JP2003226823A - Black composite particle powder for liquid semiconductor sealant and liquid semiconductor sealant - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide black composite particle powder which has high black color degree, flowability and colorability, has excellent dispersibility in a binder resin, and is used for liquid semiconductor sealants, and to obtain a liquid semiconductor sealant which has a low viscosity, a high volume resistivity value, an excellent black color degree, excellent moisture resistance and an excellent flexural strength. <P>SOLUTION: The black composite particle powder which is used for the liquid semiconductor sealants and comprises black composite particle powder prepared by coating the surfaces of extender pigment particles with a paste and then adhering carbon black to the coating and having an average particle diameter of 1.0 to 30.0 μm is characterized in that the amount of the adhered carbon black is 1 to 100 pts.wt. per 100 pts.wt. of the extender pigment. The liquid semiconductor sealant comprises a binder resin and the black composite particle powder used for the liquid semiconductor sealants. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention provides a black composite particle powder for a liquid semiconductor encapsulating material, which has high blackness, moisture resistance, fluidity and coloring power and is excellent in dispersibility in a binder resin. Along with the use of the black composite particle powder for a liquid semiconductor encapsulating material, it is an object to obtain a liquid semiconductor encapsulating material having a low viscosity, a high volume resistivity value, and excellent blackness, moisture resistance and bending strength. And

[0002]

2. Description of the Related Art In order to physically and chemically protect and immobilize electronic parts such as ICs, LSIs, transistors, thyristors and diodes, resin encapsulation with a thermosetting resin has been conventionally performed. There is.

In recent years, with the increase in size of encapsulated plastic packages, silica particle powder has been added as a filler to a liquid semiconductor encapsulating material for the purpose of improving mechanical strength.

However, silica particles have silanol groups (Si-OH) on the particle surfaces, and it is known that the silanol groups easily adsorb water by hydrogen bonds.

A plastic package is used in a soldering process for mounting on a printed wiring board.
Since it is exposed to a high temperature of ℃ or more, the absorbed moisture is vaporized at a high temperature, which causes problems such as cracks in the package and gaps on the surface of the Si chip.

On the other hand, it is desirable that the plastic package has a black color so as not to transmit light, and therefore, carbon black is usually used as a colorant. However, since carbon black is a fine particle having an average particle size of about 0.005 to 0.05 μm, it is difficult to disperse it in the resin composition.
Since the powder had a bulk density of about 0.1 g / cm ³ , it was difficult to handle and the workability was poor.
Furthermore, since the carbon black particle powder itself is electrically conductive, it is difficult to add it in a large amount for semiconductor encapsulation applications that require high insulation.

Therefore, in addition to being excellent in moisture resistance, the blackness,
A liquid semiconductor encapsulating material having high electric resistance and mechanical strength is desired, and it is expected that the above-mentioned various properties will be improved by the silica particle powder used as a filler.

It is also desired that the fluidity during molding be good.

At present, in order to improve compatibility with the binder resin, a method of surface-treating the silica particle surface with a silane coupling agent or silicone oil (Japanese Patent Laid-Open No. 244853/1996).
No. 5, JP-A-10-279667, etc.) are known. Further, in order to reduce the silanol groups on the surface of the silica particles, 100 to 1 of the silica particle powder is previously added.
A method (Japanese Patent Laid-Open No. 11-43320) in which silane coupling treatment is performed after heating in the temperature range of 000 ° C. is known.

[0010]

A black particle powder for a liquid semiconductor encapsulating material, which is excellent in moisture resistance, blackness, fluidity and coloring power, and is excellent in dispersibility in a binder resin, Although most demanded at present, black particle powder having such characteristics has not been obtained yet.

That is, the above-mentioned JP-A-8-245835 and JP-A-10-279667 describe silica particle powders whose surface is treated with a silane coupling agent or silicone oil. When the silica particle powder is used as a particle powder for a liquid semiconductor encapsulating material, since unreacted silanol groups with the coupling agent remain, the hygroscopicity is high and cracks are likely to occur in the soldering process. There is. Further, since it is necessary to separately add a black pigment such as carbon black to the binder resin, the obtained liquid semiconductor encapsulating material has poor fluidity and low electric resistance.

Further, the silica particle powder described in the above-mentioned JP-A No. 11-43320 is used in advance.
When the silica particle powder obtained by the method of performing the silane coupling treatment after heating in the temperature range of up to 1000 ° C. is used as the particle powder for the liquid semiconductor encapsulating material, the residual silanol groups are small and the hygroscopicity is low. However, since it is necessary to separately add a black pigment such as carbon black to the binder resin, the resulting liquid semiconductor encapsulating material has poor fluidity and low electrical resistance.

Therefore, the present invention provides a black particle powder for a liquid semiconductor encapsulating material, which is excellent in moisture resistance, blackness, fluidity and coloring power, and is also excellent in dispersibility in a binder resin. This is a technical issue.

[0014]

The above technical problems can be achieved by the present invention as follows.

That is, the present invention comprises a black composite particle powder having an average particle size of 1.0 to 30.0 μm in which the particle surface of an extender pigment is coated with a sizing agent and carbon black is attached to the coating. The black composite particle powder for a liquid semiconductor encapsulating material is characterized in that the amount of the carbon black attached is 1 to 100 parts by weight with respect to 100 parts by weight of the extender pigment.

Further, the present invention is a liquid semiconductor encapsulating material containing the black composite particle powder for a liquid semiconductor encapsulating material and a binder resin.

The structure of the present invention will be described in more detail as follows.

First, the black composite particle powder for a liquid semiconductor encapsulating material according to the present invention will be described.

The black composite particle powder for a liquid semiconductor encapsulating material according to the present invention has an average particle size in which a particle of an extender pigment which is a core particle is coated with a sizing agent, and carbon black is attached to the sizing agent coating. It is composed of black composite particles having a particle diameter of 1.0 to 30.0 μm.

The extender pigment in the present invention includes silica powder, white carbon, fine silica particles such as silicic acid and diatomaceous earth, clay, calcium carbonate, barium sulfate such as precipitated barium sulfate, alumina white, talc, transparent titanium oxide, Sachin white etc. are mentioned. Considering the mechanical strength of the obtained liquid semiconductor encapsulating material, silica fine particles are preferable.

The particle shape of the extender pigment may be any of spherical, granular, polyhedral, acicular, spindle-shaped, rice granular, flake-shaped, scale-shaped and plate-shaped. Considering the fluidity of the obtained black composite particle powder for a liquid semiconductor encapsulating material, the sphericity (average particle diameter / average shortest diameter) (hereinafter referred to as “sphericity”) is 1.0 or more and less than 2.0. Spherical particles or granular particles are preferable, and more preferably 1.0 to 1.5.

The average particle size of the extender pigment is 1.0 to 30.
0 μm is preferable, and more preferably 1.5 to 20.0 μm.
m, most preferably 2.0 μm or more and less than 15.0 μm. When the average particle size exceeds 30.0 μm, the resulting black composite particle powder becomes coarse particles, so the dispersibility in the binder resin decreases, and when it is less than 1.0 μm, the particles become finer. Because it is easy to cause aggregation,
It becomes difficult to uniformly coat the surface of the particles with the sizing agent and to uniformly attach the carbon black.

The BET specific surface area of the extender pigment is 0.1 m ^2.
/ G or more is preferable. BET specific surface area value is 0.1 m ² /
If it is less than g, the extender pigment is coarse, and the resulting black composite particle powder also becomes coarse particles, and the dispersibility in the binder resin decreases. Considering the dispersibility in the binder resin, the BET specific surface area value is more preferably 0.2 m ² / g or more, and most preferably 0.3 m ² / g or more. Considering the uniform coating treatment with the sizing agent on the particle surface of the extender pigment and the uniform adhesion treatment with carbon black, the upper limit value is preferably 100 m ² / g, more preferably 75 m ² / g, and most preferably 50m ² /
It is g.

The fluidity of the extender pigment of the present invention is preferably 40 or more, more preferably 43 to 8 as a fluidity index.
0, most preferably 46-80. Liquidity index is 4
When it is less than 0, it is difficult to say that the fluidity is excellent, and it is difficult to obtain the black composite particle powder for a liquid semiconductor encapsulating material which is excellent in the fluidity.

The hue of the extender pigment preferably has a C ^* value of 16.0 or less, more preferably a C ^* value of 1.
It is 4.0 or less, and most preferably 12.0 or less. C ^*
If the value exceeds 16, the hue of the core particles is strong,
It becomes difficult to obtain a black composite particle powder having high blackness.

As the sizing agent in the present invention, any agent can be used as long as it can attach carbon black to the particle surface of the extender pigment, preferably an organosilicon compound such as an alkoxysilane, a fluoroalkylsilane or a polysiloxane, One or more kinds of various coupling agents, oligomers or polymer compounds of silane type, titanate type, aluminate type and zirconate type. Considering the adhesion strength of carbon black to the particle surface of the extender pigment, more preferably alkoxysilane, fluoroalkylsilane, organosilicon compounds such as polysiloxane, silane-based,
These are various titanate, aluminate and zirconate coupling agents.

Particularly when silica fine particles are used as the core particle powder, it is preferable to use an organic silicon compound or a silane coupling agent as the sizing agent.

As the organosilicon compound, an organosilane compound formed from the alkoxysilane represented by Chemical formula 1, a polysiloxane represented by Chemical formula 2, a modified polysiloxane represented by Chemical formula 3, and a terminal modified polysiloxane represented by Chemical formula 4 are used. Siloxane and fluoroalkylsilane represented by Chemical formula 5 or a mixture thereof.

[0029]

[Chemical 1]

As the alkoxysilane, specifically,
Examples include methyltriethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, diphenyldiethoxysilane, dimethyldimethoxysilane, methyltrimethoxysilane, phenyltrimethoxysilane, diphenyldimethoxysilane, isobutyltrimethoxysilane, and decyltrimethoxysilane. To be

Considering the adhesion effect of carbon black and the degree of desorption, an organosilane compound produced from methyltriethoxysilane, methyltrimethoxysilane, dimethyldimethoxysilane, or phenyltriethoxysilane is preferable.

[0032]

[Chemical 2]

[0033]

[Chemical 3]

[0034]

[Chemical 4]

Considering the adhesion effect and the degree of desorption of carbon black, a polysiloxane having a methylhydrogensiloxane unit, a polyether modified polysiloxane and a terminal carboxylic acid modified polysiloxane whose terminal is modified with a carboxylic acid are preferable.

Specific examples of fluoroalkylsilanes include trifluoropropyltrimethoxysilane, tridecafluorooctyltrimethoxysilane, heptadecafluorodecyltrimethoxysilane, heptadecafluorodecylmethyldimethoxysilane, and trifluoropropylethoxysilane. , Tridecafluorooctyltriethoxysilane, heptadecafluorodecyltriethoxysilane, and the like.

Considering the fluidity and the coloring power of the obtained black composite particle powder, a fluorine-containing organosilane compound produced from trifluoropropyltrimethoxysilane, tridecafluorooctyltrimethoxysilane, and heptadecafluorodecyltrimethoxysilane is used. Preferably
Most preferred are fluorine-containing organosilane compounds formed from trifluoropropyltrimethoxysilane and tridecafluorooctyltrimethoxysilane.

[0038]

[Chemical 5]

Among the coupling agents, the silane coupling agents include vinyltrimethoxysilane, vinyltriethoxysilane, γ-aminopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane,
γ-mercaptopropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, N-β (aminoethyl) -γ-aminopropyltrimethoxysilane,
γ-glycidoxypropylmethyldimethoxysilane, γ
-Chloropropyltrimethoxysilane and the like can be mentioned.

As titanate coupling agents, isopropyl tristearoyl titanate, isopropyl tris (dioctyl pyrophosphate) titanate,
Isopropyltri (N-aminoethyl / aminoethyl)
Titanate, tetraoctyl bis (ditridecyl phosphate) titanate, tetra (2-2-diallyloxymethyl-1-butyl) bis (ditridecyl) phosphate titanate, bis (dioctyl pyrophosphate)
Examples thereof include oxyacetate titanate and bis (dioctyl pyrophosphate) ethylene titanate.

As the aluminate-based coupling agent,
Acetoalkoxy aluminum diisopropylate, aluminum diisopropoxy monoethyl acetoacetate, aluminum trisethyl acetoacetate, aluminum tris acetylacetonate and the like can be mentioned.

As the zirconate type coupling agent,
Zirconium tetrakis acetyl acetonate, zirconium dibutoxy bis acetyl acetonate, zirconium tetrakis ethyl acetoacetate, zirconium tributoxy monoethyl acetoacetate, zirconium tributoxy acetyl acetonate, etc. are mentioned.

The oligomer has a molecular weight of 300 or more,
Those having a molecular weight of less than 10,000 are preferable, and those having a molecular weight of 10,000 or more and about 100,000 are preferable as the polymer compound. Considering the uniform coating treatment to extender pigment,
Oligomers or polymer compounds which are liquid or soluble in various solvents are preferred.

The amount of coating with the sizing agent is preferably 0.01 to 15.0% by weight in terms of C based on the sizing agent-coated extender pigment,
It is more preferably 0.02 to 12.5% by weight, and most preferably 0.03 to 10.0% by weight. 0.01% by weight
If less than 0.1, it is 0.1 with respect to 100 parts by weight of the extender pigment.
It is difficult to attach more than parts by weight of carbon black. If it exceeds 15.0% by weight, extender pigment 1
0.1 to 100 parts by weight of carbon black for 100 parts by weight
Since it can be attached by weight, it is meaningless to coat more than necessary.

As the carbon black used for the adhesion treatment, furnace black, channel black, acetylene black and the like can be used.

The amount of carbon black deposited is determined by the extender pigment 1
0.1 to 100 parts by weight is preferable with respect to 00 parts by weight,
It is more preferably 0.2 to 90 parts by weight, and most preferably 0.3 to 80 parts by weight. If the amount is less than 0.1 part by weight, the amount of carbon black coating the particle surface of the extender pigment is too small, and it becomes difficult to obtain the black composite particle powder as the object of the present invention. When the amount exceeds 100 parts by weight, a large amount of carbon black adheres, so that it becomes difficult to control the addition amount of the black composite particle powder in the resin in order to obtain the liquid semiconductor encapsulating material having desired characteristics. .

The particle shape and particle size of the black composite particle powder for a liquid semiconductor encapsulating material according to the present invention largely depend on the particle shape and particle size of the extender pigment which is the core particle, and have a particle morphology similar to the core particle. It has the same particle size as the core particles.

That is, the black composite particle powder for a liquid semiconductor encapsulating material according to the present invention has an average particle size of 1.0 to 30.0 μm.
m, preferably 1.5 to 20.0 μm, more preferably 2.0 to 15.0 μm. When the average particle size of the black composite particle powder exceeds 30.0 μm, the particle size is too large, and the coloring power is reduced. The average particle size is 1.
If it is less than 0 μm, it becomes difficult to obtain the viscosity required for the liquid semiconductor encapsulating material.

The BET specific surface area value of the black composite particle powder is preferably 0.1 to 150 m ² / g, more preferably 0.2 to 125 m ² / g, and most preferably 0.3 to 10 m ^2.
It is 0 m ² / g. BET specific surface area value is 0.1 m ² / g
If it is less than the range, the particles are coarse and the coloring power is lowered. When the BET specific surface area is more than 100 m ² / g, the fineness of particles tends to cause agglomeration, resulting in a decrease in dispersibility in the binder resin.

The fluidity of the black composite particle powder is preferably 50 or more, more preferably 55 or more, and most preferably 60 to 90. When the fluidity index is less than 50, it cannot be said that the fluidity is excellent, and it is difficult to further improve the mechanical strength of the obtained liquid semiconductor encapsulating material.

The blackness of the black composite particle powder has an L ^* value of 2
2.0 or less, more preferably 21.0 or less,
Most preferably, it is 20.0 or less. L ^* value is 22.0
When it exceeds, the brightness becomes high and it cannot be said that the blackness is excellent. The lower limit of the L ^* value is 14.5.

The coloring power of the black composite particle powder is preferably 115% or more, more preferably 120% or more by the evaluation method described later.

The moisture resistance of the black composite particle powder according to the present invention is preferably 0.28% or less, more preferably 0.26% or less, most preferably 0.24% or less in the later-described evaluation method. Is. If the moisture resistance exceeds 0.28%, cracks are likely to occur in the obtained semiconductor sealing material, which is not preferable.

The degree of desorption of carbon black in the black composite particle powder is preferably 5 to 3, and more preferably 5 or 4 in visual observation in the evaluation method described later. When the degree of desorption of carbon black is less than 3, it is difficult to obtain the effect of the present invention.

The black composite particle powder for a liquid semiconductor encapsulating material according to the present invention has, if necessary, an aluminum hydroxide, an aluminum oxide, a silicon hydroxide, and a silicon oxide which are previously formed on the particle surface of the extender pigment in advance. It may be coated with an intermediate coating material consisting of at least one selected from the above, and the fluidity can be further improved as compared with the case where it is not coated with the intermediate coating material.

The coating amount of the intermediate coating is 0.01 to _{2 in} terms of Al, SiO ₂ or the total of Al and SiO ₂ with respect to the extender pigment coated with the intermediate coating.
0% by weight is preferred.

If the amount is less than 0.01% by weight, the effect of improving fluidity cannot be obtained. If the coating amount is 0.01 to 20% by weight, the effect of improving the fluidity can be sufficiently obtained.
There is no point in coating more than necessary in excess of wt%.

The black composite particle powder obtained by using the extender pigment having the particle surface coated with the intermediate coating has a particle size and a BET specific surface area value which are almost the same as those of the black composite particle powder not coated with the intermediate coating. , Fluidity, blackness, tinting strength,
It has moisture resistance and a degree of desorption of carbon black. The fluidity is improved by coating with an intermediate coating, and the fluidity index is preferably 55 or higher, more preferably 60 or higher.

Next, the liquid semiconductor encapsulating material according to the present invention will be described.

The liquid semiconductor encapsulating material according to the present invention comprises the above-mentioned black composite particle powder for liquid semiconductor encapsulating material, a binder resin and a curing agent, and if necessary, a curing accelerator, an inorganic filler, an organic material. Other additives such as a flame retardant, an inorganic flame retardant, a pigment, a surface treatment agent, a leveling agent, a defoaming agent, a low stress agent and a solvent may be contained.

As the binder resin, a resin usually used in a liquid semiconductor encapsulating material can be used. Specifically, a liquid epoxy resin having two or more epoxy groups in one molecule may be used, and bisphenol A type epoxy resin, novolac type epoxy resin, halogenated epoxy resin, glycidyl ether type epoxy resin, glycidyl ester type epoxy resin. Resins, glycidyl amine type epoxy resins, alicyclic epoxy resins, polymer type epoxy resins and the like can be used. Further, from the viewpoint of improving the mechanical strength of the obtained liquid semiconductor encapsulating material, a solid epoxy resin such as a biphenyl type epoxy resin may be mixed and used, if necessary.

Examples of the curing agent include phenol novolac resin, cresol novolac resin, dicyclopentadiene modified phenol resin, paraxylylene modified phenol resin, terpene modified phenol resin and the like, phthalic anhydride, maleic anhydride and tetrahydro anhydride. An acid anhydride curing agent such as phthalic acid, an amine-based curing agent such as an aliphatic polyamine, a polyamide resin and an aromatic diamine, and a Lewis acid complex compound can be used.

The liquid semiconductor encapsulating material according to the present invention contains 0.4 to 80% by weight, preferably 0.45 to 75% by weight, of the black composite particle powder according to the present invention in the liquid semiconductor encapsulating material. Is contained in an amount of 0.5 to 70% by weight.

The liquid semiconductor encapsulating material has a viscosity of 250 to 7
50PS is preferable, and 300-700P is more preferable.
S, most preferably 350 to 650 PS.

The blackness of the liquid semiconductor encapsulating material has an L ^* value of 2
It is preferably 4.0 or less, more preferably 23.0 or less,
Most preferably, it is 22.0 or less. L ^* value is 24.0
When it exceeds, the lightness becomes high and the blackness cannot be said to be sufficient. The lower limit of the L ^* value is about 14.5.

The moisture resistance of the liquid semiconductor encapsulating material is preferably 0.18% or less, more preferably 0.16% or less, and most preferably 0.14% or less. If the moisture resistance exceeds 0.18%, the resulting semiconductor encapsulating material tends to crack, which is not preferable.

The bending strength of the liquid semiconductor encapsulating material is 80M.
Pa or more is preferable, more preferably 90 MPa or more,
More preferably, it is 100 MPa or more. Bending strength is 8
When it is less than 0 MPa, it cannot be said that the mechanical strength is sufficient.

The volume resistivity of the liquid semiconductor encapsulating material is preferably 5.0 × 10 ⁷ Ω · cm or more, more preferably 1.0 × 10 ⁸ Ω · cm or more, and most preferably 5.0 ×. It is 10 ⁸ Ω · cm or more. 5.0 x 10 ⁷ Ω
If it is less than cm, the conductivity becomes too high and it is difficult to use it as a semiconductor encapsulating material. The upper limit value is 1.0 × 10 ¹⁷ Ω · cm.

Next, a method for producing the black composite particle powder for a liquid semiconductor encapsulating material according to the present invention will be described.

The black composite particle powder for a liquid semiconductor encapsulating material according to the present invention is prepared by mixing an extender pigment and a sizing agent, coating the particle surface of the extender pigment with the sizing agent, and then coating with the sizing agent. It can be obtained by mixing a pigment and carbon black.

To coat the particle surface of the extender pigment with the sizing agent, the extender pigment and the sizing agent may be mechanically mixed and stirred, or may be mechanically mixed and stirred while the sizing agent is sprayed onto the extender pigment. Almost all of the added sizing agent is coated on the particle surface of the extender pigment.

When alkoxysilane or fluoroalkylsilane is used as the sizing agent, the coated alkoxysilane or fluoroalkylsilane is an organosilane produced from the alkoxysilane, a part of which is produced by the coating step. It may be coated as a fluorine-containing organosilane compound produced from a compound or a fluoroalkylsilane. Even in this case, it does not affect the subsequent adhesion of carbon black.

In order to uniformly coat the surface of the particles of the extender pigment with the sizing agent, it is preferable that the agglomeration of the extender pigment is previously unraveled by using a crusher.

As a device for mixing and stirring the extender pigment and the sizing agent, and mixing and stirring the carbon black and the extender pigment whose particle surface is coated with the sizing agent, a shearing force is applied to the powder layer. A device capable of performing shearing, spatula, and compression at the same time, such as a wheel-type kneader, a ball-type kneader, a blade-type kneader, or a roll-type kneader is preferably used. The wheel type kneader can be used more effectively.

As the wheel type kneader, an edge runner (“mix muller”, “Simpson mill”,
(Synonyms with "Sandmill"), Marutimaru, Stutzmill, wet pan mill, Connor mill, ring muller, etc., preferably edge runner, multi-maru, Stutzmill, wet pan mill, ring muller,
More preferably, it is an edge runner. As the ball type kneader, there is a vibration mill. Examples of the blade type kneader include a Henschel mixer, a planetary mixer and a Nauta mixer. As the roll type kneader, there is an extruder.

Regarding the conditions for mixing and stirring the extender pigment and the sizing agent, the treatment conditions may be appropriately adjusted so that the sizing agent is coated on the particle surface of the extender pigment as uniformly as possible, and the linear load is 19.6 to. 1960 N / cm (2-200 Kg / c
m) is preferable, and more preferably 98-1470 N / c.
m (10 to 150 Kg / cm), most preferably 147
~ 980 N / cm (15-100 Kg / cm),
The treatment time is preferably 5 minutes to 24 hours, more preferably 10 minutes to 20 hours, and the stirring speed is 2 to 200.
0 rpm is preferred, more preferably 5-1000 rp
m, most preferably 10 to 800 rpm.

The amount of the sizing agent added is preferably 0.15 to 45 parts by weight per 100 parts by weight of the extender pigment. 0.15-4
By adding 5 parts by weight, 0.1 to 100 parts by weight of carbon black can be attached to 100 parts by weight of the extender pigment.

After coating the particle surface of the extender pigment with a sizing agent,
Add carbon black, mix and stir to attach carbon black to the sizing agent coating. If necessary, drying or heat treatment may be further performed.

The carbon black particle powder is added little by little over a period of time, particularly 5 minutes to 24 hours, preferably 5 minutes to 20 hours, or 5 parts by weight per 100 parts by weight of the extender pigment. It is preferable to add ˜25 parts by weight of carbon black particle powder in portions until the desired addition amount is reached.

Regarding the conditions for mixing and stirring, the processing conditions may be appropriately selected so that the carbon black adheres uniformly, and the linear load is 19.6 to 1960 N / cm (2 to 20).
0 Kg / cm) is preferable, and more preferably 98 to 14
70 N / cm (10 to 150 Kg / cm), most preferably 147 to 980 N / cm (15 to 100 Kg / c)
m), the treatment time is preferably 5 minutes to 24 hours, more preferably 10 minutes to 20 hours, and the stirring speed is preferably 2 to 2000 rpm, more preferably 5 to
It is in the range of 1000 rpm, most preferably 10-800 rpm.

The amount of carbon black added is the amount of extender pigment 1
It is 0.1 to 100 parts by weight, preferably 0.2 to 99 parts by weight, and more preferably 0.3 to 8 parts by weight with respect to 00 parts by weight.
0 parts by weight. If the amount of carbon black added is outside the above range, the black composite particle powder of the present invention cannot be obtained.

The heating temperature for the drying or heat treatment is usually preferably 40 to 150 ° C., more preferably 6 to 150 ° C.
The heating time is 0 to 120 ° C., and the heating time is preferably 10 minutes to 12 hours, more preferably 30 minutes to 3 hours.

When an alkoxysilane and a fluoroalkylsilane are used as the sizing agent, the organosilane compound produced from the alkoxysilane or the fluorine-containing compound produced from the fluoroalkylsilane is finally obtained through these steps. It is coated with an organosilane compound.

By subjecting the black composite particle powder according to the present invention to the above-mentioned treatment process, the added carbon black is finely divided to form an adhesion layer on the particle surface of the extender pigment uniformly and densely through the sizing agent. It is what

The extender pigment is, if necessary, prior to the mixing and stirring with the sizing agent, aluminum hydroxide,
You may coat with the intermediate coating material which consists of at least 1 sort (s) chosen from the oxide of aluminum, the hydroxide of silicon, and the oxide of silicon.

The coating with the intermediate coating is carried out by adding an aluminum compound, a silicon compound or both compounds to an aqueous suspension obtained by dispersing the extender pigment and mixing and stirring, or if necessary, mixing and stirring. By subsequently adjusting the pH value, the particle surface of the extender pigment is coated with an intermediate coating consisting of at least one selected from aluminum hydroxide, aluminum oxide, silicon hydroxide and silicon oxide. Then filtered, washed with water, dried,
Smash. If necessary, deaeration / consolidation may be further performed.

As the aluminum compound, aluminum salts such as aluminum acetate, aluminum sulfate, aluminum chloride and aluminum nitrate, alkali aluminate salts such as sodium aluminate and the like can be used.

As the silicon compound, No. 3 water glass, sodium orthosilicate, sodium metasilicate or the like can be used.

Next, a method of manufacturing the liquid semiconductor encapsulating material according to the present invention will be described.

The liquid semiconductor encapsulating material according to the present invention can be obtained by a known method by mixing and kneading the black composite particle powder, the binder resin and the curing agent. Specifically, a black composite particle powder, a binder resin and a curing agent, if necessary, further a curing accelerator, an inorganic filler, a colorant, a flame retardant, a surface treatment agent, a leveling agent, a defoaming agent, a low stress. It is obtained by uniformly mixing a mixture containing additives such as agents and solvents with a mixer, kneading with a kneader, and further defoaming in vacuum.

When the liquid semiconductor encapsulating material according to the present invention is used to encapsulate a semiconductor device without a die such as a hybrid IC, a chip-on-board, a tape carrier package, a plastic pin grid array, a plastic ball grid array. Can be performed by a known method such as a casting method, an injection method, a dipping method, drip coating or coating.

[0092]

BEST MODE FOR CARRYING OUT THE INVENTION A typical embodiment of the present invention is as follows.
It is as follows.

The average particle size of the particles is shown by the average value of the particle size of 350 particles shown in an electron micrograph (× 10,000).

The sphericity is shown by the ratio of the average particle diameter (average longest diameter) and the average shortest diameter.

The specific surface area value is shown by the value measured by the BET method.

The amount of Al and the amount of Si present on the surface of the particles of the extender pigment coated with the intermediate coating are "X-ray Fluorescence Analyzer 3063M" (manufactured by Rigaku Denki Kogyo Co., Ltd.) and JIS K0119 ". It was measured in accordance with "General rules for fluorescent X-ray analysis".

The coating amount of the sizing agent coated on the particle surface of the extender pigment and the amount of carbon black attached to the extender pigment were determined by "Horiba Metal Carbon / Sulfur Analyzer EMIA-
2200 type "(manufactured by Horiba, Ltd.) was used to measure the amount of carbon.

The fluidity of the extender pigment and the black composite particle powder was measured by using a powder tester (trade name, manufactured by Hosokawa Micron Co., Ltd.) to measure the angle of repose (degree), the degree of compression (%), the angle of spatula (degree), and the degree of cohesion. Each powder characteristic value was measured, each index was obtained by replacing each measured value with the same standard value, and each index was shown as the total fluidity index. The closer the fluidity index is to 100, the better the fluidity.

Hue of extender pigment and black of black composite particle powder
Chromaticity was measured by using a sample of 0.5 g and castor oil of 1.5 ml.
-Knead with a muller to make a paste,
Add 4.5 g of clear lacquer, knead, paint, and
Application of 150 μm (6 mil) on Storcoat paper
Coating pieces applied using a coating film (coating thickness: about 30 μm)
Was prepared, and the coated piece was subjected to “multi-source spectrophotometer MS
C-IS-2D (manufactured by Suga Test Instruments Co., Ltd.) "
Measure according to IS Z 8729.
Hue is the color index L^*Value, a^*Value, b^*Shown by value, black
Chromaticity is the color index L ^*Shown by value. Where L^*Value is lightness
And L^*The smaller the value, the better the blackness.
Indicates. Note that C^*The value represents the saturation, according to the following equation 1.
You can ask.

[0100]

## EQU1 ## C ^* value = ((a ^* value) ² + (b ^* value) ² ) ^1/2

As for the coloring power of the black composite particle powder, first, each of the primary color enamel and the developed color enamel produced according to the following method was cast on a cast-coated paper at 150 μm (6 m).
il) is applied using an applicator to prepare an applied piece, and the applied piece is referred to as "Multi-source spectrophotometer MSC-I".
S-2D "(manufactured by Suga Test Instruments Co., Ltd.) was used for measurement, and the colorimetric index L ^* value was shown in accordance with JIS Z 8729.

Then, as a standard sample of the black composite particle powder, a mixed pigment obtained by simply mixing carbon black and an extender pigment in the same ratio as the black composite particle powder was used, and the primary color enamel and the developed color enamel were processed in the same manner as above. The coated piece was prepared, the L ^* value of each coated piece was measured, and the difference was defined as the ΔLs ^* value.

[0103] The value calculated according to the following equation 2 using DerutaLs ^* value of [Delta] L ^* value and the standard sample of the black composite particles obtained showed a tinting strength (%).

[0104]

## EQU2 ## Coloring power (%) = 100 + {(ΔLs ^* value−ΔL
^* Value) × 10}

Preparation of primary color enamel: 10 g of the above sample powder
And 16 g of amino alkyd resin and 6 g of thinner were mixed and added to a 140 ml glass bottle together with 90 g of 3 mmφ glass beads, and then 4 with a paint shaker.
After mixing and dispersing for 5 minutes, 50 g of amino alkyd resin was added, and further dispersed for 5 minutes with a paint shaker,
A primary color enamel was made.

Preparation of the spread color enamel: the above primary color enamel 1
2 g and 40 g of Amylak White (titanium dioxide-dispersed aminoalkyd resin) were blended and mixed and dispersed for 15 minutes with a paint shaker to prepare a spread enamel.

The moisture resistance of the black composite particle powder was obtained by leaving the sample particle powder in an environment of a temperature of 85 ° C. and a relative humidity of 85% for 48 hours, and then measuring the weight before and after leaving it, according to the following mathematical formula 3.

[0108]

[Equation 3] Moisture resistance (%) = {(Wa-We) / Wa} × 100 Wa: Weight of sample particle powder before standing We: Weight of sample particle powder after standing

The degree of desorption of carbon black adhering to the extender pigment was evaluated according to the following method in five levels.
5 shows the least desorption.

Particle powder to be measured 2 g and ethanol 20 ml
Was placed in a 50 ml Erlenmeyer flask, ultrasonically dispersed for 60 minutes, and then centrifuged at a rotation speed of 10,000 rpm for 15 minutes to separate the particle powder to be measured and the solvent portion.
The measured particle powder obtained was dried at 80 ° C. for 1 hour, and the number of desorbed and re-aggregated carbon blacks present in the visual field shown in the electron micrograph (× 50,000) was visually observed. The extender pigment and carbon black were evaluated in 5 grades based on the electron micrograph (× 50,000) of the black particle powder obtained by simply mixing the extender pigment and the carbon black without using a sizing agent. 1: Same as when the extender pigment and carbon black were simply mixed without using a sizing agent. 2: 30 or more and less than 50 per 100 extender pigments. 3: 10 or more and less than 30 per 100 extender pigments. 4: About 5 to 10 per 100 extender pigments. 5: Less than 5 per 100 extender pigments.

The dispersibility of the black composite particle powder in the binder resin is determined by applying the liquid semiconductor encapsulating material obtained by the formulation described later onto a plastic substrate and curing it at 150 ° C. for 2 hours. Was photographed using an optical microscope (BH-2, manufactured by Olympus Optical Co., Ltd.), and the number was determined by counting the number of undispersed agglomerated particles in the obtained microphotograph (× 200 times). did. 5 shows that the dispersion state is the best. 1: 0.25 mm 50 or more per ² 2: 0.25 mm less than 50 10 or more per ² 3: 0.25 mm ² per 5 or more 10 than 4: 1 or more per 0.25 mm ² Less than 5 5: No undispersed material is observed

The viscosity of the liquid semiconductor encapsulating material was measured by measuring the viscosity of the obtained liquid semiconductor encapsulating material at 25 ° C. using an “E type viscometer EMD-R” (manufactured by Tokyo Keiki Co., Ltd.). The value at 0.5 rpm is shown.

The blackness of the liquid semiconductor encapsulating material is determined by applying the liquid semiconductor encapsulating material obtained by the formulation described below onto a plastic substrate and curing the resin plate at 150 ° C. for 2 hours with a multi-light-source spectrophotometer. "Multi-Spectro
-Color-Meter "(manufactured by Suga Test Instruments Co., Ltd.) was used for measurement, and the colorimetric index L ^* value was shown in accordance with JIS Z 8929.

The volume resistivity value of the liquid semiconductor encapsulating material is
A resin plate prepared in the same manner as the resin plate used in the evaluation method of blackness was punched out to prepare a cylindrical measurement sample.

Next, the sample to be measured was exposed to an environment of a temperature of 25 ° C. and a relative humidity of 60% for 12 hours or more, and then this sample to be measured was set between stainless steel electrodes, and "Wheatstone bridge (TYPE2768 Yokogawa Kitatsushin Electric Co., Ltd. (Manufactured by the company) "and a resistance value R (Ω) was measured by applying a voltage of 15V.

Then, the area A (cm ² ) and the thickness t (cm) of the upper surface of the sample to be measured (cylindrical) are measured, and the respective measured values are inserted into the following equation 4 to obtain the volume specific resistance value X ( Ω ・
cm) was calculated.

[0117]

Equation 4] volume resistivity (Ω · cm) = R × (A / t 0)

Regarding the moisture resistance of the liquid semiconductor encapsulating material, the resin plate prepared in the same manner as the resin plate of the above-mentioned evaluation method of blackness was left in an environment of temperature 85 ° C. and relative humidity 85% for 48 hours and then left. The weights before and after the measurement were measured, and the weight was determined according to the equation (5).

[0119]

[Equation 5] Moisture resistance (%) = {(Wa-We) / Wa} × 100 Wa: Weight of resin plate before leaving We: Weight of resin plate after standing

The bending strength of the liquid semiconductor encapsulating material is JIS
According to K6911, a bending bar having a size of 10 × 4 × 100 mm was molded under the conditions of 175 ° C., 6.9 MPa, and a molding time of 2 minutes, and the bending strength at room temperature of the cured product at 150 ° C. for 2 hours was measured.

<Production of Black Composite Particle Powder> Silica particle powder (particle shape: spherical, average particle diameter 3.22 μm, sphericity 1.02, BET specific surface area value 0.8 m ² / g, fluidity index 48, L ^* Value 93.2, a ^* value 0.4, b ^* value 0.
6, C ^* value of 0.7), 7.0 g of methyl hydrogen polysiloxane (trade name: TSF484: GE Toshiba Silicone Co., Ltd.) was added to the silica particle powder while operating the edge runner, and 588 N / cm
The mixture was stirred for 30 minutes with a linear load of (60 Kg / cm). The stirring speed at this time was 22 rpm.

Next, carbon black (particle shape: granular, average particle size 0.022 μm, BET specific surface area value 13)
3.5 m ² / g, L ^* value 14.6) 700 g were added over 30 minutes while operating the edge runner, and further mixed and stirred for 30 minutes with a linear load of 588 N / cm (60 Kg / cm), After carbon black was attached to the methylhydrogenpolysiloxane coating, it was dried at 80 ° C. for 60 minutes using a dryer to obtain a black composite particle powder. The stirring speed at this time was 22 rpm.

The obtained black composite particle powder was granular particles having a particle size of 3.22 μm and a sphericity of 1.03. B
ET specific surface area value is 4.1 m ² / g, fluidity index is 74,
Blackness L ^* value is 18.4, tinting strength is 126%, moisture resistance is 0.
21%, the degree of desorption of carbon black was 4, and the coating amount of methylhydrogenpolysiloxane was 0.27% by weight in terms of C. The carbon black attached was 9.04% by weight in terms of C (corresponding to 10 parts by weight with respect to 100 parts by weight of the silica particle powder).

From the observation result of the electron micrograph of the obtained black composite particle powder, almost no added carbon black particles were observed, so that almost all of the carbon black adhered to the methylhydrogenpolysiloxane coating. Was recognized.

<Production of Liquid Semiconductor Encapsulating Material> 2.0 parts by weight of the black composite particle powder, 14.0 parts by weight of bisphenol A type epoxy resin, silica particle powder (particle shape: spherical, average particle diameter 3.22 μm). , Sphericity 1.02, BET
Specific surface area value 0.8 m ² / g) 68.2 parts by weight, methylhexahydrophthalic anhydride 10.0 parts by weight, curing accelerator 0.5 parts by weight and silane coupling agent 5.3 parts by weight Universal mixer Then, the mixture was degassed in a vacuum chamber to obtain a liquid semiconductor encapsulating material.

The obtained liquid semiconductor encapsulating material has a viscosity of 4
26 PS, dispersibility is 5, blackness L ^* value is 20.6, volume specific resistance value is 2.4 × 10 ¹⁰ Ω · cm, and moisture resistance is 0.
The bending strength was 10% and the bending strength was 104 MPa.

[0127]

The most important point in the present invention is that the black composite particle powder for a liquid semiconductor encapsulating material, in which the particle surface of the extender pigment is coated with a sizing agent and carbon black is attached to the coating, has a blackness In addition to being excellent in fluidity, hygroscopicity and coloring power, it is also excellent in dispersibility in the binder resin.

Further, the reason why the black composite particle powder for liquid semiconductor encapsulating material according to the present invention has excellent fluidity is as follows.
The present inventor believes that this is because the extender pigment having excellent fluidity such as silica fine particles is used as the core particles.

The present inventor believes that the moisture resistance of the black composite particle powder for a liquid semiconductor encapsulating material according to the present invention is excellent. Silica particle powder that is generally added as an inorganic filler material to a resin composition that constitutes a liquid semiconductor encapsulating material has a silanol group (Si-OH) on the particle surface, and this silanol group is water bonded by hydrogen bond. It is known that it easily adsorbs
It is considered that the black composite particle powder of the present invention has carbon black adhered to the particle surface, and thus can be made more hydrophobic than the extender pigment and can suppress the adsorption of water.

[0130]

EXAMPLES Next, examples and comparative examples will be shown.

Core particles 1-2: Extender pigments having the characteristics shown in Table 1 were prepared as core particle powders.

[0132]

[Table 1]

Core particle 3 Using 20 kg of silica particle powder of core particle 1 and 150 l of water, a slurry containing silica particle powder was obtained. The pH value of the dispersion slurry containing the obtained silica particle powder is set to 10.5.
And Next, water is added to the slurry to adjust the slurry concentration to 9
Adjusted to 8 g / l. 150 l of this slurry was heated to 60 ° C. and 1.0 mol / l of Na was added to this slurry.
2722 ml of AlO ₂ solution (A to silica particle powder
(corresponding to 0.5% by weight in terms of 1) was added and the mixture was kept for 30 minutes, and then the pH value was adjusted to 7.5 with acetic acid. After maintaining in this state for 30 minutes, filtration, washing with water, drying and pulverization were carried out to obtain silica particle powder having a particle surface coated with aluminum hydroxide.

Table 3 shows various characteristics of the silica particle powder whose surface is coated with aluminum hydroxide.
Shown in.

Core particle 4 A surface-treated core particle powder was obtained in the same manner as the core particle 3 except that the kind of the core particle and the kind and amount of the additives in the surface treatment step were variously changed.

Table 2 shows the treatment conditions at this time, and Table 3 shows various characteristics of the obtained surface-treated extender pigment. Incidentally, the type A of the coating material in the surface treatment step represents a hydroxide of aluminum.

[0137]

[Table 2]

[0138]

[Table 3]

Carbon blacks A and B: Carbon blacks having the characteristics shown in Table 4 were prepared as carbon blacks.

[0140]

[Table 4]

Examples 1 to 4 and Comparative Examples 1 to 3: Types of core particles, types of additives in coating step with sizing agent, addition amount, line load and time of edge runner treatment, carbon in adhesion step of carbon black Black composite particle powder was obtained in the same manner as in the embodiment of the present invention except that the kind of black, the addition amount, the line load of the edge runner treatment and the time were variously changed.

Table 5 shows the production conditions at this time, and Table 6 shows various characteristics of the obtained black composite particle powder.

[0143]

[Table 5]

[0144]

[Table 6]

Examples 5 to 8 and Comparative Examples 4 to 8: Liquid semiconductor encapsulating materials were obtained in the same manner as in the embodiments of the present invention except that the kind of the black composite particle powder was variously changed.

Table 7 shows the manufacturing conditions at this time and various characteristics of the obtained liquid semiconductor encapsulating material.

[0147]

[Table 7]

[0148]

The black composite particle powder for a liquid semiconductor encapsulating material according to the present invention has high blackness, moisture resistance, fluidity and coloring power, and is excellent in dispersibility in the binder resin. It is suitable as a liquid semiconductor encapsulating material.

The liquid semiconductor encapsulating material according to the present invention has a low viscosity, a high volume resistivity value, a blackness, a moisture resistance and a bending property by using the black composite particle powder for a liquid semiconductor encapsulating material. Since it has excellent strength, it is suitable as a liquid semiconductor encapsulating material.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) H01L 23/29 H01L 23/30 R 23/31 F term (reference) 4H017 AA04 AA22 AA27 AA29 AA39 AB08 AB15 AD02 AD06 AE05 4J037 AA02 CA02 EE02 EE03 EE08 FF05 FF25 4M109 AA01 BA01 CA21 EA03 EB08 EC01 EC03 EC07

Claims (2)

[Claims] 1. A black composite particle powder having an average particle size of 1.0 to 30.0 μm, in which the particle surface of an extender pigment is coated with a sizing agent and carbon black is attached to the coating. Is 1 to 100 parts by weight with respect to 100 parts by weight of the extender pigment, a black composite particle powder for a liquid semiconductor encapsulating material. 2. A liquid semiconductor encapsulating material comprising the black composite particle powder for a liquid semiconductor encapsulating material according to claim 1 and a binder resin.