JP2002363380A - Epoxy resin-based black titanium oxide masterbatch and its manufacturing method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a masterbatch (a high concentration dispersion of a colorant) which does not cause the aggregation of a colorant even when heated and left to stand. SOLUTION: The epoxy resin-based black titanium oxide masterbatch for a semiconductor device sealing medium is a filler masterbatch to be constituted of a filler masterbatch obtained by dispersing a filler containing at least a colorant in an epoxy resin and a diluting resin capable of melt diluting the masterbatch, and the colorant is a mixture of a black titanium oxide to be represented by formula (1): TiWOX (wherein W is an integer of 1-3; and X is a number of 1.0-7.0) and the amount of the colorant is 5-70 wt.% based on the total amount (A) of the epoxy resin and the black titanium oxide; the amount of the epoxy resin having specific properties is 95-30 wt.% based on the total amount (A); furthermore another filler is optionally incorporated thereinto; and the filler is dispersed in the form of particles of <=10 μm. A method for manufacturing the same is disclosed.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a substrate and an integrated circuit (IC).
cuit) A method for producing an epoxy resin-based black titanium oxide masterbatch for a resin-based encapsulant for enclosing a small gap between chips.

[0002]

2. Description of the Related Art Demands for higher performance and higher functionality of electronic devices have become stronger and stronger in the IT (Information Technology) era. Accordingly, it is well known that semiconductor devices used in electronic devices are becoming smaller, thinner and have more pins.

A semiconductor device needs to mechanically protect a fine and complicated electronic circuit formed on the surface of the semiconductor device by cutting it off from external bad environmental conditions. Specifically, sealing is performed with a sealing material to protect from various kinds of dust, moisture, impact, vibration, harmful gas, and the like.

In the transition of the sealing material, metal materials, ceramics, glass, and the like were used at first, but in recent years, resin-based sealing has become the majority. This is because those using metal or ceramics are excellent in airtightness and high in reliability, but are high in cost and much inferior in processing workability as compared with resin-based sealing. Therefore, at present, metals and ceramics are used only for some special purposes.

On the other hand, resin-based sealing is performed at a clock frequency of 200.
A CPU (Central Processing Unit) of more than 1 MHz has the added advantage that signal voltage is less attenuated, and more than 90% of the sealing market uses resin-based sealing. Epoxy resin, silicone resin, phenol resin, polyimide resin, polyphenylene sulfide resin, and the like are used as the resin used for sealing. Among these sealing resins, low viscosity, high adhesion, high electrical insulation, low humidity, high mechanical strength, high chemical resistance, heat resistance,
The reality is that epoxy resin is overwhelmingly used.

In order to enhance the reliability of the resin-based encapsulant, a large amount of silica filler is blended in order to reduce the stress generated by the difference in the coefficient of linear expansion between the encapsulant and the IC chip. It is customary to make the device smaller, that is, generally, the sealing material is composed of a curing agent, a coloring agent, various additives, etc. in addition to the inorganic filler filler such as these resins and silica. It is a composite material.

Epoxy resin encapsulants have been used for their excellent performance because of their excellent performance in conventional molding, more recently P-PGA (Plasti
c-Pin Grid Array, P-BGA (Plastic-Ball Grid)
Array), Flip chip or CSP
(Chip Size Package / Chip Scale Package) and the like, it is well known that they are beginning to be used as encapsulants for advanced semiconductor devices.

[0008] Among them, CSPs are often smaller and have a complicated structure as compared with conventional devices. The gap between the CSP substrate and the IC chip is the conventional 75-100 μm
However, in recent years, the bump size has been reduced due to the narrow pitch accompanying the increase in the number of pitches, and the number of gaps has been increasing around 30 to 50 μm. 1 mil (25.
4 μm) or less are being developed. Furthermore, in recent years, the lead frame interval is approaching 10 μm, and it is said that it will fall to 10 μm in the near future.

The encapsulant for such a state-of-the-art semiconductor device is required to have more delicate workability than ever before;
The yellowing of the encapsulant coming from the phenolic resin and amines compounded as a curing agent can be mitigated by the encapsulant with high coloring power; and the pigment that gives the color aggregates during heating and melting in the encapsulation process. It is required that the pigment be a colorant-based pigment that does not become a foreign substance, and its development is desired.

[0010]

Heretofore, carbon black has been mainly used as a colorant for a sealing material.
As a typical method of manufacturing a sealing material, carbon black and an epoxy resin, a curing agent, a curing accelerator, a silica filler, a release agent and other additives are blended, mixed, heated and kneaded, and then sealed. There is a method of manufacturing materials. However, in this method, particularly when a sealing material having good fluidity is used, the carbon black cannot be sufficiently dispersed and remains as an agglomerate, causing a charge to be trapped between lead frames or a disconnection of a connector wire. There is a drawback that the danger of causing phenomena easily occurs.

In order to solve this problem, usually, a masterbatch in which carbon black is dispersed in an epoxy resin in advance, that is, a resin dispersion of carbon black is first prepared, and this is diluted with a large amount of resin used. Has taken.

In this method, since a resin dispersion is used in another aspect, there is no contamination by carbon black powder in the encapsulant manufacturing process, and the manufacturing environment is extremely favorable. Carbon black is very effective in molds. However, in the case of wire connection, beam connection, new technology pump connection and through hole connection tape type, carrier type and various types of resin-sealed CSP, the size of carbon black aggregates in the resin dispersion is strictly controlled. Even if it is manufactured, if it is actually used, it is melted and diluted at high temperature with an epoxy resin or a phenol resin as a curing agent, and if it is heated and left at around 170 ° C., carbon black will aggregate,
It has been found that as a result of sealing, 1) charging is caused by being sandwiched between lead frames, and 2) disconnection of connector wires.

As a result, there has been a strong demand for the development of “a masterbatch which does not cause aggregation of the colorant even when it is heated and allowed to stand, ie, a high-concentration dispersion of the colorant”.

The present invention has been made to solve the above problems. The technical idea of the present invention is summarized in the following points. 1) A high-concentration dispersion (master batch) of a coloring material is used at the time of sealing. At this time, the dispersion is performed under a temperature condition close to the condition at the time of sealing, and a change in a dispersion state caused by a phase change. Reduces the aggregation of the colorant. 2) Therefore, at the time of high-temperature heat dispersion, dispersion is performed under the condition of the finest dispersion. 3) Under these conditions, coarse particles serving as nuclei for agglomeration are removed under nearly perfect conditions. 4) Using an inorganic coloring material, wrap the dispersed particles in a dispersion medium of a different polarity to isolate them from the cohesive force of the particles. It is. By these combined integration, a method of manufacturing a master batch for a sealing material which is close to ideal is completed.

[0015]

The means of the present invention are as follows. (I) A filler masterbatch which can be provided for a semiconductor device encapsulant, comprising a filler masterbatch in which a filler containing at least a coloring material is dispersed in an epoxy resin, and a diluting resin capable of melting and diluting the masterbatch. a is, the coloring material has the general formula Ti _W O _X (1) (here W is an integer of 1 3, X represents a number from 1.0 to 7.0) a compound represented by Wherein the amount of the coloring agent is 5 to 70% by weight based on the total amount of the epoxy resin and the black titanium oxide; the epoxy resin is solid at 25 ° C, and has an epoxy equivalent of 140 to 250 eq / g, softening point and melting point of 50-120 ° C. and 45-180 ° C. respectively, the amount of epoxy resin is 95-30% by weight based on the total amount of epoxy resin and black titanium oxide; Optionally containing other fillers; the filler is dispersed in particles of 10 μm or less, and contains a coloring material when melted and diluted with a diluting resin to form a sealing material for sealing a semiconductor device at a high temperature. An epoxy resin-based black titanium oxide masterbatch for a semiconductor device encapsulant capable of preventing generation of coarse particles due to agglomeration of a filler; (II) In the epoxy resin-based black titanium oxide masterbatch of the above (I), a diluting resin is used. In addition to the epoxy resin of the above (I), a general formula (Where R _{7 to} R ₁₁ represent a hydrogen atom or a methyl group,
May be the same or different), a general formula (Where R _{7 to} R ₁₄ represent a hydrogen atom or a methyl group,
A master batch according to the above (I), which is a mixture of a tetrafunctional phenolic resin (3) and a trifunctional phenolic resin (2) represented by the following formulas: the filler is dispersed comprises at least a coloring material, in the production method of the filler masterbatch can serve for the purpose of high temperature sealing of semiconductor devices, the master batch formula Ti _W O _X (1) (where W represents an integer of 1 to 3, and X represents a number of 1.0 to 7.0), using black titanium oxide, which is a mixture of compounds represented by 5 to 70% by weight based on the total amount; solid at 25 ° C, epoxy equivalent of 140 to 250e
an epoxy resin having a q / g, a softening point and a melting point of 50 to 120 ° C. and 45 to 180 ° C., respectively, in an amount of 95 to 30% by weight based on the total amount of the epoxy resin and the black titanium oxide; In a dispersing machine equipped with a device for heating and circulating a substance to be subjected to dispersion, a device for heating and filtering the dispersion, and a stirrer for stirring the medium; Using a 0 mm medium, at a temperature of 50 to 200 ° C., and dispersing by hot-melt under the condition that the peripheral speed of the stirrer of the disperser is 1.6 m or more per second; By
It is characterized by producing a masterbatch that can prevent generation of coarse particles due to agglomeration of a filler containing a coloring material when a sealing material that is melted and diluted with a diluting resin to seal a semiconductor device at a high temperature is used. Production method of epoxy resin black titanium oxide masterbatch for semiconductor device encapsulant;
It is.

The combinations of the diluting resins used are as follows. General formula (Where R _{7 to} R ₁₁ represent a hydrogen atom or a methyl group,
May be the same or different) (Where R ₇ -R ₁₄ represents a hydrogen atom or a methyl group,
May be the same or different from each other) and a trifunctional phenol resin (3) and a trifunctional phenol (2)
It is a mixture with resin.

[0017]

BEST MODE FOR CARRYING OUT THE INVENTION Titanium oxide, which is a black pigment of the resin dispersion of the present invention, is powdery and has a primary average particle diameter of 0.03 to 0.5 nm as determined by an electron microscope. , The specific surface is in the range of 20-60 m ² / g, and the oil absorption is 30
４０40 ml / 100 g, and X-ray diffraction
It is composed of a mixture of two or more selected from the group consisting of O, Ti ₂ O ₃ , Ti ₃ O ₅ , and Ti ₄ O ₇ .

The dispersion medium of the resin dispersion of the present invention, 2
Various epoxy resins can be used as the epoxy resin solid at 5 ° C. For example, polyfunctional solid epoxy resin, crystalline epoxy resin, bifunctional solid epoxy resin,
Triglycidyl isocyanurate, bisphenol F type epoxy resin, bisphenol A type epoxy resin and the like can be mentioned. These epoxy resins can be used alone or
Used in combination with more than one species.

In the present invention, the polyfunctional epoxy resin comprises 1
An epoxy resin in which the total number of epoxy groups in the molecule is 3 or more. As such a polyfunctional epoxy resin, for example, a commercially available tetrafunctional naphthalene type epoxy resin represented by trade name EXA-4701 (manufactured by Dainippon Ink) and a commercially available trade name EPPN-501HY (Japan) Triphenylmethane type, dicyclobentadiene type represented by Chemical Co., Ltd., trade name Techmore VG310 manufactured by Mitsui Chemicals, Inc.
1 L, orthocresol / novolak type epoxy resin and the like.

A crystalline epoxy resin is a solid epoxy resin in which a number of crystal peaks appear by X-ray diffraction. The crystalline epoxy resin has a physically sharp melting point, and has little intermolecular interaction during melting. It has a property of extremely lowering the viscosity. Examples of such a crystalline epoxy resin include bisphenol type, biphenyl type, stilbene type and the like.

In the present invention, when the above-mentioned solid epoxy resin is used alone, the epoxy resin is used at 25 ° C.
In the case where two or more types are used, the epoxy resin mixture obtained by mixing shows a solid at 25 ° C. The solid epoxy resin has an epoxy equivalent of 140 to 250 g / eq and a softening point of 50.
It is preferable to use a material having a melting point of from 60 to 80 ° C and a melting point of from 50 to 13 ° C.
It is preferable to use one at 0 ° C.

As a dispersion container for dispersion, a dispersion container equipped with a heating device capable of setting the above softening point or melting point is used.
The material of the container is not particularly limited as long as it does not cause corrosion such as glass, ceramics, fluororesin, stainless steel, or the like. However, a metal container can be suitably used from the viewpoint of heat conductivity.

The structure of the heating and dispersing device may be any one provided with a device capable of stirring inside and heating and melting the internal epoxy resin, and the shape is preferably cylindrical. The inside of the cylinder may be agitated with a stirring blade in a state where one of the cylindrical tubes is closed and the closed part is set up. Further, as a horizontal type, a circular type may be adopted in which both ends of the cylinder are closed and a part thereof is opened. However, in this case, a dissolution tank and a circulation device must be separately provided. In short, the disperser only needs to be able to disperse the molten epoxy resin and black titanium oxide in a desired dispersion state.

The dispersing blade preferably has a diameter of 50 to 95% of the inner diameter of the cylinder, and a peripheral speed of 1.6 m / sec or more, preferably 1.6 to 140 m / sec, is selected and stirred. Although one stirring blade may be used, it is preferable to disperse a plurality of blades by arranging the blades in series in order to uniformly stir the medium serving as the dispersion medium.

The heating temperature is 50-200 ° C., preferably 8
0-180 ° C. Media particle size is 0.1-4.0
mm, preferably 0.3 to 1.0 mm, and the amount of the medium used is preferably 30 to 95% by volume, particularly preferably 50 to 90% by volume, based on the effective space of the dispersing machine.

[Heat filtration device] Heating temperature 50 to 200
C., preferably a filter type filtration device capable of setting the temperature between 80 and 180.degree. During filtration, pressurized or depressurized, mechanical vibration or sonic vibration is applied to increase the filtration speed and increase efficiency. Therefore, the apparatus may have such a function.

[Filter] If the filter is made of stainless steel, a twill weave can be used up to a diameter of 5 μm, but if it is 10 μm or less, it is most preferable to use a sintered stainless steel fiber under a high temperature vacuum. For example, Naslon Filter NF-03, NF-05, NF-06 manufactured by Nihon Seisen Co., Ltd.
Etc. can be suitably used. In addition, a sintered body of silica or alumina may be used as long as a desired opening can be obtained.

[Material of the medium as a dispersion medium] The type of the medium is an epoxy resin such as glass, zirconia, alumina, titania and Teflon (registered trademark), and a medium inert to titanium oxide. Is preferred. In the case of a glass-based material, it is preferable to use a high-by-type type that causes less damage to the medium due to stirring and has less impurities.

[Temperature Control of Heat Dispersion and Filtration Apparatus] In the heat dispersion and filtration apparatus, the temperature of the heat dispersion and filtration apparatus is set because the viscosity of the dispersion changes depending on the temperature and the dispersion becomes non-uniform. Within ± 4 ℃ of temperature,
It is preferable to control the temperature within ± 2 ° C., more preferably ± 1 ° C.

The heating device is preferably an electric furnace, a ribbon heater, a band heater, a heating medium circulating heater or a surface heating element. Temperature control at the set temperature is ± 2 ° C, preferably ± 2 ° C.
It is preferable to use a temperature control device capable of controlling at 1 ° C. When a temperature difference occurs between the upper and lower heating zones, it is preferable to divide and control the heating. The heating temperature is determined by the softening point and melting point of the resin in the range of 50 to 200 ° C, but is preferably set from a temperature of 80 to 180 ° C.

It is preferable to use a glass-based, zirconia-based, alumina-based, titania-based, Teflon-based or the like inert medium for the epoxy resin and titanium oxide for the beads serving as the dispersion medium (media). When the medium is a glass medium, it is preferable to use a Harvey-type medium that causes less damage due to stirring and has less impurities. Further, those made of zirconia can be more preferably used.

The particle diameter of the beads is 0.1 to 4.0 m.
m can be appropriately selected and used according to the degree of dispersion. From the workability, 0.3 to 1.0 mm is preferable.

The amount of the medium used may occupy usually 30 to 95% by volume, preferably 50 to 90% by volume, based on the undispersed effective space of the disperser.

It is desirable that the rotation speed of the stirring blade for dispersion is appropriately set according to the dissolution viscosity of the resin. When the dispersion is insufficient, the setting of the number of rotations is also increased because the viscosity is slightly high, but it is desirable to slightly reduce the number of rotations because the viscosity decreases as the dispersion proceeds. The rotation speed is 1.
It is desirable to adjust appropriately in the range of 6 to 140 m / sec, but preferably 1.6 to 50 m / sec, more preferably 1.6 to 30 m / sec.

It is desirable to adjust the dispersion time appropriately as the time of staying in the disperser until the desired dispersion level is reached, and to perform dispersion. The thus-obtained molten dispersion is immediately filtered through a pre-heated filter to remove foreign substances.

The heating temperature of the heating filtration device is 50 to 200 ° C.
Preferably, a filter type filtration device capable of setting the temperature between 80 and 180 ° C. must be provided. At the time of filtration, by applying pressure or pressure reduction, mechanical vibration or sonic vibration, the filtration speed is increased and the efficiency is increased. Therefore, such equipment may be provided. The control of the temperature of the filtration device is performed within ± 4 ° C. of the set temperature since the filtration speed fluctuates because the viscosity of the dispersion changes due to the temperature.
It is preferable to control the temperature within ± 2 ° C., more preferably ± 1 ° C.

The heating temperature of the filter is determined by the softening point and melting point of the resin in the range of 50 to 200 ° C.
It can be used suitably when set from a temperature between ~ 180 ° C

The filter having an opening of 10 μm, preferably 8 μm, more preferably 3 μm or less is used. Alternatively, the above-mentioned filtration may be performed after preliminary filtration with a filter having a large aperture.

The filter is 5 μm when made of stainless steel.
Twill weave can be used up to the diameter, but when it is 10 μm or less, it is most preferable to use stainless steel fiber sintered under high temperature vacuum. For example, Naslon Filter NF-303, NF manufactured by Nihon Seisen Co., Ltd.
-05, NF-06 and the like can be suitably used. In addition, a sintered body of silica or alumina may be used as long as a desired opening can be obtained.

The resulting dispersion is cooled to room temperature and ground to a desired size. A known pulverizer can be used for the pulverization unless foreign matter is mixed. For example, a small-scale electric mixer can be used effectively, while a large-capacity electric mill manufactured by Dalton Co., Ltd. can be effectively used. When the pulverized particle diameter is 4 mm or less, preferably 2 mm or less, it can be easily mixed with a diluting resin or an epoxy resin resin.

According to the present invention, all of the black titanium oxide dispersed particles of the epoxy resin-based black titanium oxide masterbatch have a particle size of 10 μm or less.
Even in the case of mixing and dispersing with a diluting resin, an epoxy resin-based black titanium oxide masterbatch for coloring a sealing material having a stable dispersion without aggregation is obtained.

Next, the present invention will be described more specifically with reference to Examples, but this is merely an example and does not limit the present invention. First, prior to the examples, the following materials and measurement standards are shown.

[Black Pigment] [Black Titanium Oxide-1] Reddish black obtained by heating titanium powder (Ti) and titanium oxide (TiO ₂ ) in vacuum at 1600 ° C. until the blackness becomes constant. It is a powder and mainly consists of TiO and Ti ₂ O ₃ from X-ray diffraction.
-Titanium oxide which is TiO _1.33 by DTA analysis.

[Black Titanium Oxide-2] In a mixed gas of titanium chloride (Ticl ₂ ) and hydrogen (H ₂ ), 1000
Is a bluish black powder obtained by reacting at ℃, mainly consisting of Ti ₃ O ₄ and Ti ₄ O ₇ from X-ray diffraction, TG-DTA
Analysis shows that titanium oxide is Ti ₃ O _4.02 .

[Carbon Black CB-1] Carbon black manufactured by Mitsubishi Chemical Corporation (trade name: Mitsubishi Carbon Black # 3030) having a specific surface area of 35 m ² / g by nitrogen adsorption.
DBP oil absorption 134ml / 100g, primary particle diameter 53n
m.

[Carbon black CB-2] Carbon black (trade name: 410) manufactured by Asahi Carbon Co., Ltd. Specific surface area by nitrogen adsorption 22 m ² / g, DBP oil absorption 73 ml /
100 g, having a primary particle diameter of 85 nm.

X-ray Diffraction Apparatus and Measurement Conditions Max Science X-ray diffractometer, acceleration voltage 40 k
V, current value 20 mA, 1.0 deg / min.

DTA apparatus and measurement conditions Rigaku Denki thermal analyzer, sample weight 70-80 mg,
Pan Platinum, atmosphere Air temperature rise 20 ° C / min,
0.8 seconds sampling, reference alumina.

Specific Surface Area Measurement by Nitrogen Adsorption Carbon Black Handbook November 25, 1971 P
178-183.

Measurement of DBP Adsorption Amount Handbook of Carbon Black Issued November 25, 1971 P
A method according to 440-441.

Measurement of Primary Particle Size Measured from electron micrographs, Carbon Black Handbook, according to P510-512 issued on November 25, 1971.

[Epoxy resin] [Epoxy resin EP-1] Tetrafunctional naphthalene type epoxy resin (trade name: EXA-470) manufactured by Dainippon Ink and Chemicals, Inc.
1) Solid at 25 ° C., epoxy equivalent 167 g / ep, softening point 68 ° C.

[Epoxy resin EP-2] Triphenylmethane type epoxy resin (trade name: EPPN, manufactured by Nippon Kayaku Co., Ltd.)
-501HY), solid at 25 ° C, epoxy equivalent 170g
/ Ep, softening point 62 ° C.

[Epoxy resin EP-3] Solid epoxy resin (trade name: GK-4292) manufactured by Nippon Steel Chemical Co., Ltd., 25
Solid at ℃, epoxy equivalent 247g / ep, melting point 121
° C.

[Epoxy resin EP-4] Solid epoxy resin (trade name: GK-4137) manufactured by Nippon Steel Chemical Co., Ltd., 25
Solid at ℃, epoxy equivalent 174 g / ep, melting point 79 ℃.

[Epoxy resin EP-5] Solid epoxy resin (trade name: GK-5079) manufactured by Nippon Steel Chemical Co., Ltd., 25
Solid at ℃, epoxy equivalent 190g / ep.

[Epoxy resin EP-6] Solid epoxy resin (trade name: TEPIC-S) manufactured by Nissan Chemical Industries, Ltd., 25 ° C.
With solid, epoxy equivalent 100g / ep.

[Phenol resin] [Phenol resin PH-1] Allylated phenol novolak (trade name: MEH-8005H) manufactured by Showa Kasei Co., Ltd.
Liquid at 25 ° C., hydroxyl equivalent 135 g / eq. In this filtration, the filtration yield has little effect on the color control 99%
The above was evaluated as ◎, slightly affected 95 to 98% as 、, affected 90 to 95% as Δ, and 90% or less as x.

The obtained dispersion is left together with a 50-fold amount of the same resin as the master batch resin at 170 ° C. for 15 minutes, and a part thereof is placed on a glass preparation and cooled to room temperature. This was observed with an optical microscope, and 15 μm
As described above, the presence or absence of aggregates of 15 μm to 10 μm and 10 μm or less is examined. Unavailable when 15 μm or more is present, that is, ×, 15 to 10 μm Δ, 5 to 10 μm ○, 5
μm or less was evaluated as ◎.

[Criteria for Filterability] Regardless of the pressure, the weight of the master batch after separation of the beads at 150 μm, the weight of the master batch before the filter, and the amount remaining on the filter after the pressure filtration are determined by the filtration weight. The yield was determined. Filtration weight yield = (BA) / B × 100 A: Weight of residue on filter (g) B: Weight of master batch after separating beads at 150μ (g)

99% that does not require any pigment correction for coloring control
The above was rated as ◎, 95 to 98% that hardly needed was rated as ○, 90 to 95% affected was rated as Δ, and 90% or less of unusable was rated as ×.

[Criteria for judging the size of agglomerates] The obtained dispersion (master batch) was mixed with the same epoxy resin,
After diluting 10 to 100 times at 170 ° C. with another epoxy resin or phenol resin and leaving at 170 ° C. for 15 minutes, a part thereof is put on a glass preparation, cooled to room temperature, and observed with an optical microscope. 15 μm or more, 15 μm
The presence or absence of aggregates of 10 μm and 10 μm or less was examined. 1
When 5 μm or more was present in the visual field, it was unusable, that is, ×, 15 to 10 μm was rated as Δ, 5 to 10 μm was rated as ○, and 5 μm or less was rated as ◎.

Example 1 11.67% by weight of the above EP-1 as an epoxy resin,
27.22% by weight of black titanium oxide-1 as a black pigment and glass beads (dispersion medium) of 1 mm in particle diameter 6
50 g of a mixture consisting of 1.11% by weight was passed
m, placed in a 15 cm high stainless steel container, 150 ° C
After heating and melting, the peripheral speed of the stirring blade (diameter 35 mm) was set to 2.
The mixture was stirred and dispersed at 2 m / sec for 2 hours. In a heated state, the beads were removed in advance with a stainless steel net having an opening of 150 μm, and then a pressurized heat filtration apparatus heated to 120 ° C. with a stainless steel filter (trade name: NF-06) made by Nippon Seisen having an opening of 5 μm. , And the temperature was sufficiently raised to a predetermined temperature. Then, the mixture was filtered under pressure of 1 kg / air with air to obtain a master batch. 1g of masterbatch is epoxy resin (EP-1) 6
0 g, and the aggregate at 170 ° C. for 15 minutes was measured according to the above criteria.

Example 2 A masterbatch was produced under the same conditions as in Example 1 except that the peripheral speed of the stirring blade was 1.6 m / sec, and the agglomerates were measured.

Example 3 Epoxy resin was 6.27% by weight of EP-1 and black titanium oxide-114.62 was used as a black pigment.
Weight%, particle diameter 1 mm zirconia beads 79.1 weight% (almost the same volume as the glass beads of Example 1), the peripheral speed of the stirring blade is 3.3 m / sec, and the Nippon Seisen stainless steel filter NF having an opening of 3 μm. A masterbatch was manufactured under the same conditions as in Example 1 except that −03 was set, and then the aggregates were measured.

Comparative Example 1 Example 1 was repeated except that the peripheral speed of the stirring blade was 0.07 m / sec.
A masterbatch was produced under the same conditions as described above, and then the agglomerates were measured.

Comparative Example 2 A stainless steel filter NF-0 made by Nippon Seisen having a stirring blade having a peripheral speed of 0.3 m / sec and a filter having an opening of 20 μm was used.
A masterbatch was manufactured under the same conditions as in Example 1 except that the sample was set to 8, and then the agglomerates were measured.

[0068]

Example 4 A masterbatch was produced under the same conditions as in Example 1 except that the black pigment was changed to black titanium oxide-2, and then the agglomerates were measured.

Example 5 A masterbatch was produced under the same conditions as in Example 4 except that the glass beads were changed to 0.5 mm, and the agglomerates were measured.

Comparative Example 4 A masterbatch was produced under the same conditions as in Example 4 except that the beads were 8.0 mm glass beads, and the agglomerates were measured.

Comparative Example 5 Epoxy resin was 7.78% by weight of EP-1, and carbon black CB-1 31.11 was used as a black pigment.
A masterbatch was produced under the same conditions as in Example 4 except that the weight% and the 1 mm glass beads were set to 61.11% by weight, and then the agglomerates were measured.

Comparative Example 6 A masterbatch was produced under the same conditions as in Example 5 except that the black pigment was carbon black CB-2, and the agglomerates were measured.

[0074]

Example 6 A masterbatch was produced under the same conditions as in Example 1 except that the resin was an epoxy resin EP-2, and then the agglomerates were measured.

Example 7 A masterbatch was produced under the same conditions as in Example 1 except that the resin was epoxy resin EP-3, and then the agglomerates were measured.

Example 8 A masterbatch was produced under the same conditions as in Example 1 except that the resin was changed to epoxy resin EP-4, and then the agglomerates were measured.

Example 9 A masterbatch was produced under the same conditions as in Example 1 except that the resin was changed to epoxy resin EP-5, and then the agglomerates were measured.

Example 10 A masterbatch was produced under the same conditions as in Example 1 except that the resin was an epoxy resin EP-6, and then the agglomerates were measured.

Example 11 In the master batch, the resin used in Example 1 (EP-
A masterbatch was produced under the same conditions as in Example 1 except that 1) was used and the phenol resin PH-1 was used instead of EP-1 as the diluting resin, and then the aggregates were measured.

[0081]

[0082]

According to the present invention, there can be obtained an epoxy resin-based black titanium oxide masterbatch in which a high-concentration coloring pigment having a high coloring property and no re-aggregation property due to heating is blended. By melting and diluting this master batch with a diluting resin, an excellent sealing material having high coloring properties and not causing reaggregation even when heated and allowed to stand can be obtained.

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[Procedure amendment]

[Submission Date] August 16, 2001 (2001.8.1)
6)

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] Claim 1

[Correction method] Change

[Correction contents]

[Procedure amendment 2]

[Document name to be amended] Statement

[Correction target item name] Claim 3

[Correction method] Change

[Correction contents]

[Procedure amendment 3]

[Document name to be amended] Statement

[Correction target item name] 0015

[Correction method] Change

[Correction contents]

[0015]

The means of the present invention are as follows. (I) A filler masterbatch which can be provided for a semiconductor device encapsulant, comprising a filler masterbatch in which a filler containing at least a coloring material is dispersed in an epoxy resin, and a diluting resin capable of melting and diluting the masterbatch. a is, the coloring material has the general formula Ti _W O _X (1) (here W is an integer of 1 3, X represents a number from 1.0 to 7.0) a compound represented by Wherein the amount of the coloring agent is 5 to 70% by weight based on the total amount of the epoxy resin and the black titanium oxide; the epoxy resin is solid at 25 ° C, and has an epoxy equivalent of 140 to 250 g / eq, softening point and melting point of 50-120 ° C. and 45-180 ° C. respectively, the amount of epoxy resin is 95-30% by weight based on the total amount of epoxy resin and black titanium oxide; Optionally containing other fillers; the filler is dispersed in particles of 10 μm or less, and contains a coloring material when melted and diluted with a diluting resin to form a sealing material for sealing a semiconductor device at a high temperature. An epoxy resin-based black titanium oxide masterbatch for a semiconductor device encapsulant capable of preventing generation of coarse particles due to agglomeration of a filler; (II) In the epoxy resin-based black titanium oxide masterbatch of the above (I), a diluting resin is used. In addition to the epoxy resin of the above (I), a general formula (Where R _{7 to} R ₁₁ represent a hydrogen atom or a methyl group,
May be the same or different), a general formula (Where R _{7 to} R ₁₄ represent a hydrogen atom or a methyl group,
A master batch according to the above (I), which is a mixture of a tetrafunctional phenolic resin (3) and a trifunctional phenolic resin (2) represented by the following formulas: A filler containing at least a coloring material is dispersed therein, in a method for producing a filler master batch that can be used for high-temperature sealing of a semiconductor device,
The masterbatch general formula Ti _W O _X (1) (here W is an integer of 1 3, X represents a number from 1.0 to 7.0) is a mixture of the compounds represented by Black titanium oxide as a coloring material, containing 5 to 70% by weight based on the total amount of epoxy resin and black titanium oxide; solid at 25 ° C, epoxy equivalent of 140 to 250 g
Epoxide resin having a softening point and a melting point of 50 to 120 ° C. and 45 to 180 ° C., respectively, in an amount of 95 to 30% by weight based on the total amount of the epoxy resin and the black titanium oxide; and any other filler. In a disperser equipped with a device for heating and circulating the substance to be subjected to dispersion, a device for heating and filtering the dispersion, and a stirrer for stirring the medium; 0.1 to 4.0 mm. By hot-melt dispersion at a temperature of 50 to 200 ° C. and a peripheral speed of a stirrer of a disperser of 1.6 m or more per second; by melt-filtration to make the filler into dispersed particles of 10 μ or less. ,
It is characterized by producing a masterbatch that can prevent generation of coarse particles due to agglomeration of a filler containing a coloring material when a sealing material that is melted and diluted with a diluting resin to seal a semiconductor device at a high temperature is used. Production method of epoxy resin black titanium oxide masterbatch for semiconductor device encapsulant;
It is.

[Procedure amendment 4]

[Document name to be amended] Statement

[Correction target item name] 0052

[Correction method] Change

[Correction contents]

[Epoxy resin] [Epoxy resin EP-1] Tetrafunctional naphthalene type epoxy resin (trade name: EXA-470) manufactured by Dainippon Ink and Chemicals, Inc.
1), solid at 25 ° C, epoxy equivalent 167 g / eq, softening point 68 ° C.

[Procedure amendment 5]

[Document name to be amended] Statement

[Correction target item name] 0053

[Correction method] Change

[Correction contents]

[Epoxy resin EP-2] Triphenylmethane type epoxy resin (trade name: EPPN, manufactured by Nippon Kayaku Co., Ltd.)
-501HY), solid at 25 ° C, epoxy equivalent 170g
/ Eq, softening point 62 ° C.

[Procedure amendment 6]

[Document name to be amended] Statement

[Correction target item name] 0054

[Correction method] Change

[Correction contents]

[Epoxy resin EP-3] Solid epoxy resin (trade name: GK-4292) manufactured by Nippon Steel Chemical Co., Ltd., 25
Solid at ℃, epoxy equivalent 247g / eq, melting point 121
° C.

[Procedure amendment 7]

[Document name to be amended] Statement

[Correction target item name] 0055

[Correction method] Change

[Correction contents]

[Epoxy resin EP-4] Solid epoxy resin (trade name: GK-4137) manufactured by Nippon Steel Chemical Co., Ltd., 25
Solid at ℃, epoxy equivalent 174 g / eq, melting point 79 ℃.

[Procedure amendment 8]

[Document name to be amended] Statement

[Correction target item name] 0056

[Correction method] Change

[Correction contents]

[Epoxy resin EP-5] Solid epoxy resin (trade name: GK-5079) manufactured by Nippon Steel Chemical Co., Ltd., 25
Solid at ℃, epoxy equivalent 190g / eq.

[Procedure amendment 9]

[Document name to be amended] Statement

[Correction target item name] 0057

[Correction method] Change

[Correction contents]

[Epoxy resin EP-6] Solid epoxy resin (trade name: TEPIC-S) manufactured by Nissan Chemical Industries, Ltd., 25 ° C.
With a solid, epoxy equivalent of 100 g / eq. ────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission Date] September 26, 2002 (2002.9.2)
6)

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] Claims

[Correction method] Change

[Correction contents]

[Claims]

Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (reference) C09K 3/10 C09K 3/10 QZ H01L 23/29 H01L 23/30 R 23/31 F term (reference) 4F070 AA46 AB21 AB23 AC15 AD10 AE01 AE04 FA03 FB03 FB04 FB07 FC02 FC09 4H017 AA04 AA24 AA39 AB08 AB17 AC01 AC02 AD06 AE05 4J002 BD123 CC001 CC051 CC052 CC071 CC072 CC121 DA037 DE097 DE136 DE147 DL007 FA087 FD01 A03A02 AF00 BA02 EA01 FA01 FA02 FB01 FB02 FB08 HA12 JA07 KA06 4M109 AA01 EA02 EB08 EB11

Claims (8)

[Claims] 1. A filler which can be provided for a semiconductor device encapsulant, comprising a filler masterbatch in which a filler containing at least a coloring material is dispersed in an epoxy resin, and a diluting resin capable of melting and diluting the masterbatch. a masterbatch, coloring agent, the general formula Ti _W O _X (1) (here W is an integer of 1 3, X represents a number from 1.0 to 7.0) are represented by Black titanium oxide, which is a mixture of the following compounds, wherein the amount of the coloring agent is 5 to 70% by weight based on the total amount of the epoxy resin and the black titanium oxide; 140 to 250 eq / g, softening point and melting point are 50 to 120 ° C and 45 to 180 ° C, respectively, and the amount of epoxy resin is 95 to 30% by weight based on the total amount of epoxy resin and black titanium oxide. A filler that is dispersed in particles of 10 μm or less and melted and diluted with a diluting resin to form a sealing material for sealing a semiconductor device at a high temperature; Epoxy resin-based black titanium oxide masterbatch for semiconductor device encapsulants, which can prevent the generation of coarse particles due to the aggregation of fillers containing. 2. The diluent resin may be a compound of the general formula other than the epoxy resin according to claim 1. (Where R _{7 to} R ₁₁ represent a hydrogen atom or a methyl group,
May be the same or different) (Where R _{7 to} R ₁₄ represent a hydrogen atom or a methyl group,
The masterbatch according to claim 1, wherein the masterbatch is a mixture of a tetrafunctional phenolic resin (3) and a trifunctional phenolic resin (2), which may be the same or different. 3. A filler is dispersed comprises at least a coloring material in an epoxy resin, in the manufacturing method of the filler masterbatch can serve for the purpose of high temperature sealing of semiconductor devices, the master batch formula Ti _W O _X (1) (here W is an integer of 1 3, X represents a number from 1.0 to 7.0) the black titanium oxide is a mixture of the compounds represented by as the coloring material, 5 to 70% by weight based on the total amount of epoxy resin and black titanium oxide; solid at 25 ° C, epoxy equivalent of 140 to 250 e
an epoxy resin having a q / g, a softening point and a melting point of 50 to 120 ° C. and 45 to 180 ° C., respectively, in an amount of 95 to 30% by weight based on the total amount of the epoxy resin and the black titanium oxide; In a disperser equipped with a device for heating and circulating the substance to be dispersed, a device for heating and filtering the dispersion, and a stirrer for stirring the medium; Using 0mm media, 5
Melting and dispersing at a temperature of 0 to 200 ° C. at a peripheral speed of a stirrer of the disperser of 1.6 m or more per second; melt-filtration to form a filler having a particle size of 10 μm or less; A semiconductor device encapsulation, which is capable of preventing generation of coarse particles due to agglomeration of a filler containing a coloring material when the encapsulant is diluted and used as an encapsulant for encapsulating a semiconductor device under a high temperature. A method for producing an epoxy resin-based black titanium oxide masterbatch for a stop material. 4. The production method according to claim 3, wherein a product having a size of 3 μm or less is obtained in the melt filtration step. 5. The black titanium oxide is composed of TiO and Ti ₂ O _3.
The production method according to claim 3, which is a mixture of 6. A black titanium oxide comprising Ti ₃ O ₅ and Ti ₂
The method according to claim _{3, wherein} the mixture is a mixture of O3. 7. The method according to claim _{3, wherein the} black titanium oxide is Ti ₃ O _5-5.2 . 8. The method according to claim 3, wherein the black titanium oxide is TiO _1.0-1.5 .