JP2016098353A - Black pigment, coloring composition and coloring member - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a black pigment, a coloring composition and a coloring member excellent in blackness and colorability and capable of reducing possibility of generation of leakage failure even applied to high definition wires.SOLUTION: A black pigment consisting of amorphous carbon containing a SPstructure and a SPstructure with percentage of the SPstructure of 35% to 70% based on the total of the SPstructure and the SPstructure, a coloring composition by dispersing a pigment component containing the same in a liquid dispersant and a coloring member containing the black pigment are excellent in blackness and colorability and can reduce possibility of generation of leakage failure even applied to high definition wires.SELECTED DRAWING: None

Description

  The present invention relates to a black pigment, a coloring composition, and a coloring member.

In recent years, with the increase in performance and downsizing / thinning of electronic devices, in the field of electronic component devices, the integration of electronic component devices has been increased by reducing the size of resistors, capacitors, filters, etc. Miniaturization, thinning, etc. are progressing. Along with this, the distance between pitches of wiring such as between the inner leads of the electronic component device, between the pads, and between the wires is narrowed. On the other hand, carbon black, iron oxide, titanium oxynitride, or the like is used as a colorant for a sealing material used in an electronic component device (see, for example, Patent Document 1).
Such a colorant also has high insulating properties for light shielding materials (black matrix) for image forming elements such as liquid crystal color filters, adhesives for fixing electrode terminals of capacitors and batteries, coating materials, and exterior films for electronic components. It is used as a black pigment.

JP 2012-96946 A

  However, when an agglomerated material with low insulating properties is sandwiched between wirings having a narrow pitch distance, the electrical characteristics of the electronic component device are poor. Although carbon black is excellent in blackness and colorability, it has conductivity, so it was applied as a seal for high-definition wiring accompanying the recent increase in the density of electronic components, and as an adhesive or coating material for electrode terminals. In some cases, there was a risk of leak failure (short circuit). Iron oxide has problems of aggregation due to magnetism, inferior dispersibility, and low heat resistance. Since titanium oxynitride has semiconductivity, it has poor insulation and may cause a leak failure.

  The present invention has been made in view of such circumstances, and has a black pigment and a coloring composition that are excellent in blackness and colorability and can reduce the possibility of occurrence of leakage defects even when applied to high-definition wiring. And it aims at providing a coloring member.

The present inventors have conducted extensive studies to solve the above problem results, and a SP ³ structure and the SP ² structure, of the SP ³ structure to the sum of the SP ³ structure and the SP ² structure ratio specific It has been found that the black pigment in the range is excellent in blackness and colorability, and the coloring composition and coloring member containing the black pigment can reduce the possibility of occurrence of leakage defects even when applied to high-definition wiring. .
The present invention has been completed based on such findings.

That is, the present invention provides the following [1] to [6].
[1] It is made of amorphous carbon powder containing an SP ³ structure and an SP ² structure, and the ratio of the SP ³ structure is 35% or more and 70% or less with respect to the total of the SP ³ structure and the SP ² structure. A black pigment characterized by
[2] The black pigment as described in [1] above, wherein the conductivity obtained by the dielectric resonance method is 1.0 S / m or less.
[3] The black pigment as described in [1] or [2] above, wherein the amorphous carbon powder has a weight average particle diameter of 50 μm or less.
[4] The black pigment according to any one of [1] to [3], wherein the amorphous carbon powder has a specific surface area of 10 to 1000 m ² / g.
[5] A coloring composition comprising a pigment component containing the black pigment according to any one of [1] to [4], dispersed in a liquid dispersion medium.
[6] A colored member comprising the black pigment according to any one of [1] to [4].

  According to the present invention, it is possible to provide a black pigment, a colored composition, and a colored member that are excellent in blackness and colorability and can reduce the possibility of occurrence of leakage defects even when applied to high-definition wiring.

It is sectional drawing which shows typically the sealing state of an electronic component (chip capacitor). It is sectional drawing which shows a film capacitor typically. It is a top view which shows typically the color filter (black matrix) of a liquid crystal. It is sectional drawing of the dielectric resonator which has arrange | positioned the measurement sample.

First, the black pigment of the present invention will be described.
The black pigment of the present invention is made of an amorphous carbon powder containing an SP ³ structure and an SP ² structure. The ratio of SP ³ structure, relative to the combined total of the SP ³ structure and SP ² structure, 70% or less than 35%.

The ratio of the SP ³ structure to the total of the SP ³ structure and the SP ² structure (hereinafter also simply referred to as SP ³ ratio) is preferably 40 to 70%, more preferably 40 to 65%.
If the SP ³ ratio is less than 35%, the insulating property of the black pigment may be lowered, and if it exceeds 70%, the blackness and the colorability may be lowered.
Note that amorphous carbon may include structures such as —CO and —COOH derived from functional groups attached to the particle surface and the like.

Here, the SP ³ structure forms a σ bond represented by an SP ³ hybrid orbital. If the SP ³ structure is contained in a large amount, the light shielding ratio is lowered and the colorability is inferior. The SP ² structure is composed of σ bonds and π bonds represented by SP ² hybrid orbitals, and if it contains a lot of SP ² structures, the π electrons are easily moved, so that the insulating property is poor.
Therefore, by including the SP ³ structure and the SP ² structure in specific ratios, the black pigment made of amorphous carbon powder exhibits good colorability and insulation, thereby including the black pigment of the present invention. The coloring composition and the coloring member can obtain sufficient contrast by marking with a laser, for example, can be clearly marked, and can prevent leakage defects even when applied to high-definition wiring.

The SP ² structure and the SP ³ structure, by XPS analysis using X-ray photoelectron spectroscopy, and the integrated intensity of a peak having a peak center from 1540 cm ^-1 derived from SP ² bond to 1650 cm ^-1, the SP ³ bond it can be determined from the ratio of the integrated intensity of a peak having a peak centered at 1500 cm ^-1 from the origin to 1200 cm ^-1.

  The method for producing the amorphous carbon is not particularly limited. For example, the amorphous carbon is used as a raw material by using a heating means such as a resistance heating method, a laser heating method, an arc discharge method, a high frequency plasma method, a plasma jet method, or a microwave heating method. Examples include a method of vaporizing a carbon source and cooling and resolidifying the vaporized carbon vapor.

Specifically, a method of generating carbon vapor by arc discharge between the electrodes of the carbon rod in a vacuum or an inert gas atmosphere is most preferably used.
As the inert atmosphere gas, helium gas having a high carbon evaporation rate is preferably used.
Processing temperature becomes like this. Preferably it is 500-1200 degreeC, More preferably, it is 500-1000 degreeC. By setting the treatment temperature within the above range, the ratio of the SP ³ structure to the total of the SP ³ structure and the SP ² structure of the amorphous carbon obtained can be 35% or more and 70% or less. Further, by setting the temperature to 500 ° C. or higher, the SP ³ ratio of the amorphous carbon can be set to 35% or higher, and the insulating carbon can have good insulating properties. By setting the temperature to 1200 ° C. or lower, the SP ^{3 of the} amorphous carbon can be obtained. The ratio can be made 70% or less, and the blackness and light shielding property of the cured product can be improved.
The atmospheric pressure for vaporizing carbon is preferably 20 kPa or more. By adjusting the pressure under the above conditions, the resulting amorphous carbon has an SP ³ ratio of 35% or more and 70% or less, and the electric resistivity of the amorphous carbon. Can be controlled to 1 × 10 ⁴ Ω · m or more, and good insulating properties can be obtained. The electric resistivity of the amorphous carbon increases the higher the SP ³ ratio, SP ³ proportions by 40% or more 1 × 10 ⁸ Omega · m or more, further 1 × by 50% or more 10 It can be ¹⁰ Ω · m or more.

The black pigment of the present invention preferably has a conductivity obtained by a dielectric resonance method of 1.0 S / m or less. Thereby, it has the above-mentioned favorable insulation. For example, the conductivity measurement by the dielectric resonance method is performed as follows.
FIG. 4 is a cross-sectional view of the dielectric resonator 101 in which the measurement sample 107 is arranged. A measurement sample 107 (height: 4 mm) is mounted on a sample stage 104 (relative dielectric constant: 2.0, thickness: 1 mm) made of a low dielectric constant material of the dielectric resonator 101. The dielectric resonator 101 includes a cylindrical dielectric 102 (relative dielectric constant: 45.2, dielectric loss tangent: 76.5 × 10 ⁻⁵ , diameter: 15 mm, height: 7.5 mm) and a low dielectric constant material. A support base 103 (relative permittivity: 2.0, dielectric loss tangent: 2 × 10 ⁻⁴ , outer diameter: 20 mm, inner diameter: 6 mm, height: 10 mm), a cylindrical shielding conductor 105, and a lower shielding conductor 106 It is configured. The interval between the sample stage 104 and the lower shielding conductor 106 is 24.5 mm, and the inner diameter of the cylindrical shielding conductor 105 is 24.5 mm.
A semi-rigid coaxial cable having a through hole formed at the + y direction side end (105a) and the −y direction side end (105b) of the cylindrical shield conductor 105 and a loop antenna formed at the tip is inserted from each through hole, Is connected to a network analyzer (product name: 8722ES, manufactured by Agilent) to resonate the TE resonance mode of the dielectric resonator 101 and measure its resonance characteristics.
When the TE resonance mode of the dielectric resonator 101 is resonating, the electromagnetic field leaked from the sample stage 104 also enters the inside of the measurement sample 107, so that the conductivity of the measurement sample 107 is the resonance characteristic of the dielectric resonator 101. To affect. Accordingly, the resonance characteristics of the dielectric resonator 101, in particular, the measured value of the no-load Q (Qu), and the resonance characteristics of the measurement sample 107 in which the conductivity of the measurement sample 107 is changed, in particular, the electromagnetic field simulation result of Qu are measured. The conductivity of the sample 107 can be obtained.

The amorphous carbon powder is preferably a powder having a weight average particle diameter of 50 μm or less, more preferably 1 to 50 μm. By setting the weight average particle size to 50 μm or less, the colorability is improved, and as a result, a sufficient contrast can be obtained by the marking, and a clear marking can be performed.
The weight average particle diameter is a value measured by a laser diffraction / scattering particle size distribution measuring apparatus (for example, manufactured by Shimadzu Corporation, apparatus name: SALD-3100).

Further, the powder of the amorphous carbon is preferably a nitrogen adsorption method specific surface area by (BET method) is 10 to 1000 m ² / g, more preferably 12~800m ² / g. By setting it as 10 m < ² > / g or more, a dispersibility can improve and colorability can be made favorable. By setting it as 1000 m < ² > / g or less, the fall of a bulk density can be prevented, for example, the fluidity | liquidity of a coloring composition can be made favorable.

In the present invention, the amorphous carbon can be pulverized to have a desired particle size.
The method for pulverizing the amorphous carbon is not particularly limited, and general pulverizers such as a cutting mill, a ball mill, a cyclone mill, a hammer mill, a vibration mill, a cutter mill, a grinder mill, and a speed mill can be used. Furthermore, you may provide the classification process which adjusts the powder of the amorphous carbon obtained by the said grinding | pulverization to the particle aggregate which has a predetermined particle size distribution by sieve classification and air classification.

Further, the carbon particles may be fired after molding a thermosetting resin material such as a phenol resin or a polyimide resin to a predetermined particle size. For example, after adding phenols to water and ethanol to dissolve them, aldehydes twice as much as phenols are added and stirred, and 10% by mass ammonia water is added as a catalyst and reacted for a predetermined time. A method for obtaining dispersed spherical carbon particles is known. Furthermore, in the said reaction, it can control to a desired particle diameter by adjusting the ethanol concentration and ammonia concentration of a solvent. The monodispersed spherical carbon particles thus obtained are preferably heat-treated under conditions of 500 ° C. to 1200 ° C. in a vacuum or an inert gas atmosphere, so that a monodispersed amorphous carbon powder can be obtained.
The electrical properties of the black pigment contained in the colored composition and the colored member described later and the powder characteristics of the amorphous carbon can be obtained by removing the dispersion medium of the colored composition and the colored member by a method such as drying and filtration, or by organic This can be confirmed by analyzing the black pigment or amorphous carbon separated by dissolving and removing the resin component.

  The amorphous carbon is used as a black pigment, that is, a black colorant. The amorphous carbon is a derivative obtained by hydrogenation, oxidation, alkylation, amination, halogenation, cycloaddition or inclusion, or coupling. What was surface-treated with an agent can also be used.

The amorphous carbon includes an insulating SP ³ structure, which is a characteristic of the diamond structure, and a conductive SP ² structure, which is a characteristic of the carbon black or the graphite structure. The SP is equivalent to the total of the SP ³ structure and the SP ² structure. ^Since the ratio of the ^three structures is 35% or more, there is a feature that insulation is imparted.
As described above, the SP ³ structure is a characteristic of the diamond structure, and the SP ² structure is a characteristic of the carbon black or the graphite structure. The SP ³ structure and the SP ² structure obtained from the XPS analysis can be considered to be derived from amorphous carbon, diamond, and graphite contained therein. Therefore, if the presence of the SP ³ structure and the SP ² structure is confirmed in the coloring composition and the coloring member and the ratio of the SP ³ structure to the total of the SP ³ structure and the SP ² structure is within the above range, the coloring composition and the coloring It may be considered that the member contains the black pigment of the present invention.
On the other hand, fullerene, which is a special material, exhibits insulation even though the SP ³ structure ratio is as low as 30% or less. This is because the movement of electrons is blocked by making the SP ² structure into a spherical structure. Since the fullerene is produced by a special control method, the production efficiency is low and it is very expensive.
On the other hand, the amorphous carbon in the present invention can be produced by a general process for producing carbon black or graphite, so that production efficiency is high and inexpensive.

The coloring composition of the present invention will be described.
The colored composition of the present invention is a liquid colored composition containing the above-described black pigment alone or as one of a plurality of pigment components in a liquid dispersion medium. When the above-described black pigment is included as one of a plurality of pigment components, other pigments used in combination are not particularly limited, and known pigments can be used. However, in order not to impair the insulating properties of the black pigment, the other specific pigments used in combination also have an electrical resistivity of 1 × 10 ⁴ Ω · m or more, or a conductivity obtained by a dielectric resonance method of 1.0 S. / M or less is preferably used.

  As the liquid dispersion medium, a solvent used together with carbon black can be used. For example, an aqueous solvent, an alcohol solvent, an ester solvent, an ether solvent, a ketone solvent, a hydrocarbon depending on the use of the coloring composition A system solvent or the like is preferably used. Specifically, water, methanol, ethanol, n-propanol, isopropanol, ethylene glycol, propylene glycol and other alcohols, α- or β-terpineol and other terpenes, acetone, methyl ethyl ketone, cyclohexanone, N-methyl-2 -Ketones such as pyrrolidone, aromatic hydrocarbons such as toluene, xylene, tetramethylbenzene, cellosolve, methyl cellosolve, ethyl cellosolve, carbitol, methyl carbitol, ethyl carbitol, butyl carbitol, propylene glycol monomethyl ether, Propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, triethylene glycol monomethyl ether, triethylene Glycol ethers such as glycol monoethyl ether, ethyl acetate, butyl acetate, cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, carbitol acetate, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl Examples thereof include single or mixed solvents such as acetates such as ether acetate, and water, ethanol, isopropanol, methyl ethyl ketone, N-methyl-2-pyrrolidone, toluene and the like are preferable. For polar solvents such as water and water-soluble solvents, nonionic surfactants such as alkylene oxide monoalkyl ether, alkylene oxide monoalkyl ether acetate, alkylene glycol diacetate, (meth) acrylates, and divinyl ethers are used. It is preferable to add, and it is preferable to add dispersion resins, such as a polyvinyl acetal resin and a urethane resin, to nonpolar solvents, such as toluene.

In addition to the pigment component and the liquid dispersion medium, the coloring composition may contain additives such as a dispersant and a wetting agent, and a binder, a curing agent, a polymerization agent, a leveling agent, an antifoaming agent, and a pore-forming agent as necessary. Good.
What is necessary is just to adjust suitably content of the black pigment in a coloring composition according to the use and objective of a coloring composition. For example, when used as a black matrix of a color filter used in a liquid crystal color display or an organic EL display, a good light-shielding property is imparted by containing a black pigment in a ratio of 20 to 60% by mass in the coloring composition. be able to. Moreover, when using as a resist ink, an inkjet ink, etc., what is necessary is just to contain the pigment component which combined the said black pigment and another pigment in the coloring composition in the ratio of 5-15 mass%. As a result, the pigment is stably dispersed, the viscosity with respect to coating is maintained, and a uniform film can be formed.
The coloring composition of the present invention can be used for an insulating adhesive, an insulating coating (coating), etc., in addition to the above-described uses.

  The colored member of the present invention is a member containing the above-described black pigment, and in addition to a member colored with a liquid colored composition containing a black pigment, for example, a resin film or sheet containing the above-described black pigment, an electronic component (passive Element) sealing material, electronic circuit and conductor wiring coating. In addition, various colored members made of natural rubber, synthetic rubber, silicone rubber, silicone resin or the like containing the above black pigment are also included in the present invention.

FIG. 1 is a cross-sectional view schematically showing a mounting substrate 10 on which a chip-type passive element 1 is mounted and sealed with a coloring member 4 of the present invention which is a sealing material. Electrodes (not shown) of the passive element 1 such as a capacitor, a resistor, and a piezoelectric element are electrically connected to a pad 3 provided on the surface of the printed board 2. The coloring member 4 is sealed so as to cover the passive element 1 and the pad 3. With the miniaturization and high integration of the chip-type passive element 1, the interval between adjacent pads 3 is very narrow. By using the coloring member 4 having excellent insulating properties, between the pads 3 and between the passive elements 1. Leak failure can be reduced. The coloring member 4 does not need to cover the entire passive element 1 and may cover only the connection portion with the pad 3.
Such a colored member 4 is, for example, a precursor (hereinafter simply referred to as a precursor) containing (A) an epoxy resin, (B) a phenol resin curing agent, (C) an inorganic filler, and (D) the above-described black pigment. (Also called body).

As the epoxy resin of component (A), as long as it has two or more epoxy groups in one molecule, the molecular structure, molecular weight, etc. are not particularly limited and are generally used for sealing electronic parts. Can be widely used. Specific examples of the epoxy resin include phenolic novolac type epoxy resins, cresol novolac type epoxy resins, aliphatic epoxy resins such as dicyclopentadiene derivatives, and aromatic epoxy resins such as biphenyl type, naphthyl type and bisphenol type. Etc. These epoxy resins may be used alone or in combination of two or more.
The content of the component (A) with respect to the total amount of the precursor is preferably 5 to 30% by mass, more preferably 5 to 25% by mass, and still more preferably 10 to 20% by mass from the viewpoint of moldability and reliability. It is.

  (B) As a phenol resin hardening | curing agent of a component, if it has two or more phenolic hydroxyl groups in 1 molecule, a molecular structure, molecular weight, etc. will not be restrict | limited in particular, Generally as a hardening | curing agent of an epoxy resin What is being used can be widely used. Specific examples of the phenol resin curing agent include phenolic novolak resins, cresol novolak resins, aliphatic phenol resins such as dicyclopentadiene derivatives, aromatic phenol resins such as biphenyl type, naphthyl type, and bisphenol type. Can be mentioned. These phenol resin curing agents may be used alone or in combination of two or more.

  The (A) component epoxy resin and the (B) component phenol resin curing agent are the epoxy group (a) and (B) component phenol resin curing of the (A) component epoxy resin in the precursor. It is preferable to make it contain so that ratio (a) / (b) (equivalent ratio) with the phenolic hydroxyl group (b) which an agent has may be in the range of 0.1-2.0, 0.5-1.5 It is more preferable to make it contain so that it may become this range. By setting the equivalent ratio within the above range, the moldability of the precursor, the heat resistance and the moisture resistance of the colored member 4 after curing can be improved.

  The content of the component (B) with respect to the total amount of the precursor is preferably 1 to 15% by mass, more preferably 3 to 15% by mass, and further preferably 5 to 10% by mass from the viewpoint of moldability and reliability. It is.

  As the inorganic filler of component (C), metal oxide powder such as silica powder and alumina powder, metal nitride powder such as silicon nitride powder and aluminum nitride powder, metal carbide powder such as silicon carbide powder, calcium carbonate powder, Examples include silicone powder and glass fiber. These inorganic fillers may be used individually by 1 type, and 2 or more types may be mixed and used for them.

The inorganic filler as the component (C) preferably has an average particle size of 1 to 60 μm and a maximum particle size of 200 μm or less.
The content of the component (C) with respect to the total amount of the precursor is preferably 60 to 95% by mass, more preferably 65 to 93% by mass, and still more preferably 70 to 90% by mass. By setting it as 60 mass% or more, the moldability of a precursor, the mechanical characteristics of the colored member 4 after hardening, heat resistance, and moisture resistance can be made excellent. Moreover, the marking by the laser with respect to this coloring member 4 can be made clear. By setting it as 95 mass% or less, the fluidity | liquidity and moldability of a precursor can be made favorable.

  The content of the black pigment of the component (D) with respect to the total amount of the precursor is preferably 0.01 to 5.0% by mass, more preferably 0.02 to 4.0% by mass, and still more preferably 0.00. 1 to 3.0% by mass. By setting it as 0.01 mass% or more, the visibility of the marking by a laser becomes favorable. By setting the content to 5.0% by mass or less, the fluidity of the precursor can be improved.

  The precursor of the colored member 4 as a sealing material is mainly composed of the above-described (A) epoxy resin, (B) phenol resin curing agent, (C) inorganic filler, and (D) the above-described black pigment. However, a curing accelerator generally blended in this kind of composition as necessary as long as the effects of the present invention are not impaired; natural waxes, synthetic waxes, esters, linear aliphatic metals Mold release agents such as salts, acid amides and paraffins; low stress imparting agents such as rubber-based and silicone-based polymers; coupling agents as inorganic filler treating agents can be further blended. Further, a colorant such as cobalt blue can be appropriately blended within a range not impairing the effects of the present invention.

  The precursor comprises (A) an epoxy resin, (B) a phenol resin curing agent, (C) an inorganic filler, (D) the above-described black pigment, and various components blended as described above, a mixer, etc. Then, the mixture is mixed by heating, melted and kneaded with a hot roll or a kneader, cooled and solidified, and then pulverized to an appropriate size.

In addition, the black pigment as the component (D) is previously mixed with at least a part, preferably all, of the epoxy resin as the component (A) and / or the phenol resin curing agent as the component (B), and is heated and melted and kneaded. The pre-kneaded product obtained in this way may be mixed with other components. By using such a pre-kneaded material, the moldability of the precursor and the insulation reliability of the colored member 4 after curing can be further improved.
A release agent, other colorant, coupling agent and the like can be appropriately added to the pre-kneaded product.
The colored member 4 of the present invention obtained by heat-curing the above-mentioned precursor is composed of amorphous carbon powder containing an SP ³ structure and an SP ² structure, and is a total of the SP ³ structure and the SP ² structure. On the other hand, a black pigment having a SP ³ structure ratio of 35% to 70% is included.

  By sealing the passive element 1 using the colored member 4, leakage defects between the pads 3 and between the passive elements 1 can be reduced, and sufficient contrast can be obtained by marking using a laser so that a clear marking can be obtained. It can be carried out. Examples of the passive element 1 include a capacitor, a resistor, and a piezoelectric element. However, the passive element 1 is not particularly limited, and examples thereof include an inductor, a transformer, a crystal resonator, a heater, and a battery.

For such a mounting substrate 10, the colored member 4 can be marked using a carbon dioxide gas laser, a YVO ₄ laser, a YAG laser, an excimer laser, or the like. Marking with various lasers can be performed using the same method as before, and is not particularly limited.
The mounting substrate 10 sealed with the coloring member 4 as described above can obtain a sufficient contrast even when marking is performed using the same method as the conventional method, can perform clear marking, and has high-definition wiring. Even if it is applied to the above, the occurrence of a leak failure can be prevented.

FIG. 2 is a cross-sectional view schematically showing a case mold type film capacitor. In case mold type film capacitor 20 (hereinafter also simply referred to as film capacitor 20), bus bar 6 made of a copper plate or the like is connected to electrodes 5 provided on both end faces of metallized film capacitor element which is passive element 1, and metallized. The film capacitor element and the bus bar 6 are accommodated in the accommodating portion of the case 7 having the upper surface opening type. The housing portion of the case 7 is filled with the colored member 4 of the present invention as a mold resin, and protects the metallized film capacitor element (passive element 1) from the external environment. The case 7 is not essential, and the colored member 4 itself may be used as an exterior of the metallized film capacitor element.
As the mold resin, a silicone resin, a urethane resin, an epoxy resin, or the like is used in terms of insulation, impact resistance, moisture resistance, and the like. Since the colored member 4 of the present invention contains the above-described black pigment, it becomes a mold resin having good colorability and insulation. In addition, the coloring member 4 may contain an inorganic filler, a flame retardant, an antioxidant, and the like. In addition, since the above-mentioned black pigment is excellent in thermal conductivity, the colored member 4 also has high thermal conductivity, and there is an advantage that heat dissipation of the film capacitor is improved.
When the bus bar 6 is arranged so as to cover the upper part of the metallized film capacitor element for the purpose of reducing inductance and improving moisture resistance, the sheet-like colored member 4 is used as an insulating sheet arranged between the pair of bus bars 6. You can also

FIG. 3 is a plan view schematically showing a color filter used for a liquid crystal color display or an organic EL display. In the color filter 30, R (red), G (green), and B (blue) pixels are arranged in a stripe shape, a mosaic shape, a triangle shape, etc. on a transparent substrate made of glass or the like, and irradiated with a backlight from the back surface. Color is generated by additive mixing of transmitted light of R, G, and B pixels. A black matrix is formed around each pixel in a lattice pattern to shield the light from the backlight and prevent color mixing of adjacent pixels. Since the coloring member 4 of the present invention contains the above-described black pigment and is excellent in light shielding properties and insulation properties, it can be suitably used as such a black matrix.
The black matrix can be produced, for example, by applying a black resist containing a resin, a monomer, a polymerization initiator, and a dispersion of the above-described black pigment to a substrate, and forming a pattern by photolithography.

  As mentioned above, although the specific example was given and demonstrated about the black pigment of this invention, a coloring composition, and a coloring member, the use of the black pigment of this invention, a coloring composition, and a coloring member is not restricted to these. The present invention can be applied to various uses without departing from the gist of the present invention.

  EXAMPLES Next, although an Example demonstrates this invention concretely, this invention is not limited at all by these examples.

(Synthesis Example 1)
Evaluation samples were synthesized by the following general thermal CVD method. Specifically, acetylene, a raw material gas composed of carbon dioxide and an inert gas was synthesized by heat treatment in a heating furnace container heated to 1000 ° C. In the source gas, the partial pressure of acetylene is 10 × 10 ² Pa, and the partial pressure of carbon dioxide is 7 × 10 ³ Pa. The partial pressure ratio of acetylene and carbon dioxide (acetylene / carbon dioxide) is 5.
In the above synthesis process, thermal CVD reaction synthesis was performed for 30 minutes to synthesize amorphous carbon. The synthesized amorphous carbon was pulverized for 2 hours using a dry jet mill pulverizer to obtain amorphous carbon powder having a weight average particle diameter of 4 μm.
The obtained amorphous carbon had an SP ³ structure of 45 atomic%, an SP ² structure of 42 atomic%, and the amorphous carbon had a conductivity of 0.8 S / m.

Example 1
Each component is blended in the proportions shown in Table 2, mixed at room temperature (25 ° C.) using a mixer, and 90 to 95 ° C. using a pressure type kneader (manufactured by Kurimoto Steel Works, model name: KRC-T-2). The mixture was heated and kneaded at a temperature of 2 minutes, cooled and solidified, and then pulverized to an appropriate particle size using a mill pulverizer (Tajima Chemical Machinery Co., Ltd., model name: ND-30) to prepare a colored member precursor. .

(Examples 2-5, Comparative Examples 1-3)
In the same manner as in Example 1, the components were blended in the proportions shown in Table 2 to obtain a colored member precursor.

  The precursors obtained in Examples 1 to 5 and Comparative Examples 1 to 3 are transfer molded at 175 ° C. for 2 minutes, and further post-cured at 175 ° C. for 8 hours to obtain a colored member. A 1.0 mm molded article for test was obtained. In addition, the evaluation chip capacitor was sealed under the same conditions to produce a mounting substrate.

The raw materials used in Examples and Comparative Examples are as follows.
(Epoxy resin)
o-cresol novolak resin (manufactured by Sumitomo Chemical Co., Ltd., trade name: EOCN-195XL-70; epoxy equivalent 198)
(Phenolic resin curing agent)
Phenol novolac resin (manufactured by Showa Polymer Co., Ltd., trade name: BRG-557; hydroxyl group equivalent 105)
(Inorganic filler)
Fused spherical silica powder (manufactured by Denki Kagaku Kogyo Co., Ltd., trade name: FB-60; average particle size 23 μm)
(Black pigment)
Amorphous carbon carbon black obtained in Synthesis Example 1 (Mitsubishi Chemical Corporation, trade name: MA-600; average particle size 20 nm, conductivity 6.8 S / m)
C60 fullerene (manufactured by Frontier Carbon Co., Ltd., trade name: Nanom Purple; weight average particle size 20 μm)
(Other ingredients)
Carnauba wax (product name: Carnauba wax, manufactured by Toyo Petrolite Co., Ltd.)
Coupling agent (Nihon Unicar Co., Ltd., trade name: A-187)
Curing accelerator (Hokuko Chemical Co., Ltd., trade name: PP-200)

With the following evaluation method, the ratio between the SP ³ structure and the SP ² structure of amorphous carbon, carbon black, and C60 fullerene obtained in Synthesis Example 1 as a black pigment, and the electrical conductivity were measured. The results are shown in Table 1.

[Ratio of SP ³ structure to SP ² structure]
The black pigment powder for measurement was set on a glass substrate for one cup of a spatula, and the ratio of the SP ³ structure and the SP ² structure was measured. Microscopic laser Raman spectrometer (manufactured by Horiba, Ltd., LabRam HR-800) using a peak intensity having a peak centered at 1650 cm ^-1 from 1540 cm ^-1 obtained by micro-Raman spectroscopy and SP ² structure, from 1200 cm ^-1 the peak intensity with a peak centered at 1500 cm ^-1 and SP ³ structure, after performing peak fitting, the peak intensity ratio of the SP ² structure and the SP ³ structure, the ratio of SP ³ structure and the SP ² structure did.

[conductivity]
FIG. 4 is a cross-sectional view of the dielectric resonator 101 in which the measurement sample 107 is arranged. A measurement sample 107 (height: 4 mm) is mounted on a sample stage 104 (relative dielectric constant: 2.0, thickness: 1 mm) made of a low dielectric constant material of the dielectric resonator 101. The dielectric resonator 101 includes a cylindrical dielectric 102 (relative dielectric constant: 45.2, dielectric loss tangent: 76.5 × 10 ⁻⁵ , diameter: 15 mm, height: 7.5 mm) and a low dielectric constant material. A support base 103 (relative permittivity: 2.0, dielectric loss tangent: 2 × 10 ⁻⁴ , outer diameter: 20 mm, inner diameter: 6 mm, height: 10 mm), a cylindrical shielding conductor 105, and a lower shielding conductor 106 It is configured. The distance between the sample stage 104 and the lower shielding conductor 106 was 24.5 mm, and the inner diameter of the cylindrical shielding conductor 105 was 24.5 mm. The above-described various black pigment powders were used as the measurement sample 107, and the conductivity of the measurement sample 107 was determined as follows.
A semi-rigid coaxial cable having a through hole formed at the + y direction side end (105a) and the −y direction side end (105b) of the cylindrical shield conductor 105 and a loop antenna formed at the tip is inserted from each through hole, Was connected to a network analyzer (product name: 8722ES, manufactured by Agilent) to resonate the TE resonance mode of the dielectric resonator 101 and measure its resonance characteristics.
When the TE resonance mode of the dielectric resonator 101 is resonating, the electromagnetic field leaked from the sample stage 104 also enters the inside of the measurement sample 107, so that the conductivity of the measurement sample 107 is the resonance characteristic of the dielectric resonator 101. To affect. Accordingly, the resonance characteristics of the dielectric resonator 101, in particular, the measured value of the no-load Q (Qu), and the resonance characteristics of the measurement sample 107 in which the conductivity of the measurement sample 107 is changed, in particular, the electromagnetic field simulation result of Qu are measured. The conductivity of the sample 107 was determined.

  About each said precursor, spiral flow was measured by the method shown below and the moldability was evaluated. Moreover, about each said molded article for a test, while evaluating the external appearance and laser marking property, the light transmittance was measured. Furthermore, the insulation reliability was evaluated by the method shown below about the mounting board | substrate sealed using each precursor. These results are shown in Table 2.

[Formability]
Using a spiral flow mold according to EMMI-1-66, the precursor was transferred and cured into a spiral flow mold heated to 175 ° C., and the flowed length was measured. It shows that it is excellent in fluidity | liquidity, so that the length which flowed is large.
[appearance]
The color of the appearance of the test molded product was visually observed. The appearance was evaluated based on the following criteria.
○: Good △: Slightly good (no problem in practical use)
×: Defect (those with practical problems)
[Laser marking properties]
Using a YAG laser marking device manufactured by Keyence Corporation, marking the molded product for testing under the conditions of output 14A, frequency 5.0 kHz, marking speed 400 mm / s, and character line width 0.2 mm, the following standards The laser marking property was evaluated.
○: Good △: Slightly good (no problem in practical use)
×: Defect (those with practical problems)
[Light transmittance]
Using a spectrophotometer V-570 manufactured by JASCO Corporation, the light transmittance with a thickness of 1 mm was measured in the wavelength region of 300 to 800 nm.
[Insulation reliability]
A continuity test was conducted to check for leakage between pads.

  As is apparent from the results in Table 2, the appearance of the molded product containing the black pigment of the present invention is good, the light transmittance is 0%, excellent in light-shielding properties, and excellent in laser marking properties. It was. Furthermore, the mounting substrate sealed with the precursor containing the black pigment of the present invention was also free from leak defects and excellent in insulation reliability.

  The colored member using the black pigment and the colored composition of the present invention is excellent in laser marking properties, does not cause leakage defects, and has excellent insulation reliability. It can be applied as a coloring member such as an insulating material or a light shielding material.

DESCRIPTION OF SYMBOLS 1 Passive element 2 Printed circuit board 3 Pad 4 Coloring member 5 Electrode 6 Bus bar 7 Case 10 Mounting board 20 Film capacitor 30 Color filter 101 Dielectric resonator 102 Columnar dielectric body 103 Support stand 104 Sample stand 105 Cylindrical shielding conductor 105a, 105b Cylinder Side end portion of shielding conductor 106 Lower shielding conductor 107 Measurement sample

Claims (6)

It is made of amorphous carbon powder containing an SP ³ structure and an SP ² structure, and the ratio of the SP ³ structure to the total of the SP ³ structure and the SP ² structure is from 35% to 70%, Black pigment.   The black pigment according to claim 1, wherein the electric conductivity obtained by the dielectric resonance method is 1.0 S / m or less.   3. The black pigment according to claim 1, wherein the amorphous carbon powder has a weight average particle diameter of 50 μm or less. 4. The black pigment according to claim 1, wherein a specific surface area of the amorphous carbon powder is in a range of 10 to 1000 m ² / g. 5.   A coloring composition comprising: a pigment component comprising the black pigment according to claim 1 dispersed in a liquid dispersion medium.   A colored member comprising the black pigment according to claim 1.