JP2016113566A - Resin composition for encapsulation, semiconductor device, and structure - Google Patents

Abstract

The present invention provides a sealing resin composition that is excellent in laser-printing properties of a laser such as a YAG laser and that can realize a sealing material colored other than black. The sealing resin composition of the present invention comprises an epoxy resin (A), an inorganic filler (B), a black colorant (C), and a color other than the black colorant (C). An agent (D). And the colorimetric value L * prescribed | regulated by CIE1976L * a * b * colorimetric system of the hardened | cured material of the said resin composition for sealing is 30 or more, and the said colorimetric value L * is 30 or more and less than 80 In this case, the saturation C * is 7 or more. Here, the cured product of the sealing resin composition is obtained by using a low-pressure transfer molding machine under the conditions of a mold temperature of 175 ° C., an injection pressure of 9.8 MPa, and a curing time of 300 seconds. Can be obtained by transfer molding into a mold. The size of the cured product is 50 mm in diameter and 3 mm in thickness. [Selection figure] None

Description

  The present invention relates to a sealing resin composition, a semiconductor device, and a structure.

  The semiconductor device is formed, for example, by sealing and molding a semiconductor element mounted on a substrate using a sealing resin composition. As such a sealing resin composition, for example, a resin composition containing an epoxy resin is used.

  Patent Document 1 (Japanese Patent Application Laid-Open No. 2011-89096) describes a technique related to a sealing resin composition containing an epoxy resin, a curing agent, and a colorant as essential components.

JP 2011-89096 A

  According to the study by the present inventors, in the conventional sealing resin composition, when a colorant other than the black colorant is added, the sealability of a laser such as a YAG laser of the obtained sealing material deteriorates. It became clear that there was a case.

According to the present invention,
A sealing resin composition comprising an epoxy resin (A), an inorganic filler (B), a black colorant (C), and a colorant (D) other than the black colorant (C). There,
Using a low-pressure transfer molding machine, the above sealing resin composition was transfer molded into a mold under the conditions of a mold temperature of 175 ° C., an injection pressure of 9.8 MPa, and a curing time of 300 seconds, and had a diameter of 50 mm and a thickness of 3 mm. When producing a cured product of the sealing resin composition,
When the cured product has a colorimetric value L ^* defined by the CIE 1976 L ^* a ^* b ^* color system of 30 or more and the colorimetric value L ^* is 30 or more and less than 80, the chroma C ^* is 7 or more. A sealing resin composition is provided.

Moreover, according to the present invention,
A substrate;
A semiconductor element mounted on one surface of the substrate;
A sealing material that is composed of a cured product of the sealing resin composition and seals the semiconductor element and the one surface of the base material;
A semiconductor device is provided.

Moreover, according to the present invention,
A substrate;
A plurality of semiconductor elements mounted on one surface of the substrate;
A sealing material configured by a cured product of the sealing resin composition and sealing the plurality of semiconductor elements and the one surface of the base material;
A structure is provided.

  ADVANTAGE OF THE INVENTION According to this invention, the resin composition for sealing which can implement | achieve the sealing material excellent in the laser-printing property of a YAG laser etc. and colored other than black can be provided.

It is sectional drawing which shows an example of the semiconductor device which concerns on this embodiment. It is sectional drawing which shows an example of the structure which concerns on this embodiment.

  Hereinafter, embodiments will be described with reference to the drawings. In all the drawings, the same reference numerals are given to the same components, and the description will be omitted as appropriate. Moreover, the figure is a schematic diagram and does not necessarily match the actual dimensional ratio. Also, “A to B” in the numerical range represents “A or more and B or less” unless otherwise specified.

The sealing resin composition according to the present embodiment includes an epoxy resin (A), an inorganic filler (B), a black colorant (C), and a colorant other than the black colorant (C) ( D). And the colorimetric value L ^* prescribed | regulated by the CIE1976L ^* a ^* b ^* colorimetric system of the hardened | cured material of the said resin composition for sealing is 30 or more. Here, the cured product of the sealing resin composition is obtained by using a low-pressure transfer molding machine under the conditions of a mold temperature of 175 ° C., an injection pressure of 9.8 MPa, and a curing time of 300 seconds. Can be obtained by transfer molding into a mold. The size of the cured product is 50 mm in diameter and 3 mm in thickness.

The present inventor believes that the sealing resin composition is an epoxy resin (A), an inorganic filler (B), a black colorant (C), and a colorant other than the black colorant (C) (D ), It has been newly found that the sealability of a laser such as a YAG laser of a sealing material colored other than black is improved.
In this embodiment, a black colorant (C) is added to the sealing resin composition containing the colorant (D) to such an extent that the resulting sealing material does not become black, so that a YAG laser, etc. It is possible to realize a sealing material that is excellent in laser marking performance and colored other than black.

  Hereinafter, the sealing resin composition, the semiconductor device 100, and the structure 102 according to the present embodiment will be described in detail.

First, the sealing resin composition will be described.
The encapsulating resin composition is used to form an encapsulant that encapsulates a semiconductor element mounted on a substrate. The sealing molding using the sealing resin composition is not particularly limited, and can be performed by, for example, a transfer molding method or a compression molding method.
The sealing resin composition is, for example, a tablet or a granular material. When the sealing resin composition is in the form of a tablet, for example, the sealing resin composition can be molded using a transfer molding method. Moreover, when the resin composition for sealing is a granular material, the resin composition for sealing can be shape | molded using the compression molding method, for example. That the resin composition for sealing is a granular material refers to the case where it is either powdery or granular.
The base material is, for example, a wiring board such as an interposer or a lead frame. The semiconductor element is electrically connected to the base material by wire bonding or flip chip connection.

A semiconductor device obtained by sealing a semiconductor element by sealing molding using a sealing resin composition is not particularly limited. For example, QFP (Quad Flat Package), SOP (Small Outline Package), BGA (BGA) Ball Grid Array), CSP (Chip Size Package), QFN (Quad Flat Non-Leaded Package), SON (Small Outline Non-Leaded Package), LF-BGA (Lead Frame BGA) and the like.
The sealing resin composition according to the present embodiment can also be applied to a structure formed by MAP (Mold Array Package) molding, which is often applied to molding of these packages in recent years. In this case, the said structure is obtained by sealing the several semiconductor element mounted on a base material collectively using the resin composition for sealing.

  Examples of the semiconductor element include, but are not limited to, an integrated circuit, a large-scale integrated circuit, a transistor, a thyristor, a diode, and a solid-state imaging element. The semiconductor element to be encapsulated by the encapsulating resin composition according to the present embodiment is a so-called element that does not involve light input / output, excluding optical semiconductor elements such as a light receiving element and a light emitting element (such as a light emitting diode). Say.

  The sealing resin composition comprises an epoxy resin (A), an inorganic filler (B), a black colorant (C), and a colorant (D) other than the black colorant (C). Including. Thereby, it is possible to realize a sealing resin composition that is excellent in laser-printing property of a laser such as a YAG laser and that can obtain a sealing material colored other than black.

The sealing material formed with the sealing resin composition according to the present embodiment is colored in a color other than black. Specifically, using a low-pressure transfer molding machine, the above resin composition for sealing was transfer molded to a mold under the conditions of a mold temperature of 175 ° C., an injection pressure of 9.8 MPa, and a curing time of 300 seconds, and the diameter was 50 mm. When a cured product of the sealing resin composition having a thickness of 3 mm was produced, the colorimetric value L ₁ ^* defined by the CIE 1976 L ^* a ^* b ^* color system of the cured product was 30 or more.
A sealing material having the colorimetric value L ^* of less than the lower limit is less likely to cause a problem of deterioration in laser marking performance such as a YAG laser. Therefore, in the present embodiment, the effect of the present invention can be effectively obtained when the colorimetric value L ^* is not less than the lower limit value.
Here, when the colorimetric value L ^* is 30 or more and less than 80, when the saturation C ^* is 7 or more, the problem of deterioration of the laser sealability is likely to occur, so that the effect of the present invention is effectively obtained. be able to. Here, C ^* is calculated by {(a ^* ) ² + (b ^* ) ² } ^1/2 .

  The sealing resin composition according to this embodiment is usually a resin composition that gives a non-transparent cured product. Here, the non-transparent cured product specifically refers to the above sealing resin using a low-pressure transfer molding machine under conditions of a mold temperature of 175 ° C., an injection pressure of 9.8 MPa, and a curing time of 300 seconds. When the composition is transfer molded into a mold to produce a cured resin composition having a diameter of 50 mm and a thickness of 3 mm, the light transmittance at a wavelength of 400 nm in the film thickness direction of the cured product is preferably 50. % Or less, more preferably 25% or less, particularly preferably 10% or less. The light transmittance is measured using, for example, an ultraviolet-visible light spectrophotometer.

(Epoxy resin (A))
In this embodiment, examples of the epoxy resin (A) include biphenyl type epoxy resins; bisphenol type epoxy resins such as bisphenol A type epoxy resins, bisphenol F type epoxy resins, and tetramethylbisphenol F type epoxy resins; stilbene type epoxy resins. A novolac epoxy resin such as a phenol novolac epoxy resin and a cresol novolac epoxy resin; a polyfunctional epoxy resin such as a triphenolmethane epoxy resin and an alkyl-modified triphenolmethane epoxy resin; a phenylene skeleton and / or a biphenylene skeleton Phenol aralkyl type epoxy resins, phenol aralkyl type epoxy resins such as naphthol aralkyl type epoxy resins having a phenylene skeleton and / or a biphenylene skeleton Dihydroxynaphthalene-type epoxy resins, naphthol-type epoxy resins such as epoxy resins obtained by glycidyl etherification of dihydroxynaphthalene dimers; triazine nucleus-containing epoxy resins such as triglycidyl isocyanurate and monoallyl diglycidyl isocyanurate; dicyclopentadiene Examples include bridged cyclic hydrocarbon compound-modified phenol type epoxy resins such as modified phenol type epoxy resins, and these may be used alone or in combination of two or more.
Among these, from the viewpoint of further suppressing discoloration of the sealing material, it is preferable to include one or more selected from the group consisting of a bisphenol type epoxy resin, a biphenyl type epoxy resin, and a phenol aralkyl type epoxy resin.

  As the epoxy resin (A), from the viewpoint of further suppressing discoloration of the sealing material, a phenol aralkyl type epoxy resin represented by the following formula (1), a biphenyl type epoxy resin represented by the following formula (2), and It is particularly preferable to include at least one selected from the group consisting of bisphenol-type epoxy resins represented by the following formula (3).

（式（１）中、Ａｒ^１はフェニレン基またはナフチレン基を表し、Ａｒ^１がナフチレン基の場合、グリシジルエーテル基はα位、β位のいずれに結合していてもよい。Ａｒ^２はフェニレン基、ビフェニレン基またはナフチレン基のうちのいずれか１つの基を表す。Ｒ_ａおよびＲ_ｂは、それぞれ独立に炭素数１〜１０の炭化水素基を表す。ｇは０〜５の整数であり、ｈは０〜８の整数である。ｎ^３は重合度を表し、その平均値は１〜３である）

(In Formula (1), Ar ¹ represents a phenylene group or a naphthylene group, and when Ar ¹ is a naphthylene group, the glycidyl ether group may be bonded to either the α-position or the β-position. Ar ² is a phenylene group. And R _a and R _b each independently represent a hydrocarbon group having 1 to 10 carbon atoms, g is an integer of 0 to 5, and h represents _a group selected from the group consisting of a biphenylene group and a naphthylene group. Is an integer of 0 to 8. n ³ represents the degree of polymerization, and the average value is 1 to 3)

（式（２）中、複数存在するＲ_ｃは、それぞれ独立に水素原子または炭素数１〜４の炭化水素基を表す。ｎ^５は重合度を表し、その平均値は０〜４である）

(In Formula (2), a plurality of R _{c s} each independently represent a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms. N ⁵ represents the degree of polymerization, and the average value thereof is 0 to 4).

（式（３）中、複数存在するＲ_ｄおよびＲ_ｅは、それぞれ独立に水素原子または炭素数１〜４の炭化水素基を表す。ｎ^６は重合度を表し、その平均値は０〜４である）

(In the formula (3), a plurality of R _d and R _e each independently represents a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms. N ⁶ represents a degree of polymerization, and an average value thereof is 0 to 4). Is)

In the present embodiment, the content of the epoxy resin (A) in the sealing resin composition is preferably 2% by mass or more when the entire sealing resin composition is 100% by mass, and preferably 3% by mass. % Or more is more preferable, and 4% by mass or more is particularly preferable. By making content of an epoxy resin (A) more than the said lower limit, sufficient fluidity | liquidity can be implement | achieved at the time of shaping | molding, and the improvement of a fillability or a moldability can be aimed at.
On the other hand, the content of the epoxy resin (A) in the encapsulating resin composition is preferably 40% by mass or less, and 30% by mass or less when the entire encapsulating resin composition is 100% by mass. Is more preferable, and it is especially preferable that it is 15 mass% or less. Improve moisture resistance reliability and reflow resistance for a semiconductor device including a sealing material formed using a sealing resin composition by setting the content of the epoxy resin (A) to the upper limit value or less. Can do.

(Inorganic filler (B))
In this embodiment, what is generally used for the resin composition for semiconductor sealing can be used as an inorganic filler (B). Examples thereof include silica such as fused silica and crystalline silica, alumina, talc, titanium oxide, silicon nitride, aluminum nitride, and the like. Among these, from the viewpoint of excellent versatility, it is preferable to use silica, and it is more preferable to use fused silica. Further, the inorganic filler (B) is preferably spherical, and more preferably spherical silica. These inorganic fillers (B) may be used individually by 1 type, and may use 2 or more types together.
Thereby, the fluidity | liquidity of the resin composition for sealing at the time of shaping | molding can be improved, and it can contribute to the improvement of shaping | molding stability.

In the present embodiment, the content of the inorganic filler (B) in the encapsulating resin composition is preferably 50% by mass or more when the entire encapsulating resin composition is 100% by mass, 70 It is more preferably at least mass%, particularly preferably at least 80 mass%. By setting the content of the inorganic filler (B) to the above lower limit value or more, the semiconductor device obtained by improving the low hygroscopicity and low thermal expansion of the sealing material formed using the sealing resin composition The moisture resistance reliability and reflow resistance can be improved more effectively.
On the other hand, the content of the inorganic filler (B) in the sealing resin composition is preferably 95% by mass or less, and 93% by mass when the entire sealing resin composition is 100% by mass. More preferably, it is more preferably 90% by mass or less. By making content of an inorganic filler (B) below the said upper limit, the fluidity | liquidity and filling property at the time of shaping | molding of the resin composition for sealing can be improved more effectively.

The average particle diameter D ₅₀ of the inorganic filler (B) is preferably 0.01 μm or more and 50 μm or less, and more preferably 0.1 μm or more and 30 μm or less. By the average particle diameter D ₅₀ of less than the above lower limit, the fluidity of the encapsulating resin composition is made excellent, it is possible to improve the formability more effectively. Further, by the average particle diameter D ₅₀ and more than the above upper limit can reliably prevent the gate clogging occurs. The average particle diameter _{D 50} is a commercially available laser particle size distribution analyzer (e.g., manufactured by Shimadzu Corporation, SALD-7000) is the average particle size as measured by.

In the present embodiment, examples of the black colorant (C) include black titanium oxide, pitch, and carbon black. These can be used alone or in combination of two or more. When the encapsulating resin composition contains the black colorant (C), it is possible to improve the printing performance of a laser such as a YAG laser of an encapsulating material colored other than black.
As the black colorant (C), black titanium oxide is preferable from the viewpoint of more effectively obtaining the effect of improving the laser marking performance of a sealing material colored other than black, such as a YAG laser.

Black titanium oxide exists as Ti _n O _(2n-1) (n is a positive integer). As the black titanium oxide Ti _n O _(2n−1) used in the present embodiment, it is preferable to use one having n of 4 or more and 6 or less. By setting n to 4 or more, the dispersibility of black titanium oxide in the encapsulating resin composition can be improved. On the other hand, by setting n to 6 or less, it is possible to improve the sealability of a laser such as a YAG laser. Here, the black colorant (C) preferably contains at least one of Ti ₄ O ₇ , Ti ₅ O ₉ , and Ti ₆ O ₁₁ as black titanium oxide.

  Pitch is a residue obtained by distilling tar obtained by dry distillation of organic substances such as petroleum, coal, and wood. The pitch as the black colorant (C) is not particularly limited, but is, for example, petroleum pitch or coal pitch. Further, as the pitch, mesophase spherules that are generated by cooling the isotropic pitch, the mesophase pitch, or the mesophase pitch and separated as an insoluble component of quinoline can be used. Among these, it is more preferable to use mesophase spherules from the viewpoint of improving the printability of a laser such as a YAG laser and the dispersibility in the sealing resin composition.

In the present embodiment, the content of the black colorant (C) in the sealing resin composition is such that the sealing resin composition is used from the viewpoint of improving the printing performance of a laser such as a YAG laser of the obtained sealing material. When the entire product is 100% by mass, it is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and particularly preferably 0.07% by mass or more.
On the other hand, in this embodiment, the content of the black colorant (C) in the encapsulating resin composition is the entire encapsulating resin composition from the viewpoint of realizing an encapsulant colored other than black. When it is 100% by mass, it is preferably less than 1.0% by mass, more preferably 0.8% by mass or less, further preferably 0.5% by mass or less, and 0.2% by mass. It is particularly preferred that

(Colorant (D))
In the present embodiment, the colorant (D) other than the black colorant (C) is not particularly limited as long as a desired color strength can be obtained, and any colorant can be used. . For example, one or two selected from blue colorants, yellow colorants, green colorants, red colorants, white colorants, orange colorants, purple colorants, brown colorants, etc. The above can be used.

Blue colorants include ultramarine, bitumen, cobalt blue, alkali blue lake, phthalocyanine blue, indanthrene blue, indigo, Victoria blue lake, fast sky blue, aniline blue, ultramarine blue, calco oil blue, methylene blue chloride, Blue pigments such as methylene blue or blue dyes can be used.
Yellow colorants include yellow lead, zinc white, yellow iron oxide, cadmium yellow, chrome yellow, hansa yellow, titanium yellow, benzine yellow, selenium yellow, quinoline yellow, permanent yellow, monoazo yellow, disazo yellow, insoluble azo, Examples thereof include yellow pigments or yellow dyes such as azo pigments such as condensed azo and azo lake.
Examples of the green colorant include green pigments or green dyes such as chrome green, chromium oxide, emerald green, naphthol green, green gold, acid green lake, malachite green lake, phthalocyanine green, and polychlorobrom copper phthalocyanine.
Red colorants include Bengala, Cadmium Red, Antimony Red, Permanent Red, Irgadin Red, Perylene Red, Rhodamine Lake, Alizarin Lake, Thioindigo Red, PV Carmine, Monolite Face Tread, Quinacridone, Watching Red, Resol Condensation of red, brilliantamine, dapon oil red, pyrazolone red, rhodamine B lake, lake red C, rose bengal, oxine red, alizarin lake, anthraquinone, indigo, isoindoline diketopyrrolopyrrole, chromofine red, etc. Red pigments such as polycyclic pigments or red dyes can be used.
As the white colorant, white pigments or white dyes such as titanium oxide, zinc white, zinc sulfide, lead white, lithobon, and antimony oxide can be used.
As the orange colorant, an orange pigment or an orange dye such as chrome vermilon, permanent orange, Vulcan first orange, or indanthrene brilliant orange can be used.
As the purple colorant, purple pigments or purple dyes such as cobalt purple, manganese purple, first violet, methyl violet lake, indanthrene brilliant violet, dioxazine violet can be used.
As the brown colorant, a brown pigment such as iron oxide, permanent brown, para-brown, or a brown dye can be used.
These may be used alone or in combination of two or more.

  In the present embodiment, the content of the colorant (D) in the sealing resin composition is not particularly limited as long as sufficient coloring power can be obtained, but the entire sealing resin composition is 100 masses. %, It is 0.01 mass% or more and 5 mass% or less, More preferably, it is 0.1 mass% or more and 3 mass% or less. If content of a coloring agent (D) is in the said range, coloring power can be improved further, without impairing the other characteristic of a sealing material.

(Antioxidant (E))
The sealing resin composition preferably further contains an antioxidant (E) from the viewpoint of further suppressing discoloration of the sealing material.

In addition, the present inventor has disclosed that a sealing resin composition colored other than black has a hindered phenol compound, a hindered amine compound, and an antioxidant (E) having two or more hindered phenol groups in one molecule. When one or two or more types selected from thioether compounds are included, the oxidative deterioration of each component in the sealing resin composition can be effectively suppressed, and as a result, a sealing material with little color change is realized. I have newly discovered what I can do.
Therefore, in this embodiment, as antioxidant (E), from a viewpoint which can suppress discoloration of a sealing material more effectively, the hindered phenol type compound which has two or more hindered phenol groups in 1 molecule, It is more preferable to include one or more selected from hindered amine compounds and thioether compounds.

  As the hindered phenol group, a hindered phenol group represented by the following formula (5) is preferable.

ただし、式（５）において、Ｒ_１はそれぞれ独立に炭素数１〜４のアルキル基、好ましくはメチル基またはｔ−ブチル基、特に好ましくはｔ−ブチル基を表す。

However, in Formula (5), each R ₁ independently represents an alkyl group having 1 to 4 carbon atoms, preferably a methyl group or a t-butyl group, and particularly preferably a t-butyl group.

  Examples of the hindered phenol compound having two or more hindered phenol groups in one molecule include 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) -1,3. , 5-Triazine-2,4,6 (1H, 3H, 5H) -trione, 4,4 ', 4 "-(1-methylpropanyl-3-ylidene) tris (6-tert-butyl-m-cresol ), 6,6′-di-tert-butyl-4,4′-butylidenedi-m-cresol, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 3 , 9-bis {2- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1-dimethylethyl} -2,4,8,10- Traoxaspiro [5.5] undecane, 1,3,5-tris (3,5-di-tert-butyl-4-hydroxyphenylmethyl) -2,4,6-trimethylbenzene, 2,2′-thio Diethylbis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], N, N ′-(1,6-hexanediyl) bis [3,5-bis (1,1-dimethyl) Ethyl) -4-hydroxybenzenepropanamide], bis [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionic acid] [ethylenebis (oxyethylene)], 1,6-hexanediol bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], etc. These may be used alone or in combination of two or more.

  Examples of hindered amine compounds include tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) butane-1,2,3,4-tetracarboxylate, tetrakis (2,2,6,6-tetramethyl). -4-piperidyl) butane-1,2,3,4-tetracarboxylate, 1,2,3,4-butanetetracarboxylic acid and 1,2,2,6,6-pentamethyl-4-piperidinol and 3, 9-bis (2-hydroxy-1,1-dimethylethyl) -2,4,8,10-tetraoxaspiro [5.5] undecane mixed ester, 1,2,3,4-butanetetracarboxylic Acid and 2,2,6,6-tetramethyl-4-piperidinol and 3,9-bis (2-hydroxy-1,1-dimethylethyl) -2,4,8,10-tetraoxaspiro [ .5] Mixed esterified product with undecane, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1-undecanoxy-2,2,6,6-tetramethylpiperidin-4-yl) carbonate, 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate, 2,2,6,6-tetramethyl Reaction product of -4-piperidyl methacrylate, 2,2,6,6-tetramethylpiperidin-4-ylhexadecanoate and 2,2,6,6-tetramethylpiperidin-4-yloctadecanoate, etc. Is mentioned. These may be used alone or in combination of two or more.

  Examples of the thioether compound include 2,2-bis {[3- (dodecylthio) -1-oxopropoxy] methyl} propane-1,3-diylbis [3- (dodecylthio) propionate], di (tridecyl) -3,3. Examples include '-thiodipropionate. These may be used alone or in combination of two or more.

  Among these, 3,9-bis {2- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) from the viewpoint of realizing a more excellent semiconductor device due to a balance between appearance and high-temperature storage characteristics. Propionyloxy] -1,1-dimethylethyl} -2,4,8,10-tetraoxaspiro [5.5] undecane, 1,3,5-tris (3,5-di-tert-butyl-4- Hydroxybenzyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione and pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate It is particularly preferred that one or more selected from the group consisting of:

  In the present embodiment, the content of the antioxidant (E) in the sealing resin composition is preferably 0.1% by mass or more and 2.0% when the entire sealing resin composition is 100% by mass. It is not more than mass%, more preferably not less than 0.2 mass% and not more than 1.0 mass%. If the content of the antioxidant (E) is within the above range, the oxidative deterioration of each component constituting the sealing resin composition can be more effectively suppressed without impairing other properties of the sealing material. .

(Curing agent (F))
The sealing resin composition may further contain a curing agent (F).
In this embodiment, as a hardening | curing agent (F), it can divide roughly into three types, for example, a polyaddition type hardening | curing agent, a catalyst type hardening | curing agent, and a condensation type hardening | curing agent.
Examples of polyaddition type curing agents include aliphatic polyamines such as diethylenetriamine (DETA), triethylenetetramine (TETA), and metaxylylene diamine (MXDA), diaminodiphenylmethane (DDM), and m-phenylenediamine (MPDA). In addition to aromatic polyamines such as diaminodiphenylsulfone (DDS), polyamine compounds containing dicyandiamide (DICY), organic acid dihydrazide, etc .; alicyclics such as hexahydrophthalic anhydride (HHPA), methyltetrahydrophthalic anhydride (MTHPA) Acid anhydrides including aromatic acid anhydrides such as acid anhydride, trimellitic anhydride (TMA), pyromellitic anhydride (PMDA), and benzophenone tetracarboxylic acid (BTDA); phenol resin curing agents; polysulfide, thioes Le, polymercaptan compounds such as thioether; an isocyanate prepolymer, an isocyanate compound such as a blocked isocyanate; organic acids such as carboxylic acid-containing polyester resins.

Examples of the catalyst-type curing agent include tertiary amine compounds such as benzyldimethylamine (BDMA) and 2,4,6-trisdimethylaminomethylphenol (DMP-30); 2-methylimidazole, 2-ethyl-4 -Imidazole compounds such as methylimidazole (EMI24); Lewis acids such as BF ₃ complexes.

  Examples of the condensation type curing agent include a resol type phenol resin; a urea resin such as a methylol group-containing urea resin; and a melamine resin such as a methylol group-containing melamine resin.

Among these, a phenol resin-based curing agent is preferable from the viewpoint of balance of flame resistance, moisture resistance, electrical characteristics, curability, storage stability, and the like. The phenol resin-based curing agent is a monomer, oligomer, or polymer in general having two or more phenolic hydroxyl groups in one molecule, and its molecular weight and molecular structure are not particularly limited. For example, phenol novolak resin, cresol novolak Resin, novolak-type phenol resin such as bisphenol novolac; polyfunctional phenol resin such as trisphenolmethane-type phenol resin; modified phenol resin such as terpene-modified phenol resin and dicyclopentadiene-modified phenol resin; phenylene skeleton and / or biphenylene skeleton Phenol aralkyl type resins such as phenol aralkyl resins having a phenylene skeleton and / or biphenylene skeleton, and the like; bisphenols such as bisphenol A and bisphenol F Lumpur compounds. These may be used alone or in combination of two or more.
Among these, from the viewpoint of further suppressing discoloration of the sealing material, it is preferable to include one or more selected from the group consisting of a phenol aralkyl resin, a novolac type phenol resin, and a polyfunctional type phenol resin.

  Among these, from the viewpoint of realizing a more excellent semiconductor device due to a balance between appearance and high-temperature storage characteristics, the group consisting of a phenol aralkyl resin and a novolac type phenol resin represented by the following formula (4) as the curing agent (F) It is particularly preferable that at least one selected from the group consisting of:

（式（４）中、Ａｒ^３はフェニレン基またはナフチレン基を表し、Ａｒ^３がナフチレン基の場合、水酸基はα位、β位のいずれに結合していてもよい。Ａｒ^４はフェニレン基、ビフェニレン基およびナフチレン基のうちのいずれか１つの基を表す。Ｒ^７およびＲ^８はそれぞれ独立に炭素数１〜１０の炭化水素基を表す。ｉは０〜５の整数であり、ｊは０〜８の整数である。ｎ^４は重合度を表し、その平均値は１〜３である。）

(In formula (4), Ar ³ represents a phenylene group or a naphthylene group, and when Ar ³ is a naphthylene group, the hydroxyl group may be bonded to either the α-position or the β-position. Ar ⁴ is a phenylene group or biphenylene. And R ⁷ and R ⁸ each independently represents a hydrocarbon group having 1 to 10 carbon atoms, i is an integer of 0 to 5, and j is 0 to 0. .n ⁴ is an integer of 8 represents a polymerization degree, the average value is 1-3.)

In the present embodiment, the content of the curing agent (F) in the sealing resin composition is preferably 0.5% by mass or more when the entire sealing resin composition is 100% by mass, The content is more preferably 1% by mass or more, and particularly preferably 2% by mass or more. By setting the content of the curing agent (F) to the above lower limit value or more, sufficient fluidity can be realized at the time of molding, and filling properties and moldability can be improved.
On the other hand, the content of the curing agent (F) in the sealing resin composition is preferably 15% by mass or less, preferably 10% by mass or less, when the entire sealing resin composition is 100% by mass. It is more preferable that it is, and it is especially preferable that it is 8 mass% or less. Improving moisture resistance reliability and reflow resistance for a semiconductor device including a sealing material formed using a sealing resin composition by setting the content of the curing agent (F) to the upper limit value or less. Can do.

(Other ingredients (G))
For the sealing resin composition, one or more of various additives such as a coupling agent, a curing accelerator, a mold release agent, an ion scavenger, a low stress component, a flame retardant, and the like are appropriately used as necessary. Can be blended.
Coupling agents include, for example, known cups such as epoxy silane, mercapto silane, amino silane, alkyl silane, ureido silane, vinyl silane, methacryl silane and other silane compounds, titanium compounds, aluminum chelates, and aluminum / zirconium compounds. One type or two or more types selected from ring agents can be included. Among these, as what expresses the effect of this invention more effectively, it is more preferable to contain an epoxy silane or aminosilane, and it is especially preferable from a viewpoint of fluidity | liquidity to contain secondary aminosilane.
Examples of the curing accelerator include organic phosphines, tetra-substituted phosphonium compounds, phosphobetaine compounds, adducts of phosphine compounds and quinone compounds, phosphorus atom-containing compounds such as adducts of phosphonium compounds and silane compounds; 1,8-diazabicyclo (5,4,0) undecene-7, benzyldimethylamine, 2-methylimidazole and the like, one kind selected from nitrogen atom-containing compounds such as amidine and tertiary amine, and quaternary salts of the above amidine and amine Or two or more types can be included. Among these, it is more preferable that a phosphorus atom containing compound is included from a viewpoint of improving curability. In addition, from the viewpoint of improving the balance between moldability and curability, it has latent properties such as tetra-substituted phosphonium compounds, phosphobetaine compounds, adducts of phosphine compounds and quinone compounds, and adducts of phosphonium compounds and silane compounds. It is more preferable to include those.
The mold release agent may contain, for example, natural wax such as carnauba wax, synthetic wax such as montanic acid ester wax, higher fatty acid such as zinc stearate and metal salts thereof, and one or more selected from paraffin. it can.
The ion scavenger includes, for example, hydrotalcite.
The low stress component includes, for example, silicone oil and silicone rubber.
The flame retardant can include one or more selected from, for example, aluminum hydroxide, magnesium hydroxide, zinc borate, zinc molybdate, and phosphazene.

  As the sealing resin composition, for example, the above-mentioned components are mixed by known means, further melt-kneaded with a kneader such as a roll, kneader or extruder, cooled and pulverized, and tableted after pulverization. For example, it is possible to use a tablet that has been molded into a tablet shape, or that has been appropriately adjusted in dispersity, fluidity, and the like.

Next, the semiconductor device 100 will be described.
FIG. 1 is a cross-sectional view showing an example of a semiconductor device 100 according to the present embodiment. The semiconductor device 100 is a semiconductor package including a base material 10, a semiconductor element 20 mounted on the base material 10, and a sealing material 30 that seals the semiconductor element 20. FIG. 1 illustrates the case where the semiconductor device 100 is a BGA package. In this case, a plurality of solder balls 50 are provided on the back surface of the substrate 10 opposite to the surface on which the semiconductor element 20 is mounted.
The semiconductor element 20 is electrically connected to the base material 10 through the bonding wire 40. On the other hand, the semiconductor element 20 may be flip-chip mounted on the base material 10.

  In this embodiment, the sealing material 30 is comprised by the hardened | cured material of the above-mentioned sealing resin composition. As a result, it is possible to realize the manufacture of the semiconductor device 100 that is excellent in the marking performance of a laser such as a YAG laser and includes a sealing material colored other than black. The sealing material 30 is formed, for example, by sealing and molding the sealing resin composition using a known method such as a transfer molding method or a compression molding method.

A mark is printed on the upper surface of the sealing material 30 by a laser such as a YAG laser, for example. This mark is made up of, for example, at least one of letters, numbers, or symbols consisting of straight lines or curves. The mark indicates, for example, the product name, product number, lot number, or manufacturer name of the semiconductor package. The mark may be stamped by, for example, a YVO ₄ laser, a carbonic acid laser, or the like.

Next, the structure 102 will be described.
FIG. 2 is a cross-sectional view showing an example of the structure 102 according to the present embodiment. The structure 102 is a molded product formed by MAP molding. For this reason, a plurality of semiconductor packages are obtained by dividing the structure 102 into pieces for each semiconductor element 20.
The structure 102 includes a base material 10, a plurality of semiconductor elements 20, and a sealing material 30. The plurality of semiconductor elements 20 are arranged on the base material 10. In FIG. 2, the case where each semiconductor element 20 is electrically connected to the base material 10 through the bonding wire 40 is illustrated. However, the present invention is not limited to this, and each semiconductor element 20 may be flip-chip mounted on the base material 10. Note that the substrate 10 and the semiconductor element 20 can be the same as those exemplified in the semiconductor device 100.

  The sealing material 30 seals the plurality of semiconductor elements 20. The sealing material 30 is comprised by the hardened | cured material of the resin composition for sealing mentioned above. As a result, it is possible to realize a structure 102 having an excellent sealability of a laser such as a YAG laser and including the sealing material 30 colored other than black and a semiconductor device obtained by separating the structure 102. . The sealing material 30 is formed, for example, by sealing and molding the sealing resin composition using a known method such as a transfer molding method or a compression molding method.

A mark is printed on the upper surface of the sealing material 30 by a laser such as a YAG laser, for example. This mark is made up of, for example, at least one of letters, numbers, or symbols consisting of straight lines or curves. The mark indicates, for example, the product name, product number, lot number, or manufacturer name of the semiconductor package. The mark may be stamped by, for example, a YVO ₄ laser, a carbonic acid laser, or the like.

  As mentioned above, although embodiment of this invention was described, these are illustrations of this invention and various structures other than the above are also employable.

  Hereinafter, the present embodiment will be described in detail with reference to examples and comparative examples. In addition, this embodiment is not limited to description of these Examples at all.

(Resin composition for sealing)
About each of Examples 1-10 and Comparative Examples 1-2, the resin composition for sealing was prepared as follows. First, according to the formulation shown in Table 1, each component was pulverized and mixed using a mixer, and then roll kneaded at 80 ° C. for 5 minutes. Next, this was cooled and pulverized to obtain a sealing resin composition.
Details of each component in Table 1 are as follows. In addition, the mixture ratio of each component shown in Table 1 points out the mixture ratio (mass%) with respect to the whole resin composition for sealing.

(Epoxy resin (A))
Epoxy resin 1: phenol aralkyl type epoxy resin containing biphenylene skeleton (Nippon Kayaku Co., Ltd., NC-3000)
Epoxy resin 2: bisphenol A type epoxy resin (manufactured by Mitsubishi Chemical Corporation, Epicoat YL6810)
Epoxy resin 3: biphenyl type epoxy resin (manufactured by Mitsubishi Chemical Corporation, Epicoat YX4000K)
Epoxy resin 4: Orthocresol novolac type epoxy resin (manufactured by Nippon Kayaku Co., Ltd., EOCN-1020-55)

(Inorganic filler (B))
Inorganic filler 1: spherical fused silica (Micron, S-CO, average particle size: 21 μm)
Inorganic filler 2: Spherical fused silica (manufactured by Admatechs, SO-25R, average particle size: 0.5 μm)

(Black colorant (C))
Black colorant 1: black titanium oxide (black titanium oxide (Ti ₄ O ₇ ), volume resistivity 7.3 × 10 ⁴ Ω · cm)
Black colorant 2: Mesophase spherule (Osaka Gas Chemical Co., Ltd., MCMB green product)

(Colorant (D))
Colorant 1: Blue colorant (manufactured by Dainichi Seika Kogyo Co., Ltd., cyanine blue 6820, classification: phthalocyanine blue, main component: pigment blue 15: 3 (β crystal of copper phthalocyanine)
Colorant 2: Yellow colorant (manufactured by Dainichi Seika Kogyo Co., Ltd., Seika First Yellow 2054C, classification: monoazo yellow, main component: pigment yellow 74 (2-[(2-methoxy-4-nitrophenyl) azo] -N -(2-methoxyphenyl) -3-oxobutanamide)
Colorant 3: Red colorant (manufactured by Dainichi Seika Kogyo Co., Ltd., Chromofine Red 6605T, classification: Chromofine Red, main component: 4,4′-diamino-1,1′-bianthracene-9,9 ′, 10,10′-tetraone)

(Antioxidant (E))
Hindered phenolic compound 1: 3,9-bis {2- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1-dimethylethyl} -2,4 8,10-tetraoxaspiro [5.5] undecane (ADEKA STAB AO-80 manufactured by ADEKA)

(Curing agent (F))
Phenol resin-based curing agent 1: phenol aralkyl resin having a biphenylene skeleton (GPH-65 manufactured by Nippon Kayaku Co., Ltd./MEH-7851SS manufactured by Meiwa Kasei Co., Ltd.)
Phenol resin-based curing agent 2: Phenol novolak resin (manufactured by Sumitomo Bakelite, PR-HF3)

(Other ingredients (G))
Mold release agent 1: Montanate ester wax (manufactured by Clariant, Lycowax PED191)
Curing accelerator 1: a mixture of curing accelerator A described in paragraph 0021 of JP-A-2004-231765 and curing accelerator B shown in paragraph 0084 of JP-A-2007-246671 at a weight of 1: 3

<Evaluation of ease of discoloration of sealing material>
The ease of discoloration of the sealing material was evaluated by measuring the color difference of the sealing resin compositions obtained in Examples and Comparative Examples.

(Preparation of test piece)
First, using a low-pressure transfer molding machine (“KTS-15” manufactured by Koki Seiki Co., Ltd.), the above-mentioned sealing resin was applied to the mold under conditions of a mold temperature of 175 ° C., an injection pressure of 9.8 MPa, and a curing time of 300 seconds. A cured product of the sealing resin composition was obtained by transfer molding the composition. This cured product had a diameter of 50 mm and a thickness of 3 mm.
Next, with respect to the obtained cured product, L ₁ ^* value, a ₁ ^* value, b ₁ ^* value were obtained using Color Reader CR-13 (measurement mode: transmission, number of measurements: n = 3) manufactured by Konica Minolta Sensing Co., Ltd. It was measured. The CIE 1976 L ^* a ^* b ^* color system values were converted into numerical values by the main body of the apparatus, and CIE 1976 L ^* a ^* b ^* color system data were obtained. C ₁ ^* was obtained by {(a ₁ ^* ) ² + (b ₁ ^* ) ² } ^1/2 . The obtained results are shown in Table 1.

(Post-curing treatment)
Next, the cured product was post-cured at 175 ° C. for 2 hours. The cured product after post-curing treatment in the same manner as described _{above, L} ^{2 *} _{value, a} ^{2 *} value _was measured _b ^{2 *} value. Next, a color difference ΔE ₁ was calculated from the following formula. The obtained results are shown in Table 1. C ₂ ^* was obtained by {(a ₂ ^* ) ² + (b ₂ ^* ) ² } ^1/2 .
ΔE ₁ = {(L ₁ ^* −L ₂ ^* ) ² + (a ₁ ^* −a ₂ ^* ) ² + (b ₁ ^* −b ₂ ^* ) ² } ^1/2

(Reflow processing)
Next, the cured product after the post-curing treatment was heat-treated at 260 ° C. for 1 minute. The cured product after the heat treatment in the same manner as described _above, were _L ^{3 *} _{value, a} ^{3 *} _value, the _b ^{3 *} values were measured. Next, the color difference ΔE ₂ was calculated from the following formula. The obtained results are shown in Table 1. C ₃ ^* was obtained by {(a ₃ ^* ) ² + (b ₃ ^* ) ² } ^1/2 .
ΔE ₂ = {(L ₂ ^* −L ₃ ^* ) ² + (a ₂ ^* −a ₃ ^* ) ² + (b ₂ ^* −b ₃ ^* ) ² } ^1/2

<Evaluation of sealability of YAG laser>
About the sealing material obtained using the resin composition for sealing obtained in the Example and the comparative example, laser printing performance, such as a YAG laser, was evaluated in the following procedure.

  Using a low-pressure transfer molding machine (“KTS-15” manufactured by Koki Seiki Co., Ltd.), the above resin composition for sealing was applied to the mold under conditions of a mold temperature of 175 ° C., an injection pressure of 9.8 MPa, and a curing time of 300 seconds. The lead frame on which the semiconductor element (silicon chip) is mounted is sealed and molded, and a 16-pin SOP (the semiconductor element uses a standard product for HAST TEG9. What is the inner lead portion of the semiconductor element and the lead frame? Bonded with a 25 μm diameter gold wire.) Was molded and post-cured at 175 ° C. for 2 hours to produce a semiconductor device.

  Next, using a mask printing type YAG laser manufactured by NEC Corporation (applied voltage 2.4 kV, pulse width 120 μs, conditions of 15 A, 30 kHz, 300 mm / sec) A mark was imprinted on the encapsulant, which is a cured product of the encapsulating resin composition, and the print visibility (laser imprintability such as YAG laser) was evaluated. If it was good, it was marked with ◎, if it was usable, it was marked with ○, and if it was not usable, it was marked with ×.

The sealing materials obtained in Examples 1 to 10 were excellent in the marking performance of a laser such as a YAG laser.
On the other hand, the sealing material obtained in Comparative Example 1 was inferior in the marking performance of a laser such as a YAG laser. The sealing material obtained in Comparative Example 2 had a low saturation C ^* and a desired color could not be obtained.

DESCRIPTION OF SYMBOLS 100 Semiconductor device 102 Structure 10 Base material 20 Semiconductor element 30 Sealing material 40 Bonding wire 50 Solder ball

Claims (11)

A sealing resin composition comprising an epoxy resin (A), an inorganic filler (B), a black colorant (C), and a colorant (D) other than the black colorant (C). There,
Using a low-pressure transfer molding machine, the sealing resin composition was transfer molded into a mold under the conditions of a mold temperature of 175 ° C., an injection pressure of 9.8 MPa, and a curing time of 300 seconds, and had a diameter of 50 mm and a thickness of 3 mm. When producing a cured product of the sealing resin composition,
When the cured product has a colorimetric value L ^* defined by the CIE 1976 L ^* a ^* b ^* color system of 30 or more and the colorimetric value L ^* is 30 or more and less than 80, the chroma C ^* is 7 or more. A sealing resin composition. In the sealing resin composition according to claim 1,
The resin composition for sealing whose content of the said black colorant (C) is less than 1.0 mass% with respect to the said whole resin composition for sealing. In the sealing resin composition according to claim 1 or 2,
A sealing resin composition in which the black colorant (C) is black titanium oxide. In the sealing resin composition according to any one of claims 1 to 3,
Further comprising an antioxidant (E),
Sealing resin in which the antioxidant (E) contains one or more selected from hindered phenol compounds, hindered amine compounds and thioether compounds having two or more hindered phenol groups in one molecule Composition. In the sealing resin composition according to claim 4,
The sealing resin composition whose content of the said antioxidant (E) is 0.1 to 2.0 mass% with respect to the said whole sealing resin composition. In the sealing resin composition according to any one of claims 1 to 5,
A sealing resin composition wherein the epoxy resin (A) is one or more selected from the group consisting of bisphenol-type epoxy resins, biphenyl-type epoxy resins, and phenol-aralkyl-type epoxy resins. In the sealing resin composition according to any one of claims 1 to 6,
Further comprising a curing agent (F),
A sealing resin composition in which the curing agent (F) is one or more selected from the group consisting of a phenol aralkyl resin, a novolac-type phenol resin, and a polyfunctional phenol resin. In the sealing resin composition according to any one of claims 1 to 7,
The resin composition for sealing which is a granular material or a tablet form. In the sealing resin composition according to any one of claims 1 to 8,
A sealing resin composition used for sealing a semiconductor element excluding an optical semiconductor element. A substrate;
A semiconductor element mounted on one surface of the substrate;
A sealing material that is configured by a cured product of the sealing resin composition according to any one of claims 1 to 9 and that seals the semiconductor element and the one surface of the base material;
A semiconductor device comprising: A substrate;
A plurality of semiconductor elements mounted on one surface of the substrate;
The sealing material which is comprised with the hardened | cured material of the resin composition for sealing as described in any one of Claims 1 thru | or 9, and seals these semiconductor elements and the said one surface of the said base materials. When,
A structure comprising:

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