KR20110078819A - Epoxy resin composition for encapsulating semiconductor element and semiconductor element package using the same - Google Patents

Abstract

PURPOSE: An epoxy resin composition for encapsulating a semiconductor element is provided to prevent electric short and/or short circuit by comprising a coloring agent with an excellent insulating property and fluidity, and to improve the moldability in the sealing of the semiconductor device. CONSTITUTION: An epoxy resin composition for encapsulating a semiconductor element comprises: titanium nitride black represented by chemical formula 1: TiN_xO_y; epoxy resins; hardeners; curing accelerators; and inorganic fillers. The titanium nitride black is coated with a phenol resin. In chemical formula 1, x is 0.01~3 and y is 1.5~10. The titanium nitride black coated with the phenol resin includes the titanium nitride black and the phenol resin in a weight ratio of 1~30 : 99~70.

Description

Epoxy resin composition for encapsulating semiconductor element and semiconductor element package using the same}

TECHNICAL FIELD This invention relates to the epoxy resin composition used when sealing a semiconductor element.

In general, in manufacturing an epoxy resin composition for sealing a semiconductor device, most semiconductor companies require coloring in black to express package identification, product number, and manufacturing company through laser marking. Therefore, carbon black is conventionally used as a colorant in the production of an epoxy resin composition for coloring, and as the carbon black has low insulation, a shortening of the gold wire gap in the semiconductor device causes electrical leakage of electrical signals and currents. There is a problem of lowering reliability.

That is, carbon black is a few nanometers as a single body, but aggregates by air and moisture in the air, and thus has particles of 45 micrometers or more and 500 micrometers or more. These carbon black particles are narrowed due to high integration of semiconductor devices. When placed in a gap (eg, 150 to 100 micrometers), electrical shorts and / or short circuits may occur due to low insulation carbon black, thereby reducing the reliability of the semiconductor device package.

Therefore, in order to solve the above problems, a technique of improving insulation using titanium black instead of carbon black has been developed. However, titanium black is not completely insulated and electrical short and / or short circuit as described above occur when impurities are contained. Still had.

In addition, the use of carbon black with low conductivity improves insulation properties (Japanese Patent Laid-Open No. 2004-211100), or a technique using titanium nitride black without surface treatment (Korean Patent Publication No. 10-2004-0008461) is proposed. However, there is a limitation in solving the above problems because there is still a problem of insulation and high surface activity and the flowability is lowered.

The present invention is to solve the above problems, including a coloring agent having excellent insulation and flowability to prevent the electrical short and / or short circuit occurs in the semiconductor device, it is possible to improve the moldability when sealing the semiconductor device An object of the present invention is to provide an epoxy resin composition for sealing a semiconductor device and a semiconductor device package using the same.

In order to achieve the above object, the present invention is titanium nitride black represented by the following formula (1); Epoxy resins; Curing agent; Curing accelerators; And including an inorganic filler, the titanium nitride provides an epoxy resin composition for sealing a semiconductor device, characterized in that coated with a phenol resin.

[Formula 1]

TiN _x O _y

(In Formula 1, x is 0.01 to 3, and y is 1.5 to 10.)

In addition, the present invention provides a semiconductor device package, characterized in that sealed with the epoxy resin composition for sealing the semiconductor device.

On the other hand, the present invention provides a titanium nitride black contained in the epoxy resin composition for semiconductor element sealing, it is dispersed in a solvent and provides a titanium nitride black, characterized in that coated with a phenol resin.

Since the epoxy resin composition for semiconductor element encapsulation of the present invention as described above includes titanium nitride black coated with a phenol resin having excellent insulation and flowability as a colorant, even if the titanium nitride black is placed in the gold wire gap in the semiconductor device, It is possible to prevent the occurrence of short and / or short circuit.

In addition, the semiconductor device package sealed with the epoxy resin composition of the present invention as described above can prevent the occurrence of electrical short and / or short-circuit can improve the reliability of the semiconductor device package, with excellent epoxy resin composition Since it is sealed, the moldability and workability of the semiconductor device package can also be improved.

Hereinafter, the present invention will be described in detail.

<Epoxy resin composition for semiconductor element sealing>

1.Titanium Nitride

The epoxy resin composition (hereinafter, referred to as "composition") for sealing a semiconductor device of the present invention includes titanium black nitride represented by the following Chemical Formula 1 as a colorant. That is, it is necessary to color the composition in order to express the identification, package number, and manufacturer for each package through laser marking. For this purpose, the composition of the present invention includes titanium black nitride represented by the following Chemical Formula 1.

[Formula 1]

TiN _x O _y

(In Formula 1, x is 0.01 to 3, and y is 1.5 to 10.)

Titanium black nitride represented by the formula (1) has a thermally and chemically very stable structure does not generate harmful gases even when a high temperature heat is applied, it is harmless to the human body can be used environmentally friendly, even by itself Although it has good insulation, it is preferable to use it by coating with a phenol resin in order to improve insulation and flowability.

Non-limiting examples of the phenol resin coated on the titanium nitride black represented by the formula (1) is a phenol aralkyl type phenol resin, phenol novolak type phenol resin, cresol novolak type phenol resin, xylox phenol resin, dicyclopentadiene Phenol resin, naphthalene type phenol resin, or a mixture thereof is mentioned.

In addition, the titanium nitride black coated with a phenol resin is preferably present in the weight ratio of titanium black nitride and phenol resin in the range of 1 to 30:99 to 70. That is, when 100 parts by weight of coated titanium nitride black is 1 part by weight of titanium nitride black, phenolic resin occupies 99 parts by weight, and when titanium nitride black is 30 parts by weight, phenolic resin may occupy 70 parts by weight. In the case where titanium nitride is more than 30 parts by weight in titanium nitride black coated with a phenol resin, coating may not be well performed due to the dispersibility of the phenol resin, and less than 1 part by weight may impair the colorability of the composition.

Here, the method of coating the phenol resin on titanium nitride black is not particularly limited. In the present invention, it is preferable to disperse the titanium nitride black in a solvent and then coat it with a phenolic resin in order to increase the coating power between the titanium nitride black and the phenol resin and to lower the surface activity of the titanium nitride nitride.

In general, since titanium nitride is a fine particle, when the phenolic resin having high viscosity is simply mixed with titanium nitride and coated, the phenol resin is not uniformly coated on the surface of the titanium nitride particles, and the titanium nitride particles are agglomerated. This will appear, when the phenolic resin is not uniformly coated, but when the aggregated titanium nitride black is used in the composition, the insulating effect is reduced. In addition, titanium nitride black, which is not coated with a phenolic resin, has a high surface activity, thereby decreasing the flowability effect.

However, in the present invention, since the titanium nitride black is dispersed in a solvent and coated with a phenolic resin so that the phenolic resin can be uniformly coated on the surface of the fine titanium nitride particles, the coating is coated with phenolic resin. The coated with the phenol resin will have a spherical particle shape, and when the spherical titanium nitride is included in the composition, the flowability of the composition can be improved).

At this time, the titanium nitride black is dispersed in a solvent and coated with a phenol resin, and the solvent and titanium nitride black are mixed and dispersed at room temperature in a ratio of 5: 5, and then the mixture (solvent + titanium nitride) is placed in a reactor and phenol is used. The resin is added and coated. After the solvent is recovered by using a cooling apparatus, titanium nitride black coated with a phenol resin may be crushed with a ball mill to homogenize the particle size of titanium nitride coated with phenolic resin.

Here, the solvent is not particularly limited as long as it can disperse titanium nitride, but it is preferable to use a solvent in which methyl isobutyl ketone and acetone are mixed to be environmentally friendly and easy to recover. Isobutyl ketone (Methyl isobutyl ketone): Acetone is preferably mixed at a ratio of 4: 1. In addition, as the solvent, methyl ethyl ketone (Methly Ethly Ketone), toluene (Toluen), xylene (Xylene) and the like may be used.

You can use

On the other hand, it is preferable that the average particle diameter of titanium black nitride coated with the phenol resin is 30-200 nm. If the average particle diameter exceeds 200 nm, the coloring power of the composition may be reduced, and the coloring difference may appear on the surface of the semiconductor device package. If the average particle diameter is less than 30 nm, the coating degree of the phenol resin coated on titanium nitride black may be difficult to maintain high insulation. Because there is.

Titanium black nitride coated with a phenol resin contained in the composition of the present invention is preferably contained in 0.05 to 5 parts by weight based on 100 parts by weight of the total composition. If the coated titanium nitride is less than 0.05 parts by weight, it may be difficult to color the composition, and if it exceeds 5 parts by weight, the resin fraction used may be relatively low, resulting in a decrease in fluidity and the mechanical strength of the composition. Because there is.

2. epoxy resin

The epoxy resin included in the composition of the present invention is not particularly limited as long as it is an epoxy resin generally used to seal semiconductor devices. Examples thereof include, but are not limited to, phenol aralkyl type epoxy resins, cresol novolak type epoxy resins, and phenol novolak type epoxy resins. , A biphenyl type epoxy resin, a bisphenol type epoxy resin, a dicyclopentadiene type epoxy resin and a naphthalene type epoxy resin can be used by selecting one or more types.

At this time, as a particularly preferable epoxy resin, the phenol aralkyl type epoxy resin of the novolak structure represented by following formula (2) is mentioned.

[Formula 2]

(In Formula 2, the average value of n is 1 to 7.)

Since the phenol aralkyl type epoxy resin of Formula 2 forms a structure based on a phenol skeleton and has a biphenyl in the middle, it can increase hygroscopicity, toughness, oxidation resistance, and crack resistance when used in the composition of the present invention. In addition, since the crosslinking density is low, a carbon layer (char) may be formed during combustion at a high temperature to block surrounding heat and oxygen, thereby increasing the flame retardancy of the composition. Such epoxy resin is preferably included in 3 to 15 parts by weight based on 100 parts by weight of the total composition in consideration of the curing reactivity, crack resistance and flame retardancy of the composition.

3. Curing agent

The curing agent included in the composition of the present invention is not particularly limited as long as it is a curing agent generally used for sealing semiconductor devices. Examples of the curing agent include, but are not limited to, phenol aralkyl type phenol resins, phenol novolak type phenol resins, cresol novolak type phenol resins, and xyl. It can select and use 1 or more types from the group which consists of a lock type phenol resin, a dicyclopentadiene type phenol resin, and a naphthalene type phenol resin.

At this time, as a particularly preferable hardening agent, the phenol aralkyl type phenol resin of the novolak structure represented by following formula (3) containing a biphenyl derivative in a molecule | numerator is mentioned.

(3)

(In Formula 3, the average value of m is 1 to 7.)

The phenol aralkyl type phenolic resin of Formula 3 may increase the flame retardancy of the composition when used in the composition of the present invention because it can block the transfer of surrounding heat and oxygen by forming a carbon layer upon combustion at high temperature. Such a curing agent is preferably included in 0.1 to 10 parts by weight based on 100 parts by weight of the total composition in consideration of curing reactivity and flame retardancy.

4. Curing accelerator

The curing accelerator included in the composition of the present invention is included to promote the reaction between the epoxy resin and the curing agent, and may be used tertiary amines, organometallic compounds, organophosphorus compounds, imidazoles, and boron compounds. .

At this time, examples of the tertiary amine include benzyldimethylamine, 2-2- (dimethylaminomethyl) phenol, salts of 2,4,6-tris (diaminomethyl) phenol and tri-2-ethylhexyl acid, and the like. Can be mentioned. Examples of the organometallic compound include chromium acetylacetonate, zinc acetylacetonate, nickel acetylacetonate, and the like. Examples of the organophosphorus compound include tris-4-methoxyphosphine, tetrabutylphosphonium bromide, butyltriphenylphosphonium bromide, triphenylphosphine, triphenylphosphine triphenylborane, triphenylphosphine-1,4-benzo And quinone adducts. Examples of the imidazoles include 2-methylimidazole, 2-aminoimidazole, 2methyl-1-vinylimidazole, 2-ethyl-4-methylimidazole, 2-heptadecylimidazole, and the like. Can be mentioned. Examples of the boron compound include trifluoroborane-n-hexylamine, trifluoroborane monoethylamine, tetrafluoroboranetriethylamine, tetrafluoroboraneamine, and the like.

Here, as a particularly preferable hardening accelerator, organophosphorus compound, an amine type, and imidazole hardening accelerator are used individually or in mixture. In addition, the curing accelerator may be used in the form of an additive compound prepared by linear reaction with an epoxy resin or a curing agent. The curing accelerator included in the composition of the present invention is preferably included in an amount of 0.001 to 1 parts by weight with respect to 100 parts by weight of the total composition in consideration of the curing reaction rate and the workability margin by temperature and time, specifically 0.01 to 0.5 It is preferably included in parts by weight.

5. Inorganic filler

Inorganic fillers included in the composition of the present invention are included for improving the mechanical properties and low stress of the composition, fused silica, crystalline silica, calcium carbonate, magnesium carbonate, alumina, magnesia, clay, talc, calcium silicate, oxide Antimony, glass fiber, etc. can be used. In this case, the fused silica refers to amorphous silica having a specific gravity of 2.3 or less, and may be made by melting crystalline silica or using synthetic silica synthesized from various raw materials, and having a linear expansion coefficient for lowering the composition. It is preferable to use the lower one.

Further, the shape and particle size of the molten silica are not particularly limited, but 50 to 99 parts by weight of spherical molten silica having an average particle diameter of 5 to 30 µm and 1 to 50 parts by weight of spherical molten silica having an average particle diameter of 0.001 to 1 µm are mixed. It is good to use the mixture to include 40 to 100 parts by weight, based on 100 parts by weight of the total inorganic filler. At this time, the spherical molten silica may include conductive carbon as a foreign material on the silica surface, but it is preferable to select one having a small amount of foreign matter mixing. Moreover, according to a use, the maximum particle diameter can be adjusted to 45um, 55um, 75um, etc., and can be used.

The inorganic filler included in the composition of the present invention is preferably included in 70 to 95 parts by weight, based on 100 parts by weight of the total composition, in consideration of physical properties such as moldability, low stress, high temperature strength, specifically 82 ~ It is preferably included in 92 parts by weight.

On the other hand, the composition of the present invention is a release agent such as higher fatty acids, higher fatty acid metal salts, ester waxes within the scope that does not impair the object of the present invention; Coupling agents such as epoxysilane, aminosilane, mercaptosilane, alkylsilane, alkoxysilane; And stress relaxants such as modified silicone oil, silicone powder, silicone resin, and the like, as necessary.

As a method for preparing the composition of the present invention described above, after determining the amount of titanium nitride nitride, epoxy resin, curing agent, curing accelerator, inorganic filler and other additives coated with the above-described phenolic resin, Henschel mixer or Rödige mixer After uniformly sufficient mixing using, melt kneading with a roll mill or kneader, and then through the cooling and grinding process to obtain a final powder product may be used.

<Semiconductor Device Package>

The present invention can provide a semiconductor device package prepared by sealing a semiconductor device with the composition of the final powder prepared as described above, wherein the method for sealing the semiconductor device is not particularly limited, but low-pressure transfer molding method, injection ( Injection) A molding method selected from a molding method and a casting molding method may be applied.

Since the semiconductor device package of the present invention is sealed with a composition containing titanium black nitride coated with a phenolic resin to improve insulation and flowability, even if the titanium black nitride of the present invention is placed in the gold wire gap of the semiconductor, The occurrence of electrical short and / or short circuit caused by titanium black can be minimized to provide a highly reliable semiconductor device package.

<Titanium nitride black>

On the other hand, the present invention can provide titanium black nitride used in the epoxy resin composition for sealing semiconductor devices, such titanium nitride black is coated with a phenol resin after being dispersed in a solvent. When the titanium nitride black is included in the epoxy resin composition for sealing a semiconductor device, the insulation and flow properties of the composition may be improved. A detailed description of this and the process of coating titanium nitride black with a phenol resin are the same as described above. It will be omitted.

Hereinafter, the present invention will be described in more detail based on Examples and Comparative Examples, but the present invention is not limited by the following Examples and Comparative Examples.

[Examples 1 to 3 and Comparative Examples 1 to 2] Composition and Fabrication of Semiconductor Device Package Using the Same

1. Manufacture of titanium black nitride coated with phenolic resin

A Coating: Coating phenol novolak type phenolic resin on titanium nitride black

A mixture of titanium black nitride (JEMCO), methyl isobutyl ketone, and acetone in a 4: 1 ratio was mixed at room temperature in a ratio of 5: 5 to disperse the titanium black nitride in the solvent, followed by dispersed nitriding. Phenol novolac-type phenol resins (HF-1, MEIWA) were added to titanium black to coat phenol novolac-type phenol resins on titanium nitride black. After the solvent was recovered using a cooling apparatus, it was crushed with a ball mill to enhance dispersion of the epoxy resin composition for sealing semiconductor elements of the first coated titanium nitride. At this time, the coated titanium nitride black 30 parts by weight titanium nitride black, phenol resin accounted for 70 parts by weight.

B coating material: phenol aralkyl type phenolic resin coating on titanium nitride black

A coating preparation process was applied in the same manner except that phenol aralkyl type phenol resin (MEH-7851S, MEIWA) was used instead of phenol novolac type phenol resin.

C coating: Titanium nitride black coated with xylox type phenolic resin

A coating preparation process was applied in the same manner, except that xylox phenol resin (Mei-7, MEH-7800S) was used instead of the phenol novolac phenol resin.

2. Preparation of epoxy resin composition for semiconductor device sealing

To prepare the composition of the present invention, as shown in Table 1 below, each component was weighed, and then uniformly mixed with a Henschel mixer to prepare a powdery primary composition, and the prepared primary composition was mixed with a 2-roll mill. After melt kneading at 100 ° for 7 minutes, the final composition was prepared by cooling and grinding.

3. Semiconductor Device Package Manufacturing

The semiconductor device was mounted on a substrate (PCB), and the final composition was molded (sealed) at 175 ° C. for 60 seconds using a multi-plunger system (MPS) molding machine, followed by post-curing at 175 ° C. for 6 hours. Was produced.

                                                       (Unit: parts by weight) Composition Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Epoxy
Suzy Phenolic Aralkyl Epoxy Resin ^{Note 1)} 5.5 5.4 5.5 5.5 5.5 Orthocresol novolac type
Epoxy Resin ^{Note 2)} 3.3 3.4 3.3 3.6 3.6 Hardener Phenolic Aralkyl Type Phenolic Resin ^Note3) 3.1 3.1 3.1 3.3 3.3 Phenol Novolac Phenolic Resin ^{Note 4)} 3.3 3.3 3.3 3.3 3.3 coloring agent A coating 0.8 - - - - B coating - 0.8 - - - C coating - - 0.8 - - TiNxOy (Unsurface) - - - 0.3 - Carbon Black ^{Note 8)} - - - - 0.3 Curing accelerator ⁵⁾ 0.3 0.3 0.3 0.3 0.3 Silica ^{Note 6)} 83.0 83.0 83.0 83.0 83.0 γ-glycithoxypropyl
Trimethoxysilane 0.4 0.4 0.4 0.4 0.4 Carnauba Wax 0.3 0.3 0.3 0.3 0.3 Sum 100 100 100 100 100 (week)
1) NC-3000, NIPPON KAYAKU
2) EOCN-1020-55, Nippon Kayaku
3) MEH-7851S, MEIWA
4) HF-1, MEIWA
5) TPP, Hokko
6) 9: 1 mixture of spherical molten silica with an average particle diameter of 18 µm and spherical molten silica with an average particle diameter of 0.5 µm
7) JEMCO
8) Carbon Black, Mitsubishi

[Test Example] Evaluation of Physical Properties and Reliability of Semiconductor Device Package

The compositions and semiconductor device packages prepared in Examples 1 to 3 and Comparative Examples 1 and 2 were evaluated in the following manner, and the results are shown in Table 2 below. At this time, the reliability test of the semiconductor device package was represented by the degree of defect (signal operation) occurrence in the PCT test.

1) Spiral Flow

: Flow length was measured using a transfer molding press at 175 ° C. and 70 Kgf / cm 2 using an evaluation mold in accordance with EMMI-1-66.

2) Glass transition temperature (Tg)

: It was evaluated by TMA (Thermomechanical Analyser).

3) Flexural strength and flexural modulus

: Prepared molded specimen (125 * 12.6 * 6.4㎜) cured composition was measured in a UTM (Universal Testing Machine) tester by measuring the width and thickness of the center of the specimen up to 0.001㎜ with a micrometer.

4) Volume resistance

: Prepared molded specimen (120 (R) * 4.0㎜) cured composition was measured by volume resistivity tester.

5) formability

: Visual inspection of the TQFP type semiconductor device package manufactured above was performed by visual inspection.

6) Reliability (PCT)

: After drying the TQFP type semiconductor device package manufactured at 125 ℃ for 24 hours, and left for 85 hours under 85 ℃ / 85% relative humidity conditions, and passes through IR reflow three times for 10 seconds at 260 ℃ 1 After preconditioning conditions were applied, and after 96 hours at 121 ° C and 2 atmospheres in a pressure cooker test (PCT) facility, the operation of the semiconductor device (chip) was evaluated.

Evaluation Item Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Spiral Flow (inch) 56 58 59 49 51 Tg (占 폚) 113 115 114 114 113 Flexural Strength (kgf / ㎡ at 35 ℃) 12 12 12 12 11 Flexural modulus (kgf / ㎡ at 35 ℃) 2310 2330 2290 2300 2260 Volume resistance 25 ° C (1.0E16 Ω * cm) 6.5 5.7 6.1 4.1 2.1 150 ° C (1.0E12 Ω * cm) 9.2 8.8 8.6 5.3 3.7 Formability Void occurrence / experiment (Visual Inspection) 0 / 1,000 0 / 1,000 0 / 1,000 3 / 1,000 2 / 1,000 PCT Reliability Bad occurrences / experiments 0/640 0/640 0/640 3/640 24/640

Looking at Table 2, the composition of the present invention (Examples 1 to 3) comprising titanium nitride black coated with a phenolic resin composition (Comparative Example 1) and composition using carbon black untreated titanium nitride black It was confirmed that the volume resistance was higher than that of Comparative Example 2, and the insulation was excellent.

In addition, the semiconductor device packages (Examples 1 to 3) sealed with the composition of the present invention was confirmed that the moldability and reliability are superior to Comparative Examples 1 and 2.

Claims (13)

Titanium black nitride represented by the following Chemical Formula 1; Epoxy resins; Curing agent; Curing accelerators; And Including inorganic fillers, The titanium nitride black epoxy resin composition for sealing a semiconductor device, characterized in that the coating with a phenol resin. [Formula 1] TiN _x O _y (In Formula 1, x is 0.01 to 3, and y is 1.5 to 10.) The method of claim 1, Titanium nitride black coated with the phenol resin is a titanium nitride and epoxy resin composition for sealing a semiconductor device, characterized in that the phenol resin is present in a weight ratio of 1 to 30: 99 to 70. The method of claim 1, The epoxy resin composition for sealing a semiconductor device, characterized in that the average particle diameter of the titanium nitride black coated with the phenol resin is 30 ~ 200nm. The method of claim 1, The titanium nitride black coated with the phenol resin is dispersed in a solvent capable of dispersing the titanium nitride black, and then the phenol resin is coated on the dispersed titanium nitride black particles. The method of claim 1, The phenol resin is selected from the group consisting of phenol aralkyl type phenol resin, phenol novolak type phenol resin, cresol novolak type phenol resin, xylox type phenol resin, dicyclopentadiene phenol resin and naphthalene phenol resin Epoxy resin composition for semiconductor element sealing. The method of claim 1, The epoxy resin is a phenol aralkyl type epoxy resin represented by the following formula (2) epoxy resin composition for sealing semiconductor elements. [Formula 2]

(In Formula 2, the average value of n is 1 to 7.) The method of claim 1, The curing agent is a phenol aralkyl type phenol resin represented by the following formula (3) epoxy resin composition for sealing semiconductor elements. (3)

(In Formula 3, the average value of m is 1 to 7.) The method of claim 1, Based on 100 parts by weight of the epoxy resin composition for sealing a semiconductor device, 0.05 to 5 parts by weight of titanium nitride black coated with the phenol resin; 3 to 15 parts by weight of the epoxy resin; 0.1 to 10 parts by weight of the curing agent; 0.001 to 1 part by weight of the curing accelerator; And Epoxy resin composition for sealing a semiconductor device comprising the inorganic filler 70 to 95 parts by weight. The semiconductor element package sealed with the epoxy resin composition for semiconductor element sealing in any one of Claims 1-8. 10. The method of claim 9, A semiconductor device package characterized by being sealed by one of the low pressure transfer molding method, the injection molding method, and the casting molding method. As titanium titanium black contained in the epoxy resin composition for semiconductor element sealing, The titanium black nitride is titanium nitride black, characterized in that coated with a phenol resin after being dispersed in a solvent. The method of claim 11, The solvent is titanium black nitride, characterized in that the solvent is a mixture of methyl isobutyl ketone and acetone. The method of claim 11, The titanium nitride black coated with the phenol resin is titanium nitride black and phenolic resin is present in the weight ratio of 1 to 30: 99 to 70 titanium nitride, characterized in that.