JP2020132750A - Sealing resin composition and electronic device using the same - Google Patents

Abstract

To provide a sealing resin composition, that is excellent in volume resistivity and laser marking visibility.SOLUTION: The sealing resin composition of the present invention is a sealing resin composition containing an epoxy resin, a curing agent, an inorganic filler, and black titanium oxide, and in which, in the Labcolor coordinate of a cured product of said sealing resin composition, that: the value of brightness Lis 29.0 to 33.5, the value of ais -2.0 to -0.1, and the value of bis -5.0 to -2.5, is satisfied.SELECTED DRAWING: None

Description

The present invention relates to a sealing resin composition and an electronic device using the same.

So far, various developments have been made in resin compositions for sealing. As this kind of technique, for example, the technique described in Patent Document 1 is known. Patent Document 1 describes an epoxy resin composition for encapsulation containing an epoxy resin, a curing agent, an inorganic filler, a mold release agent, carbon black, and white titanium oxide (Table 1 of Patent Document 1).

Japanese Unexamined Patent Publication No. 2001-207030

However, as a result of the examination by the present inventor, it has been found that the sealing resin composition described in Patent Document 1 has room for improvement in terms of volume resistivity and laser marking visibility.

As a result of further examination, the present inventor adopted black titanium oxide as the black pigment in the sealing resin composition, and the L ^* a ^* b ^* color coordinates of the cured product thereof were L ^* value, a ^* value, and b. ^{* We} have found that by designing the sealing resin composition so that the value is within an appropriate numerical range, it is possible to improve the visibility of laser printing while suppressing the decrease in volume resistance, and completed the present invention. It was.

According to the present invention
Epoxy resin and
Hardener and
Inorganic filler and
With black titanium oxide,
A resin composition for sealing, which comprises
In the L ^* a ^* b ^* color coordinates of the cured product of the sealing resin composition,
The value of lightness L ^* is 29.0 to 33.5.
The value of a ^* is -2.0 to -0.1,
The value of b ^* is -5.0 to -2.5.
A sealing resin composition is provided.

Further, according to the present invention.
An electronic device including an electronic component and a sealing material for sealing the electronic component.
The sealing material is composed of a cured product of the sealing resin composition according to any one of claims 1 to 8.
Electronic devices are provided.

According to the present invention, there is provided a sealing resin composition having excellent volume resistivity and laser marking visibility, and an electronic device using the same.

It is sectional drawing for demonstrating an example of the structure of an electronic device. FIG. 5 is a cross-sectional view showing an example of a structure of an electronic device different from that shown in FIG.

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. Moreover, the figure is a schematic view and does not match the actual dimensional ratio.

<Resin composition for sealing>
The sealing resin composition of the present embodiment contains an epoxy resin (A), a curing agent (B), an inorganic filler (C), and black titanium oxide (D).
The L ^* a ^* b ^* color coordinates of the cured product of the sealing resin composition of the present embodiment satisfy the following.
The value of the lightness L ^* is 29.0 to 33.5, preferably 29.5 to 33.2, and more preferably 30.0 to 33.0.
The value of a ^* is -2.0 to -0.1, preferably -1.4 to -0.2, and more preferably -1.3 to -0.3.
The value of b ^* is -5.0 to -2.5, preferably -5.0 to -3.0, and more preferably -4.9 to -3.5.

Here, the values of L ^* , a ^*, and b ^* are the values under the definition of 1976 by the International Commission on Illumination (CIE). L ^* , a ^* , and b ^* can be measured by using a commercially available colorimeter.
The cured product of the sealing resin composition is obtained by curing under the conditions of, for example, a molding temperature of 175 ° C., a curing time of 100 seconds, and a molding pressure of 8 MPa.

According to this embodiment, the sealing resin composition is designed so that the L ^* value, a ^* value, and b ^* value of the cured product in the L ^* a ^* b ^* color coordinates are within an appropriate numerical range. As a result, the visibility of laser marking can be improved while suppressing the decrease in volume resistivity.

Further, according to the findings of the present inventor, as a result of arranging various powdered black pigments between the electrodes and confirming the current value when a predetermined voltage (about 30 V) is applied between the electrodes, black titanium oxide It was found that the current value was smaller than that of carbon black, and it was difficult to conduct the current.

Further, the sealing resin composition may be configured not to contain carbon black as a black pigment. Here, "not contained" means that the resin composition is substantially not contained, and the content of the sealing resin composition with respect to the whole is, for example, 0.01% by mass or less, preferably 0% by mass. As a result, it is possible to realize a sealing resin composition in which short-circuit defects are reduced while maintaining the laser stamping property and the stamping visibility.

The volume resistivity of the cured product of the sealing resin composition at room temperature of 25 ° C. is, for example, 1.0 × 10 ¹⁴ Ω · cm or more, 1.0 × 10 ¹⁸ Ω · cm or less, preferably 5.0 ×. It is 10 ¹⁴ Ω · cm or more, 5.0 × 10 ¹⁷ Ω · cm or less, more preferably 1.0 × 10 ¹⁵ Ω · cm or more, 1.0 × 10 ¹⁷ Ω · cm or less.

The volume resistivity of the cured product of the sealing resin composition at 150 ° C. is, for example, 1.0 × 10 ¹⁰ Ω · cm or more, 5.0 × 10 ¹⁴ Ω · cm or less, preferably 5.0 × 10 ^{It is 10} Ω · cm or more, 1.0 × 10 ¹⁴ Ω · cm or less, more preferably 1.0 × 10 ¹¹ Ω · cm or more, 1.0 × 10 ¹³ Ω · cm or less.

In the present embodiment, for example, by appropriately selecting the type and blending amount of each component contained in the sealing resin composition, the method for preparing the sealing resin composition, and the like, the above L ^* , a ^*, and b It is possible to control the value of ^* and the volume resistivity. Among these, for example, the appropriate selection of the type and content of black titanium oxide (D), the absence of carbon black, and the like are desired for the values of L ^* , a ^*, and b ^* and the volume resistivity. It is mentioned as an element to make the numerical range of.

Hereinafter, each component contained or may be contained in the composition and various properties of the composition will be described in more detail.

・ Epoxy resin (A)
The sealing resin composition of the present embodiment contains an epoxy resin (A).
Specifically, the epoxy resin (A) can be a monomer, an oligomer, or a polymer having two or more epoxy groups in one molecule. The molecular weight and molecular structure of the epoxy resin (A) are not particularly limited.

Specifically, the epoxy resin (A) is a biphenyl type epoxy resin; a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a tetramethyl bisphenol F type epoxy resin, or the like, a bisphenol type epoxy resin; a stillben type epoxy resin; a phenol novolac type. Novolak type epoxy resin such as epoxy resin and cresol novolac type epoxy resin; polyfunctional epoxy resin such as triphenol methane type epoxy resin and alkyl modified triphenol methane type epoxy resin; selected from the group consisting of phenylene skeleton and biphenylene skeleton 1 Or a phenol aralkyl type epoxy resin such as a naphthol aralkyl type epoxy resin having 1 or 2 skeletons selected from the group consisting of a phenol aralkyl type epoxy resin having 2 skeletons, a phenylene skeleton and a biphenylene skeleton; a dihydroxynaphthalene type epoxy resin, Naftor-type epoxy resin such as epoxy resin obtained by glycidyl etherification of dihydroxynaphthalene dimer; triazine nucleus-containing epoxy resin such as triglycidyl isocyanurate and monoallyl diglycidyl isocyanurate; dicyclopentadiene-modified phenol-type epoxy resin and the like Arihashi cyclic hydrocarbon compound modified phenol type epoxy resin, etc. can be mentioned.

The epoxy resin having the biphenyl skeleton can contain a compound represented by the following general formula (1) (biphenyl aralkyl type epoxy resin).

In the above general formula (1), R ¹ and R ² each independently represent a hydrogen atom, a linear or branched alkyl group having 1 to 8 carbon atoms, or an aryl group, and n is 0 to 10. Indicates an integer.
In the general formula (1), a plurality of R ¹ and R ² may be the same or different from each other.

Further, the epoxy resin having the biphenyl skeleton can contain a compound represented by the following general formula (2).

In the above general formula (2), k1 and l1 each represent an integer of 0 to 4, m and n each represent an integer of 1 to 5, and R ³ and R ⁴ each have independent substituents. It represents a good hydrocarbon group with 1 to 10 carbon atoms, and R ³ and R ⁴ may be the same or different from each other. However, in the general formula (2), the left and right phenyl structures of the biphenyl skeleton are different.

The compound represented by the general formula (2) can be obtained by reacting a polyvalent hydroxybiphenyl with epihalohydrin.

The sealing epoxy resin composition may contain, as the epoxy resin, an epoxy resin having two or more kinds of biphenyl skeletons different from each other. By using an epoxy resin having two or more kinds of biphenyl skeletons in which the amount of chlorine is reduced, long-term connection reliability in a high temperature and high humidity environment can be improved.

The sealing resin composition may contain only one type of epoxy resin (A), or may contain two or more types of epoxy resin (A).
The amount of the epoxy resin (A) is, for example, 2% by mass based on the entire sealing resin composition (100% by mass) from the viewpoint of obtaining suitable fluidity during molding and improving the filling property and moldability. As mentioned above, it is preferably 3% by mass or more, and more preferably 4% by mass or more.
From another viewpoint, the amount of the epoxy resin (A) is based on the entire sealing resin composition (100% by mass) from the viewpoint of improving the insulating properties of the sealing material obtained by using the sealing resin composition. For example, it is 40% by mass or less, preferably 30% by mass or less, more preferably 15% by mass or less, and further preferably 10% by mass or less.

・ Hardener (B)
The sealing resin composition of the present embodiment contains a curing agent (B). The curing agent (B) is not particularly limited as long as it reacts with the epoxy resin (A) to cure it.
Specific examples of the curing agent (B) include amine-based curing agents (curing agents having an amino group) and phenol-based curing agents.

Examples of the amine-based curing agent include aliphatic diamines having 2 to 20 carbon atoms such as ethylenediamine, trimethylenediamine, tetramethylenediamine, and hexamethylenediamine, metaphenylenediamine, paraphenylenediamine, paraxylenediamine, and 4,4'-diamino. Diphenylmethane, 4,4'-diaminodiphenylpropane, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylsulfone, 4,4'-diaminodicyclohexane, bis (4-aminophenyl) phenylmethane, 1,5 − Diaminonaphthalene, metaxylene diamine, paraxylene diamine, aromatic diamines such as 1,1-bis (4-aminophenyl) cyclohexane, dicyanodiamide and the like can be mentioned.

As the phenolic resin-based curing agent, a monomer, an oligomer, or a polymer having two or more phenolic hydroxyl groups in one molecule can be used in general, and the molecular weight and molecular structure thereof are not particularly limited.
Examples of such phenolic resin-based curing agents include novolak-type resins such as phenol novolac resin, cresol novolak resin, and bisphenol novolak; polyvinylphenol; and polyfunctional types such as biphenyl aralkyl type phenol resin and phenol resin having a triphenylmethane skeleton. Phenolic resin; Modified phenolic resin such as terpen-modified phenolic resin, dicyclopentadiene-modified phenolic resin; Phenolic aralkyl resin having phenylene skeleton and / or biphenylene skeleton, aralkyl resin such as naphthol aralkyl resin having phenylene and / or biphenylene skeleton; Examples thereof include bisphenol compounds such as bisphenol A and bisphenol F, and these may be used alone or in combination of two or more. Above all, it is preferable to contain a polyfunctional phenol resin from the viewpoint of improving the moisture resistance reliability of the semiconductor package under high temperature and high humidity environment conditions.

In addition, as the curing agent (B), polyoxystyrene such as polyparaoxystyrene; alicyclic acid anhydride such as hexahydrophthalic anhydride (HHPA) and methyltetrahydrophthalic anhydride (MTHPA), trimellitic anhydride (TMA) , Acid anhydrides containing aromatic acid anhydrides such as pyromellitic anhydride (PMDA) and benzophenone tetracarboxylic acid (BTDA); polyether compounds such as polysulfide, thioester and thioether; isocyanate prepolymers, blocked isocyanates and the like. Isocyanate compound; organic acids such as carboxylic acid-containing polyester resin can be mentioned.

From the viewpoint of moisture resistance and reliability in encapsulation of electronic devices, the curing agent (B) is preferably a compound having at least two phenolic hydroxyl groups in one molecule. More specifically, novolak-type phenolic resins such as phenol novolac resin, cresol novolak resin, tert-butylphenol novolak resin, and nonylphenol novolak resin; resol-type phenol resin; polyoxystyrene such as polyparaoxystyrene; phenol aralkyl resin containing phenylene skeleton. , Biphenylene skeleton-containing phenol aralkyl resin and the like are preferably mentioned.

The sealing resin composition may contain only one type of curing agent (B), or may contain two or more types.
The amount of the curing agent (B) is preferably 1 based on the entire composition (100% by mass) from the viewpoint of improving excellent fluidity, filling property, moldability, etc. when sealing the electronic device. It is by mass% or more, more preferably 2% by mass or more, still more preferably 3% by mass or more.
As another viewpoint, from the viewpoint of improving the moisture resistance reliability and reflow resistance of the electronic device, the amount of the curing agent (B) is preferably 25% by mass or less, more preferably 25% by mass or less, based on the entire composition (100% by mass). It is 15% by mass or less, more preferably 10% by mass or less.

Regarding the amounts of the epoxy resin (A) and the curing agent (B), it is preferable that the equivalent ratio is an appropriate value. By appropriately adjusting the equivalent ratio, there is a tendency to obtain effects such as better moldability and further improvement in reliability when used as a sealing material.
For example, when the curing agent (B) is a phenolic curing agent, the equivalent ratio of the epoxy resin (A) to the curing agent (B), that is, the number of moles of epoxy groups in the epoxy resin (A) / the curing agent (B) The ratio of the number of molar phenolic hydroxyl groups in) is, for example, 0.5 to 2, preferably 0.6 to 1.8, and more preferably 0.8 to 1.5.
When the curing agent (B) is an amine-based curing agent, the amino group (-NH ₂ ) has two active hydrogens, so that the number of moles of epoxy groups in the epoxy resin (A) / the curing agent (B) The ratio of the number of moles of amino groups is, for example, 1 to 4, preferably 1.2 to 3.6, and more preferably 1.6 to 3.

-Inorganic filler (C)
The sealing resin composition of the present embodiment contains an inorganic filler (C). As the inorganic filler, those generally used in resin compositions for encapsulating electronic devices can be used.
Specific examples of the inorganic filler (C) include fused crushed silica, molten spherical silica, crystalline silica, secondary aggregated silica and other silica; alumina; titanium white; aluminum hydroxide; talc; clay; mica; glass fiber and the like. Can be mentioned. Among these, silica is preferable, and fused spherical silica is particularly preferable.
The particle shape of the inorganic filler (C) is preferably substantially spherical.
The average particle size of the inorganic filler (C) is not particularly limited, but is typically 1 to 100 μm, preferably 1 to 50 μm, and more preferably 1 to 20 μm. When the average particle size is appropriate, the fluidity at the time of molding can be further improved, and the filling property of the composition in the gorge of the electronic device can be improved.

The amount of the inorganic filler (C) is preferably 50% by mass or more, more preferably 60% by mass or more, still more preferably 65% by mass or more, based on the entire sealing resin composition (100% by mass). ..
Further, from the viewpoint of more effectively improving the fluidity and filling property of the sealing resin composition during molding, the amount of the inorganic filler (C) is based on the entire sealing resin composition (100% by mass). ), It is preferably 95% by mass or less, more preferably 90% by mass or less.
By appropriately adjusting the amount of the inorganic filler (C), the low hygroscopicity and low thermal expansion of the sealing material formed by the sealing resin composition are further improved, and the moisture resistance and reliability of the obtained electronic device are further improved. It is possible to obtain effects such as further improvement of reflow resistance and further improvement of fluidity and filling property during molding.

-Black titanium oxide (D)
The sealing resin composition of the present embodiment contains black titanium oxide (D). As described above, the black titanium oxide (D) is mainly used to impart blackness to the sealing resin composition.
Two or more kinds of black titanium oxide (D) may be used in combination in order to obtain a desired color and finely adjust the color.

The black titanium oxide (D) is not necessarily limited as long as it has an oxygen defect, but can be expressed by the general formula of TiO _x (where X is a real number and indicates 1 or more and less than 2). .. These may be used alone or in combination of two or more.

In the above general formula, the lower limit of X is, for example, preferably 1 or more, more preferably 1.2 or more, and even more preferably 1.5 or more. The upper limit of X is, for example, preferably less than 2, more preferably 1.9 or less, and even more preferably 1.85 or less. By setting X to the lower limit or higher, the insulating property can be improved. In addition, the dispersibility of black titanium oxide (D) in the sealing resin composition can be enhanced. On the other hand, by setting X to the upper limit value or less, the imprintability of a laser such as a YAG laser can be improved.

Specific examples of the black titanium oxide (D) are not particularly limited, and examples thereof include Ti ₂ O ₃ , Ti ₄ O ₇ , Ti ₅ O ₉ , Ti ₆ O ₁₁ , and the like. The black titanium oxide (D) can contain at least one or more of Ti ₄ O ₇ , Ti ₅ O ₉ , and Ti ₆ O ₁₁ .

The lower limit of the average particle diameter D ₅₀ of the black titanium oxide (D) is, for example, 0.1 μm or more, preferably 0.2 μm or more, and more preferably 0.3 μm or more. Thereby, the insulating property of the cured product can be improved.
On the other hand, the upper limit of the average particle diameter D ₅₀ is, for example, 2.0 μm or less, preferably 1.9 μm or less, and more preferably 1.8 μm or less. Thereby, the dispersibility of the black titanium oxide (D) can be enhanced.
The method for measuring the average particle size D ₅₀ of black titanium oxide (D) can be measured by using, for example, a laser diffraction type particle size distribution measuring device (LA-500 manufactured by HORIBA).

The lower limit of the content of black titanium oxide (D) in the sealing resin composition is, for example, 0.1% by mass or more, preferably 0.5% by mass, based on the entire sealing resin composition. The above is more preferably 1.0% by mass or more. As a result, the laser imprintability can be improved. Further, from the viewpoint of balancing the improvement of fluidity and the suppression of cost increase, the upper limit of the content of black titanium oxide in the sealing resin composition is, for example, 5 with respect to the entire sealing resin composition. It is 0.0% by mass or less, preferably 3.0% by mass or less, and more preferably 2.0% by mass or less.

(Other ingredients)
The sealing resin composition of the present embodiment may contain other components that do not fall under any of the above (A) to (E). Specific examples of other components include curing accelerators, coupling agents, mold release agents, ion scavengers, flame retardants, antioxidants, low stress agents, colorants and the like.
When the sealing resin composition contains other components, it may contain only one kind or two or more kinds.

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, adduct of phosphonium compound and silane compound; 1,8-diazabicyclo [ 5.4.0] -7-Undecene, benzyldimethylamine, amidines such as 2-methylimidazole or tertiary amines, quaternary salts of amidines or amines, and other nitrogen atom-containing compounds can be mentioned.

Among these, a phosphorus atom-containing compound is preferable 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.

When a curing accelerator is used, the lower limit is preferably 0.01% by mass or more, more preferably 0.%, based on the entire composition (100% by mass) in consideration of the balance with other components. It is 05% by mass or more, and the upper limit is preferably 2.0% by mass or less, more preferably 1.0% by mass or less.

Examples of the coupling agent include aminosilanes such as epoxysilane, mercaptosilane and phenylaminosilane, various silane compounds such as alkylsilane, ureidosilane, vinylsilane and methacrylsilane, titanium compounds, aluminum chelate compounds and aluminum / zirconium compounds. Known coupling agents can be mentioned.

Among these, from the viewpoint of fluidity and the like, it is more preferable to contain epoxysilane or aminosilane, and it is further preferable to contain secondary aminosilane. Specific examples of the preferred coupling agent include phenylaminopropyltrimethoxysilane.

When a coupling agent is used, the lower limit is preferably 0.01% by mass or more, more preferably 0.%, based on the entire composition (100% by mass) in consideration of the balance with other components. It is 05% by mass or more, and the upper limit is preferably 2.0% by mass or less, more preferably 1.0% by mass or less.

Examples of the mold release agent include natural waxes such as carnauba wax, synthetic waxes such as polyethylene oxide wax and montanic acid ester wax, higher fatty acids such as zinc stearate and metal salts thereof, paraffin and the like.

When a mold release agent is used, the lower limit is preferably 0.01% by mass or more, more preferably 0.%, based on the entire composition (100% by mass) in consideration of the balance with other components. It is 05% by mass or more, and the upper limit is preferably 2.0% by mass or less, and more preferably 1.0% by mass or less.

Examples of the ion scavenger include hydrotalcite.
When an ion scavenger is used, the lower limit of the content of the ion scavenger in the sealing resin composition is preferably based on the entire composition (100% by mass) from the viewpoint of improving the reliability of the electronic device. It is 0.03% by mass or more, more preferably 0.05% by mass or more, and the upper limit is preferably 2.0% by mass or less, more preferably 1.0% by mass or less.

Coloring agents such as red iron oxide; low stress components such as silicone oil and silicone rubber; natural waxes such as carnauba wax, synthetic waxes, higher fatty acids such as zinc stearate and release agents such as metal salts or paraffins thereof; Flame retardants such as aluminum, magnesium hydroxide, zinc borate, zinc molybdate, and phosphazene, and antioxidants such as hindered phenol compounds, hindered amine compounds, and thioether compounds can be used.

-Shape of composition The shape of the sealing resin composition of the present embodiment is not particularly limited. The shape is, for example, particulate, granular, tablet-like or sheet-like.

-Method for producing the composition The method for producing the sealing resin composition of the present embodiment is not particularly limited.
For example, it can be obtained by a method in which each of the above-mentioned components is mixed by a known means, further melt-kneaded by a kneader such as a roll, a kneader or an extruder, cooled, and then pulverized.
If necessary, it may be tableted into a tablet after pulverization.
If necessary, after pulverization, it may be formed into a sheet by, for example, vacuum laminating or compression molding.
If necessary, the degree of dispersion, fluidity, etc. of the obtained sealing resin composition may be adjusted.

<Electronic equipment, its manufacturing method, etc.>
An electronic device can be manufactured by using the above-mentioned sealing resin composition.
Specifically, it is possible to obtain an electronic device including an electronic component and a sealing material for sealing the electronic component (this sealing material is a cured product of the above-mentioned sealing resin composition). ..

Hereinafter, an example of the electronic device will be described with reference to the drawings.

FIG. 1 is a cross-sectional view showing the configuration of the electronic device 100. The electronic device 100 shown in FIG. 1 includes a semiconductor element 20 mounted on a substrate 30 and a sealing material 50 for sealing the semiconductor element 20.
The sealing material 50 is composed of a cured product obtained by curing the sealing resin composition of the present embodiment.

FIG. 1 shows a case where the substrate 30 is a circuit board. In this case, as shown in FIG. 1, for example, a plurality of solder balls 60 are formed on the other surface of the substrate 30 opposite to the one on which the semiconductor element 20 is mounted. The semiconductor element 20 is mounted on the substrate 30 and is electrically connected to the substrate 30 via the wire 40. On the other hand, the semiconductor element 20 may be flip-chip mounted on the substrate 30. Here, the wire 40 is made of, for example, copper.

The encapsulant 50 seals the semiconductor element 20 so as to cover the other surface of the semiconductor element 20 opposite to one surface facing the substrate 30. In FIG. 1, the sealing material 50 is formed so as to cover the other surface and the side surface of the semiconductor element 20. The sealing material 50 can be formed, for example, by molding the sealing resin composition by using a known method such as a transfer molding method or a compression molding method.

As a method of manufacturing the electronic device 100, for example,
The process of mounting the semiconductor element 20 on the substrate 30 and
A sealing step of sealing the semiconductor element 20 using the sealing resin composition of the present embodiment,
Examples thereof include manufacturing methods including.

Further, in order to manufacture an electronic device in which the electronic device 100 is electrically bonded to another substrate, a reflow step may be performed after the sealing step.

FIG. 2 is a cross-sectional view showing the configuration of the electronic device 100, which is different from FIG.
In the electronic device 100 of FIG. 2, a lead frame is used as the substrate 30. In this case, the semiconductor element 20 is mounted on the die pad 32 of the substrate 30, for example, and is electrically connected to the outer lead 34 via the wire 40. Further, the sealing material 50 is formed by using the sealing resin composition of the present embodiment in the same manner as in the example of FIG.

The sealing material 50 is formed, for example, by sealing and molding the sealing resin composition by using a known method such as a transfer molding method or a compression molding method.

A mark is stamped on the upper surface of the sealing material 50 by a laser such as a YAG laser. The mark is composed of, for example, at least one of letters, numbers, or symbols consisting of straight lines or curves. Further, the above mark indicates, for example, a product name, a product number, a lot number, a manufacturer name, or the like of a semiconductor package. Further, the mark is, for example, YVO ₄ laser may be imprinted by carbonic laser.

According to the present embodiment, it is also possible to obtain a semiconductor device having excellent laser stamping property and stamping visibility.

Although the embodiments of the present invention have been described above, these are examples of the present invention, and various configurations other than the above can be adopted. Further, the present invention is not limited to the above-described embodiment, and modifications, improvements, etc. within the range in which the object of the present invention can be achieved are included in the present invention.

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 resin composition for sealing>
According to the blending ratio shown in Table 1, each component was pulverized and mixed using a mixer, and then roll-kneaded at 80 ° C. for 5 minutes. Then, this was cooled and pulverized to obtain a sealing resin composition.

(Inorganic filler)
-Inorganic filler 1: Fused spherical silica (manufactured by Ryumori Co., Ltd., MSV-SF540, average particle diameter d50: 14 μm)
-Inorganic filler 2: fused spherical silica (manufactured by Denka, FB-100XFD, average particle diameter d50: 14 μm)
-Inorganic filler 3: fused spherical silica (manufactured by Admatex, SD2500-SQ, average particle diameter d50: 0.9 μm)
-Inorganic filler 4: fused spherical silica (manufactured by Admatex, SD5500-SQ, average particle diameter d50: 1.5 μm)

(Black titanium oxide)
-Titanium Black 1: (Ako Kasei Co., Ltd., TirackD TM-F, average particle size d50: 0.6 μm)
-Titanium Black 2: (Ako Kasei Co., Ltd., TirackDM, average particle size d50: 0.7 μm)
-Titanium Black 3: (Ako Kasei Co., Ltd., TirackD TM-HPD, average particle size d50: 0.4 μm)
-Titanium Black 4: (Ako Kasei Co., Ltd., TirackD TM-HPF, average particle size d50: 0.6 μm)

(Coupling agent)
-Coupling agent 1: Phenylaminopropyltrimethoxysilane (manufactured by Toray Dow Corning, CF4083)

(Epoxy resin)
-Epoxy resin 1: Biphenyl aralkyl type epoxy resin (manufactured by Nippon Kayaku Co., Ltd., NC-3000L)
-Epoxy resin 2: Biphenyl type epoxy resin (manufactured by Mitsubishi Chemical Corporation, YL6677)

(Hardener)
-Hardening agent 1: Biphenyl aralkyl type phenol resin (MEH-7851SS, manufactured by Meiwa Kasei Co., Ltd.)
-Hardener 2: Phenolic resin having a triphenylmethane skeleton (manufactured by Air Water, HE910-20)
-Hardening agent 3: Phenolic resin having a triphenylmethane skeleton (MEH-7500, manufactured by Meiwa Kasei Co., Ltd.)

Using the obtained sealing resin composition, evaluation was performed based on the following evaluation items. The results are shown in Table 2.

<Evaluation of color>
The compositions of each Example or Comparative Example were cured by a compression molding method under the conditions of a molding temperature of 175 ° C., a curing time of 100 seconds, and a molding pressure of 8 MPa to obtain a strip-shaped cured product.
The L ^* value, a ^* value and b ^* on the surface of this cured product were measured using a color reader CR-13 (manufactured by Konica Minolta Sensing Co., Ltd.).

<Evaluation of sealability>
(Laser stamp visibility)
For each example, the imprintability of the laser in the encapsulant in the structure used for the measurement of the color difference ΔE ^* was evaluated by the following procedure.
The laser stamping surface of the sample used for evaluating the laser stamping depth was scanned by the following method, and the obtained image was binarized under the following conditions.
(Laser processing conditions)
Type: Fiber laser Wavelength: 1090 nm
Output: 2.5W
Scanning speed: 400 mm / s
(Scan method)
The image was captured by the scan function using a copy machine. The equipment and conditions are shown below.
Equipment: MX-5140 (Sharp, copy / scanner / fax multifunction device)
Function: Scan (SMB)
Density: Automatic resolution: 600 x 600 dpi
Format: JPEG
Color mode: Full color Original: Import size: Photograph, Output size: Automatic (binarization method)
(1) ImageJ (manufactured by NIH Image) was started and the scanned file was opened.
(2) The area where the laser mark was stamped was selected so as to be a rectangle having a pixel size of 1200 × 500, and the image of the selected area was cut out.
(3) The cut-out area was band-filtered under the following conditions to remove noise.
Filter_large structures down to 30 pixels
Filter_small structures up to 3 pixels
Suppress stripes: None
Tolerance of direction; 5%
Autoscale after filtering: Enabled
Saturate image when autoscaling: enabled
Display filter: Invalid (4) The image obtained in (3) above was binarized. The threshold color was set to "B &W" (black and white), 66 of 256 gradations was set as the threshold, and the values below that were set to black.
(5) The stamped portion was cut out to a pixel size of 135 × 75.

With respect to the binarized image obtained by the above (binarization method), the visibility of the laser mark in the cut region was visually evaluated by five evaluators according to the following criteria. In addition, the numerical value (%) of binarization is shown in Table 1.
◯: Good visibility and practical use is possible.
×: Difficult to use in practice.

<Evaluation of curing characteristics and physical properties of cured product>
In order to confirm the basic performance of the sealing resin composition, the following evaluations were made regarding the curing characteristics and the physical properties of the cured product.

(Spiral Flow)
Using a low-pressure transfer molding machine (KTS-15, manufactured by Kotaki Seiki Co., Ltd.), a mold for measuring spiral flow according to ANSI / ASTM D 3123-72 was used, and the mold temperature was 175 ° C, injection pressure was 6.9 MPa, and holding pressure. The sealing resin composition was injected under the condition of a time of 120 seconds, and the flow length was measured.
Spiral flow is a parameter of fluidity, and the larger the value, the better the fluidity.

(Gel time)
The sealing resin composition of each Example or Comparative Example was placed on a hot plate set at 175 ° C. After the sample was melted, the time until it hardened was measured while kneading with a spatula. The shorter the gel time, the faster the curing rate.

(Bending strength and flexural modulus)
The encapsulating resin composition of each Example or Comparative Example was tablet-molded to obtain a tablet. The obtained tablet was injection-molded with a sealing resin composition under the conditions of a mold temperature of 175 ° C., an injection pressure of 9.8 MPa, and a curing time of 120 seconds using a transfer molding machine, and the width was 10 mm × the thickness was 4 mm ×. A cured product having a length of 80 mm was obtained. Then, the obtained test piece was post-cured at 175 ° C. for 4 hours to obtain a test piece for evaluation.
The flexural strength and flexural modulus of the obtained test piece at room temperature and 260 ° C. were measured according to JIS K 6911.

(Volume resistivity)
The encapsulating resin composition of each Example or Comparative Example was tablet-molded to obtain a tablet. The obtained tablet was injection-molded using a transfer molding machine under the conditions of a mold temperature of 175 ° C., an injection pressure of 8.3 MPa, and a curing time of 2 minutes to obtain a disk-shaped cured product having a diameter of 100 mm and a thickness of 3 mm. Got This disk-shaped molded product was post-cured at 175 ° C. for 4 hours to obtain an evaluation test piece.
A main electrode having a diameter of 300 mm, a guard electrode having a diameter of 32 mm, and a counter electrode having a diameter of 45 mm were formed on the obtained test piece using carbon paste. Then, the volume resistivity was measured by a method conforming to JIS K 6911 using a super insulation meter (R-503 manufactured by Kawaguchi Electric Works, Ltd.). The measurement conditions were room temperature or 150 ° C. and an applied voltage of 500 V.

It was shown that by using the sealing resin compositions of Examples 1 to 3, it is possible to realize a sealing material which is superior in laser stamping visibility as compared with Comparative Example 1 and can suppress a decrease in volume resistivity. .. By sealing the cured product of the sealing resin composition of Examples 1 to 3 with a sealing material for the electronic components of the electronic device, the reliability and handleability of the electronic device can be improved.

100 Electronic device 20 Semiconductor element 30 Substrate 32 Die pad 34 Outer lead 40 Wire 50 Encapsulant 60 Solder ball

Claims (9)

Epoxy resin and
Hardener and
Inorganic filler and
With black titanium oxide,
A resin composition for sealing, which comprises
In the L ^* a ^* b ^* color coordinates of the cured product of the sealing resin composition,
The value of lightness L ^* is 29.0 to 33.5.
The value of a ^* is -2.0 to -0.1,
The value of b ^* is -5.0 to -2.5.
Resin composition for sealing. The sealing resin composition according to claim 1.
The black titanium oxide contains a compound represented by TiO _x (where X indicates 1 or more and less than 2).
Resin composition for sealing. The sealing resin composition according to claim 1 or 2.
The D _{50 of the} black titanium oxide is 0.1 μm or more and 2.0 μm or less.
Resin composition for sealing. The sealing resin composition according to any one of claims 1 to 3.
The content of the black titanium oxide is 0.1% by mass or more and 5.0% by mass or less with respect to the total solid content of the sealing resin composition.
Resin composition for sealing. The sealing resin composition according to any one of claims 1 to 4.
A resin composition for sealing that does not contain carbon black. The sealing resin composition according to any one of claims 1 to 5.
The volume resistivity of the cured product of the sealing resin composition at room temperature of 25 ° C. is 1.0 × 10 ¹⁴ Ω · cm or more and 1.0 × 10 ¹⁸ Ω · cm or less.
Resin composition for sealing. The sealing resin composition according to any one of claims 1 to 6.
The volume resistivity of the cured product of the sealing resin composition at 150 ° C. is 1.0 × 10 ¹⁰ Ω · cm or more and 5.0 × 10 ¹⁴ Ω · cm or less.
Resin composition for sealing. The sealing resin composition according to any one of claims 1 to 7.
A resin composition for encapsulation, which is in the form of particles, granules, tablets or sheets. An electronic device including an electronic component and a sealing material for sealing the electronic component.
The sealing material is composed of a cured product of the sealing resin composition according to any one of claims 1 to 8.
Electronic device.

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