosetting resin composition naturally flows from the horizontal plate. For the remaining conical granules after falling off, the collapse angle can be obtained as the elevation angle from the point on the outer periphery of the bottom surface to the apex of the cone. The angle of repose of the granules before impact is called the angle of repose, and the difference between the angle of repose and the angle of repose is called the difference angle. The difference angle is an index indicating the ease of collapse of the granular thermosetting resin composition due to vibration from a transfer device such as a vibration feeder, and the larger the difference angle, the easier it is to collapse. Therefore, for example. It is preferably 10 ° or more, and more preferably 15 ° or more. Examples of the device for measuring the collapse angle and the angle of repose include a powder tester (manufactured by Hosokawa Micron Co., Ltd.).

The upper limit of the average particle size of the granular thermosetting resin composition is, for example, 1.0 mm or less, preferably 0.7 mm or less, and more preferably 0.6 mm or less. As a result, it is possible to improve the filling property of the mold having a large area. The lower limit of the average particle size is not particularly limited, but is, for example, 0.1 mm or more, may exceed 0.3 mm, or may be 0.4 mm or more. Thereby, a granular thermosetting resin composition having excellent production stability can be realized.

(Electronic device)
The electronic device 100 of this embodiment will be described. FIG. 1 is a cross-sectional view showing the configuration of the electronic device 100 of the present embodiment.

The electronic device 100 of the present embodiment can be a semiconductor device including a resin-sealed substrate 110 and an electronic component (semiconductor element 140) mounted on the resin-sealed substrate 110. In the present embodiment, the resin-sealed substrate 110 includes a cured product of the above thermosetting resin composition.

The resin-sealed substrate 110 (for example, a MIS substrate (Molded Connect Substrate)) can include at least an insulating layer 112 and a metal layer 130. The insulating layer 112 is composed of a cured product of the thermosetting resin composition of the present embodiment. As a result, it is possible to obtain a resin-sealed substrate 110 having excellent manufacturing stability and suppressed substrate warpage. The insulating layer 112 may be configured not to contain a fiber base material such as glass cloth. As a result, the resin-sealed substrate 110 can be a coreless resin substrate. Further, the coreless resin substrate may have a semiconductor chip built in the insulating layer. This semiconductor element can be electrically connected via a metal layer (for example, via wiring).

In the resin-sealed substrate 110, the metal layer 130, which is a post, electrically connects the upper surface 114 and the lower surface of the resin-sealed substrate 110 via the via wiring 120. The via wiring 120 and the via wiring 120 may be made of a metal such as copper, for example.

Further, the upper surface 114 of the resin-sealed substrate 110 may be formed of a polished surface. Further, the upper surface 114 of the resin-sealed substrate 110 and the upper surface of the metal layer 130 may form the same plane. A solder resist layer (not shown) may be formed on the upper surface 114 and the lower surface of the resin-sealed substrate 110.

The semiconductor element 140 may be fixed on the resin-sealed substrate 110 via an adhesive layer 160. The semiconductor element 140 may be electrically connected to the resin-sealed substrate 110 via wire bonding 150, or may be electrically connected by flip-chip connection. Further, the semiconductor element 140 is sealed so as to be covered with a cured product (sealing material layer 170) of a general thermosetting resin composition for sealing.

Examples of the semiconductor element 140 include integrated circuits, large-scale integrated circuits, transistors, thyristors, diodes, solid-state image sensors, and the like. Examples of the structure of the semiconductor package including the semiconductor element 140 include a ball grid array (BGA) and a MAP type BGA. Also, wafer level packages (WLP) such as chip size package (CSP), quad flat non-leaded package (QFN), embedded WLP (eWLP), Fan In WLP and Fan Out WLP, small outline non. Examples include a read package (SON), a lead frame / BGA (LF-BGA), and the like.

Subsequently, the manufacturing method of the electronic device 200 will be described based on the manufacturing process of the resin-sealed substrate 250. FIG. 2 is a process cross-sectional view of the manufacturing process of the electronic device 200.

In the present embodiment, the method for manufacturing the resin-sealed substrate 250 can include the following steps 1 to 3.
Step 1 includes a metal layer forming step of forming a patterned metal layer 230 on the supporting base material 210.
Step 2 includes an insulating layer forming step of forming an insulating layer 234 in which the metal layer 230 is embedded.
Step 3 includes a polishing step of exposing the metal layer 230 by polishing the surface (upper surface 226) of the insulating layer 234.
By repeating these steps 1 to 3, it is possible to form the interlayer connection wiring in the interlayer insulating layer composed of one or more insulating layers.
The insulating layer can be composed of a cured product of the thermosetting resin composition of the present embodiment.
Hereinafter, each step will be described.

First, as shown in FIG. 2A, the supporting base material 210 is prepared. The carrier foil 212 may be formed on the support base material 210. The supporting base material 210 is not particularly limited as long as it is a base substrate having characteristics such as flatness, rigidity and heat resistance, but for example, a metal plate can be used. Examples of the metal plate include a copper plate, an aluminum plate, an iron plate, a steel plate, a nickel plate, a copper alloy plate, a 42 alloy plate, a stainless plate, and the like. The steel plate may be in the form of a cold-rolled steel plate such as SPCC (Steel Plate Cold Commercial). Further, the metal plate may be a single-wafer processed into a frame shape, or may have a hoop-shaped continuous shape. The support base material 210 used in the present embodiment preferably has a large area so that a plurality of semiconductor elements can be arranged on a flat surface. The planar shape of the supporting base material 210 in the top view is not particularly limited, and may be, for example, a rectangular shape or a circular shape, but may be a rectangular shape from the viewpoint of productivity.

Subsequently, after forming the patterned metal layer 220, the via wiring 222 can be formed on the metal layer 220.
As the patterning method, for example, a photolithography method can be used. As a specific example, first, a photosensitive resin film made of a photosensitive resin composition is formed on the supporting base material 210. Examples of the forming method include a method of applying a photosensitive resin composition using a coater, a spinner, etc. and drying the coating film obtained, or laminating a resin sheet made of the photosensitive resin composition by thermocompression bonding or the like. A photosensitive resin film made of a photosensitive resin composition is formed by such a method. Subsequently, an opening having a predetermined pattern is formed in the photosensitive resin film. As a method for forming the opening, for example, an exposure development method, a laser processing method, or the like can be used. Subsequently, this opening is embedded with a metal film. Examples of the burying method include an electroless plating method and a plating method. Examples of the material of the metal film include copper, copper alloy, 42 alloy, nickel, iron, chromium, tungsten, gold, solder and the like, but copper may also be used. Subsequently, the photosensitive resin film is removed. Examples of the removing method include a method of peeling the photosensitive resin film using a stripping solution, a method of ashing, a method of removing the residue of the photosensitive resin film adhering to the substrate after the ashing treatment, and the like. Can be mentioned. Above all, from the viewpoint of improving production efficiency, it is preferable to adopt a method of peeling the photosensitive resin film using a stripping solution. Specific examples of the stripping solution include an organic sulfonic acid-based stripping solution containing alkylbenzene sulfonic acid, an organic amine-based stripping solution containing an organic amine such as monoethanolamine, and an aqueous system in which an organic alkali or a fluorine-based compound is mixed with water. Examples thereof include a resist stripping solution. A method of polishing the metal layer using a chemical mechanical polishing (CMP) apparatus may be performed.
As described above, a patterned metal layer is obtained. Examples of such a metal layer include a wiring circuit, via wiring, and a conductive post.

Subsequently, as shown in FIG. 2B, the insulating layer 224 is formed so as to embed the metal layer 220 and the via wiring 222. The insulating layer 224 is composed of a cured product of the thermosetting resin composition of the present embodiment. That is, the metal layer 220 and the via wiring 222 can be sealed by the cured product of the thermosetting resin composition of the present embodiment.

As a method for forming the insulating layer 224, for example, a granular thermosetting resin composition or a sheet-shaped thermosetting resin composition may be used as a sealing material, and compression molding may be used as a molding method. can.

Here, in the present embodiment, an outline of compression molding using a granular thermosetting resin composition will be described.

First, the granular thermosetting resin composition is uniformly sown on the bottom surface of the lower die cavity of the compression molding die. For example, the granular thermosetting resin composition may be conveyed by using a conveying means such as a vibration feeder and arranged on the bottom surface of the lower die cavity.
Subsequently, the support base material 210 on which the metal layer 220 and the via wiring 222 are formed is fixed to the upper mold of the compression molding die by a fixing means such as a clamp or suction. Subsequently, by narrowing the distance between the upper mold and the lower mold of the mold under reduced pressure, the granular thermosetting resin composition is heated to a predetermined temperature in the lower mold cavity and becomes a molten state. Subsequently, by connecting the upper mold and the lower mold of the mold, the thermosetting resin composition in a molten state is pressed against the metal layer 220 and the via wiring 222 fixed to the upper mold. Then, the thermosetting resin composition is cured over a predetermined time while maintaining the state in which the upper mold and the lower mold of the mold are bonded. As a result, the insulating layer 224 that seals the metal layer 220 and the via wiring 222 on the supporting base material 210 can be formed.
In the present embodiment, even when a sheet-shaped thermosetting resin composition is used instead of the granular thermosetting resin composition, the above-mentioned compression molding can be used.

Here, when performing compression molding, it is preferable to perform sealing while reducing the pressure inside the mold, and it is more preferable to perform sealing under vacuum conditions. Thereby, the patterned metal layer such as the metal layer 220 and the via wiring 222 can be embedded with the cured product (insulating layer 224) of the thermosetting resin composition without leaving the filled portion.

The molding temperature in compression molding may be, for example, 100 ° C. or higher and 200 ° C. or lower, or 120 ° C. or higher and 180 ° C. or lower. The molding pressure may be, for example, 0.5 MPa or more and 12 MPa or less, or 1 MPa or more and 10 MPa or less. The molding time may be, for example, 30 seconds or more and 15 minutes or less, or 1 minute or more and 10 minutes or less. In the present embodiment, by setting the molding temperature, pressure, and time within the above ranges, it is possible to prevent the occurrence of a portion where the sealed material in the molten state is not filled.

Further, the cured product (insulating layer 224) of the obtained thermosetting resin composition may be post-cured after sealing. The post-cure temperature may be, for example, 150 ° C. or higher and 200 ° C. or lower, or 165 ° C. or higher and 185 ° C. or lower. The post-cure time may be, for example, 1 hour or more and 5 hours or less, or 2 hours or more and 4 hours or less.

Subsequently, as shown in FIG. 2C, the surface of the insulating layer 224 (upper surface 226) is polished by a method such as grinding or chemical etching to obtain the surface of the patterned metal layer (via wiring 222). Expose. At this time, a polished surface is formed on the upper surface 226. Further, as a grinding method, for example, chemical mechanical polishing (CMP) can be used.

Subsequently, as shown in FIG. 2D, a patterned metal layer 230 is formed on the upper surface 226 of the insulating layer 224 in the same manner as the metal layer 220. Subsequently, as shown in FIG. 2E, the insulating layer 234 in which the metal layer 230 is embedded is formed in the same manner as the insulating layer 224. Subsequently, as shown in FIG. 2 (f), the upper surface 236 of the insulating layer 234 is polished by the above polishing method to form a polished surface on the upper surface 236 and expose the upper surface of the metal layer 230. Can be done. After repeating the above steps, the support base material 210 and the carrier foil 212 were peeled off to further form the via wiring 232, the metal layer 240, and the insulating layer 244 as shown in FIG. 2 (g). A resin-sealed substrate 250 is obtained. Further, a polished surface may be formed on the upper surface 246 of the resin-sealed substrate 250.

In the present embodiment, by repeating the above steps 1 to 3, the wiring layer of the resin-sealed substrate 250 can be one layer or two or more layers. The interlayer insulating layer of the resin-sealed substrate 250 is composed of a cured product of the thermosetting resin composition of the present embodiment. Therefore, the warp of the resin-sealed substrate 250 can be suppressed. Further, the resin-sealed substrate 250 having excellent manufacturing stability can be obtained.

Here, in the resin-sealed substrate 250 shown in FIG. 2H, not only one semiconductor element 260 but also a plurality of semiconductor elements 260 can be arranged in a plane. That is, the resin-sealed substrate 250 can have a structure obtained by mold molding using a mold having a large area.

FIG. 3 shows an example in which a mounting area on which a plurality of semiconductor elements (electronic components) can be mounted in a plane is provided. FIG. 3 is a top view showing an example of the configuration of the resin-sealed substrate 300 according to the present embodiment. As shown in FIG. 3, the resin-sealed substrate 300 may have a plurality of semiconductor element mounting areas 310 and 320 formed in a plane.
Semiconductor elements (electronic components) are mounted in the semiconductor element mounting areas 310 and 320 so as to be separated from each other.

Returning to FIG. 2H, the semiconductor element 260 is mounted on the resin-sealed substrate 250. As a result, the electronic device 200 is obtained. The semiconductor element 260 in the electronic device 200 can be electrically connected to the resin-sealed substrate 250 by flip-chip connection via the solder bump 280. The semiconductor element 260 on the resin sealing substrate 250 is sealed with a general thermosetting resin for sealing, and is covered with a sealing material layer 270.

In the present embodiment, as shown in FIG. 3, the resin-sealed substrate 300 on which a plurality of semiconductor elements are mounted is individually sealed after being collectively sealed. As a result, it is possible to obtain an individualized electronic device 200 as shown in FIG. 2 (f).

Although the embodiments of the present invention have been described above with reference to the drawings, these are examples of the present invention, and various configurations other than the above can be adopted.
Hereinafter, an example of the embodiment will be added.
1. 1. A thermosetting resin composition used for forming a resin-sealed substrate.
A thermosetting resin composition in which the surface energy of a cured plate obtained by curing the thermosetting resin composition at 175 ° C. is 30 mN / m or less.
2.1. The thermosetting resin composition according to the above.
A thermosetting resin composition having a gel time of 50 seconds or more at 175 ° C.
3.1. Or 2. The thermosetting resin composition according to the above.
A thermosetting resin composition having a glass transition temperature (Tg) of a cured product of the thermosetting resin composition of 145 ° C. or higher.
4.1. From 3. The thermosetting resin composition according to any one of the above items.
A thermosetting resin composition in the form of granules or sheets.
5.4. The thermosetting resin composition according to the above.
A thermosetting resin composition having a decay angle of 35 ° or less in the granular thermosetting resin composition.
6.4. Or 5. The thermosetting resin composition according to the above.
A thermosetting resin composition having an average particle size of 1.0 mm or less in the granular thermosetting resin composition.
7.1. From 6. The thermosetting resin composition according to any one of the above items.
A thermosetting resin composition containing a silicone oil.
8.1. From 7. The thermosetting resin composition according to any one of the above items.
Contains inorganic fillers
A thermosetting resin composition in which the content of the inorganic filler is 70% by mass or more with respect to the entire thermosetting resin composition.
9.8. The thermosetting resin composition according to the above.
A thermosetting resin composition having an average particle size of 5 μm or less of the inorganic filler.
10.1. To 9. A resin-sealed substrate comprising a cured product of the thermosetting resin composition according to any one of the above items.
11.10. With the resin-sealed substrate described in
An electronic device including an electronic component mounted on the resin-sealed substrate.

Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited to the description of these Examples.

(Preparation of thermosetting resin composition)
For Examples and Comparative Examples, thermosetting resin compositions were prepared as follows. First, each component was mixed with a mixer according to the formulation shown in Table 1 to obtain a mixture. Then, an inorganic filler was added to this mixture according to the formulation shown in Table 1, and then the mixture was mixed using a mixer. The resulting mixture was then roll-kneaded at 70-100 ° C.
(Preparation of crushed thermosetting resin composition)
The obtained mixture after kneading was cooled and pulverized to obtain a pulverized thermosetting resin composition.

(Preparation of thermosetting resin composition of granules)
As a material for the cylindrical outer peripheral portion 602 shown in FIG. 5 (a), an iron punched wire mesh having small holes with a hole diameter of 2.5 mm was used. A cylindrically machined punched wire mesh having a height of 25 mm and a thickness of 1.5 mm was attached on the outer circumference of the rotor 601 having a diameter of 20 cm to form a cylindrical outer peripheral portion 602. The rotor 601 was rotated at 3000 RPM, and the cylindrical outer peripheral portion 602 was heated to 115 ° C. with an exciting coil. After the rotation speed of the rotor 601 and the temperature of the cylindrical outer peripheral portion 602 are in a steady state, each component shown in Table 1 is melt-kneaded by a twin-screw extruder 609 while degassing with an degassing device. The resulting melt is supplied from above the rotor 601 through the double-tube cylindrical body 605 to the inside of the rotor 601 at a rate of 2 kg / hr, and the rotor 601 is rotated to form a cylindrical shape by centrifugal force. A granular thermocurable resin composition was obtained by passing through a plurality of small holes in the outer peripheral portion 602. The granular thermosetting resin composition discharged through the small holes of the cylindrical outer peripheral portion 602 is collected in, for example, an outer tank 608 installed around the rotor 601. Further, the rotor 601 is connected to the motor 610 and can be rotated at an arbitrary rotation speed. The cylindrical outer peripheral portion 602 having a plurality of small holes installed on the outer circumference of the rotor 601 includes the magnetic material 603 shown in FIG. 5 (b). The cylindrical outer peripheral portion 602 is caused by eddy current loss and hysteresis loss due to the passage of the alternating magnetic flux generated by energizing the exciting coil 604 provided in the vicinity thereof with the AC power generated by the AC power generator 606. It is heated. A cooling jacket 607 is provided on the outer periphery of the collision surface to cool the collision surface. Here, FIG. 5B shows a cross-sectional view of the rotor 601 and the exciting coil 604 for heating the cylindrical outer peripheral portion 602 of the rotor, and FIG. 5C shows a thermosetting resin composition melt-kneaded. A cross-sectional view of a double-tube type cylindrical body 605 for supplying an object to the rotor 601 is shown.

硬化促進剤２：トリフェニルホスフィン（ケイアイ化成社製、ＰＰ−３６０）
（無機充填材）
無機充填材１：溶融球状シリカ（龍森社製、ＭＵＦ−４６Ｖ）
無機充填材２：溶融球状シリカ（マイクロン社製、ＨＳ−２０６）
（シリコーンオイル）
シリコーンオイル１：下記式（５）で表されるシリコーンオイル（東レ・ダウコーニング社製、ＦＺ−３７３０）

Details of each component in Table 1 are as follows.
(Thermosetting resin)
Thermosetting resin 1: Biphenyl type epoxy resin (manufactured by Mitsubishi Chemical Corporation, YX4000HK)
Thermosetting resin 2: Trihydroxyphenylmethane type epoxy resin (manufactured by Mitsubishi Chemical Corporation, 1032H-60)
Thermosetting resin 3: Biphenylene skeleton-containing phenol aralkyl type epoxy resin (manufactured by Nippon Kayaku Co., Ltd., NC-3000L)
(Hardener)
Hardener 1: Trihydroxyphenylmethane type phenol resin (manufactured by Air Water Chemical Inc., HE910-20)
Hardener 2: Biphenylene skeleton-containing phenol formaldehyde resin (manufactured by Nippon Kayaku Co., Ltd., GPH-65)
(Curing accelerator)
Curing accelerator 1: Curing accelerator represented by the following formula (tetraphenylphosphonium bis (naphthalene-2,3-dioxy) phenyl silicate)

Curing Accelerator 2: Triphenylphosphine (manufactured by Keiai Kasei Co., Ltd., PP-360)
(Inorganic filler)
Inorganic filler 1: Fused spherical silica (MUF-46V, manufactured by Ryumori Co., Ltd.)
Inorganic filler 2: Fused spherical silica (manufactured by Micron, HS-206)
(Silicone oil)
Silicone oil 1: Silicone oil represented by the following formula (5) (manufactured by Toray Dow Corning, FZ-3730)

The thermosetting resin compositions of Examples and Comparative Examples in Table 1 above were evaluated as follows.

(Surface energy)
Using a compression molding machine (manufactured by TOWA Corporation), while depressurizing the inside of the cavity, the mold temperature is 175 ° C, the clamping pressure is 9.6 MPa, the injection (compression) time is 20 seconds, and the curing time is 120 seconds. A BT resin substrate having no via wiring, PKG outer dimensions: 234 mm × 71 mm × 0.2 mm, no chip mount) was obtained by using a mold release film. The surface roughness Ra of the obtained molded product was 0.1 μm. The surface roughness Ra was measured by a laser microscope (VK-9700, 9710 manufactured by KEYENCE CORPORATION).
Next, prepare a solution in which the ratio of ethanol and pure water is shaken, apply this solution to the surface of the obtained molded product with a brush, and the surface energy from the mixing ratio of ethanol / pure water that makes the solution wet. Was calculated. The surface energy of ethanol (reagent) is 22 mN / m.

(Gel time)
The obtained thermosetting resin composition is placed on a hot plate controlled at 175 ° C. and kneaded with a spatula at a stroke of about 1 time / sec. The time from when the resin composition was melted by heat to when it was cured was measured and used as the gel time. The smaller the gel time, the faster the curing.

(Glass transition temperature (Tg))
The resin composition was injection-molded using a transfer molding machine at a mold temperature of 175 ° C., an injection pressure of 9.8 MPa, and a curing time of 3 minutes to obtain a test piece having a size of 15 mm × 4 mm × 4 mm. Next, the obtained test piece was post-cured at 175 ° C. for 4 hours, and then using a thermomechanical analyzer (TMA100 manufactured by Seiko Electronics Inc.), the measurement temperature range was 0 ° C. to 320 ° C., and the temperature rise rate. The measurement was carried out under the condition of 5 ° C./min. The glass transition temperature was calculated from this result. The unit of glass transition temperature is ° C.

(Collapse angle)
Angle of repose, angle of repose, angle of difference: As shown in FIG. 4 (a), at the center of a disk-shaped horizontal plate 505 with a diameter of 80 mm attached to a powder tester (manufactured by Hosokawa Micron Co., Ltd., model PT-E). The granular thermosetting resin composition 502 was put into the horizontal plate 505 from the vertical direction using the funnel 501 to form conical granules 504 on the horizontal plate 505. The granular thermosetting resin composition was added until the cone maintained a constant shape, and the angle of repose (φ) was determined using a protractor as shown in FIG. 4 (a) to obtain the angle of repose. Next, as shown in FIG. 4B, a 109 g weight 503 on the same pedestal 506 as the horizontal plate 505 was dropped three times from a height of 160 mm, and a part of the granular thermosetting property was caused by impact. After the resin composition collapsed and fell off, the elevation angle (θ) of the granules 507 was determined using a protractor as shown in FIG. 4B, and the collapse angle was measured.

(With mold sticking)
Using a compression molding machine (manufactured by TOWA Corporation), while depressurizing the inside of the cavity, the mold temperature is 175 ° C, the clamping pressure is 9.6 MPa, the injection (compression) time is 20 seconds, and the curing time is 120 seconds. A BT resin substrate having no via wiring, PKG outer dimensions: 234 mm × 71 mm × 0.2 mm, without chip mount) was molded using a release film. If the molded product and the release film did not stick to each other when the mold was opened after molding, it was marked as ◯, otherwise it was marked as x.
As shown in FIG. 3, one surface of the obtained plate-shaped Map molded product had an area capable of securing a plurality of chip mounting areas.

(Fillability)
After the evaluation of the sticking of the mold, the surface of the package was visually observed when the package was taken out from the mold. If the surface of the package had irregularities that seemed to be unfilled, it was judged as x, and if there was no surface molding abnormality, it was judged as ○.

(Board productivity)
After the evaluation of the sticking of the mold, the warp of the package was measured when the package was taken out from the mold, and if the size of the warp was within 5 mm, it was evaluated as ◯, and if it was 5 mm or more, it was evaluated as x.

By using the granular thermosetting resin composition obtained in the examples and using compression molding according to the procedure shown in FIG. 2, a resin-sealed substrate having wiring connecting the layers was obtained. It was found that the thermosetting resin composition of the example did not stick to the mold and was excellent in the production stability of the resin-sealed substrate.

Although the present invention has been described in more detail based on the above examples, these are examples of the present invention, and various configurations other than the above can be adopted.

100 Electronic device 110 Resin encapsulation substrate 112 Insulation layer 114 Upper surface 120 Via wiring 130 Metal layer 140 Semiconductor element 150 Wire bonding 160 Adhesive layer 170 Encapsulant layer 200 Electronic device 210 Support base material 212 Carrier foil 220 Metal layer 222 Via wiring 224 Insulation layer 226 Upper surface 230 Metal layer 234 Insulation layer 236 Upper surface 240 Metal layer 246 Upper surface 250 Resin encapsulation substrate 260 Semiconductor element 270 Encapsulant layer 280 Solder bump 300 Resin encapsulation substrate 310, 320 Semiconductor element mounting area 501 Leakage 502 Granular Thermocurable resin composition 503 Weight 504 Granule 505 Water plate 506 Pedestal 507 Granule 601 Rotator 602 Cylindrical outer circumference 603 Magnetic material 604 Excitation coil 605 Double tube type cylindrical body 606 AC power generator 607 Cooling jacket 608 Outer tank 609 twin-screw extruder 610 motor

Claims (9)

A thermosetting resin composition used for forming a resin-sealed substrate.
It contains an epoxy resin and a silicone oil represented by the general formula (1).
The content of the silicone oil is 0.05% by mass or more and 1.0% by mass or less with respect to the entire thermosetting resin composition.
The surface energy of the cured plate obtained by curing the thermosetting resin composition at 175 ° C. is 22 mN / m or more and 30 mN / m or less.
A thermosetting resin composition having a gel time of 50 seconds or more at 175 ° C.

(However, in the above general formula (1), R ₁ is an organic group selected from an alkyl group having 1 to 12 carbon atoms, an aryl group, and an aralkyl group, and may be the same as or different from each other. ₂ represents an alkylene group _{having 1 to 9 carbon atoms. R 3} is a hydrogen atom or an alkyl group having 1 to 9 carbon atoms. A is selected from an epoxy group, a hydroxyl group, an amino group, a ureido group, and an aryl group. that is a functional group .R ₄ is alkyl of 1 to 12 carbon atoms, an aryl group, an organic group selected from aralkyl group, or a carbon, nitrogen, oxygen, sulfur, group composed of atoms selected from hydrogen It may be the same as or different from each other, and the average values l, m, n, a, and b have the following relationship.
l ≧ 0, m ≧ 0, n ≧ 1, l + m + n ≧ 5,
0.02 ≤ n / (l + m + n) ≤ 0.8,
a ≧ 0, b ≧ 0, a + b ≧ 1) The thermosetting resin composition according to claim 1.
A thermosetting resin composition having a glass transition temperature (Tg) of a cured product of the thermosetting resin composition of 145 ° C. or higher. The thermosetting resin composition according to claim 1 or 2.
A thermosetting resin composition in the form of granules or sheets. The thermosetting resin composition according to claim 1 or 2.
The thermosetting resin composition is in the form of granules and is in the form of granules.
A thermosetting resin composition having a decay angle of 35 ° or less in the granular thermosetting resin composition. The thermosetting resin composition according to any one of claims 1, 2 and 4.
The thermosetting resin composition is in the form of granules and is in the form of granules.
A thermosetting resin composition having an average particle size of 1.0 mm or less in the granular thermosetting resin composition. The thermosetting resin composition according to any one of claims 1 to 5.
Contains inorganic fillers
A thermosetting resin composition in which the content of the inorganic filler is 70% by mass or more with respect to the entire thermosetting resin composition. The thermosetting resin composition according to claim 6.
A thermosetting resin composition having an average particle size of 5 μm or less of the inorganic filler. A resin-sealed substrate comprising a cured product of the thermosetting resin composition according to any one of claims 1 to 7. The resin-sealed substrate according to claim 8 and
An electronic device including an electronic component mounted on the resin-sealed substrate.

Images