WO2012026577A1 - Film noir, substrat doté d'un film noir, dispositif d'affichage d'images, composition de résine noire, et liquide de dispersion de matière noire - Google Patents

Film noir, substrat doté d'un film noir, dispositif d'affichage d'images, composition de résine noire, et liquide de dispersion de matière noire Download PDF

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Publication number
WO2012026577A1
WO2012026577A1 PCT/JP2011/069286 JP2011069286W WO2012026577A1 WO 2012026577 A1 WO2012026577 A1 WO 2012026577A1 JP 2011069286 W JP2011069286 W JP 2011069286W WO 2012026577 A1 WO2012026577 A1 WO 2012026577A1
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Prior art keywords
black
film
resin
silver
fine particles
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PCT/JP2011/069286
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English (en)
Japanese (ja)
Inventor
田中　伸一
康徳 国光
博貢 加藤
剛 川瀬
Original Assignee
住友大阪セメント株式会社
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Priority claimed from JP2010189650A external-priority patent/JP5429114B2/ja
Application filed by 住友大阪セメント株式会社 filed Critical 住友大阪セメント株式会社
Priority to CN201180041475.XA priority Critical patent/CN103069316B/zh
Priority to KR1020137004842A priority patent/KR101800344B1/ko
Publication of WO2012026577A1 publication Critical patent/WO2012026577A1/fr

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    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/206—Filters comprising particles embedded in a solid matrix
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/22—Absorbing filters

Definitions

  • the present invention relates to a black film, a substrate with a black film having the black film, an image display device, a black resin composition, and a black material dispersion.
  • black materials for example, as described in Patent Document 1, metal materials such as carbon black, titanium black (low-order titanium oxide or titanium oxynitride), iron oxide, chromium, silver fine particles, and inorganic materials are used.
  • These black materials include black light-shielding film, black light-shielding glass, black paper, black cloth, black ink, displays such as plasma display panel (PDP), liquid crystal display (LCD) and organic electroluminescence (EL) display. It is used as a material that imparts black color or light shielding properties to black matrix materials, black seal materials, black mask materials, and the like of elements.
  • black matrix and black stripe for liquid crystal display elements prevent light leakage between pixels due to drive electrodes and the like in the liquid crystal display element. It is used for suppressing blurring and blurring of an image.
  • These are generally patterns of light-shielding materials in the form of stripes or grids formed on a transparent substrate such as glass or plastic sheet that is paired with the TFT element substrate using a photolithography method.
  • the black matrix or the like may be formed using a film of chromium oxide or the like, but after forming a black film in which the black material is dispersed in a photosensitive resin component, a photolithography method is used.
  • a resin black matrix produced by patterning a resin component is generally used.
  • a conventional black matrix for a liquid crystal display element is formed on a transparent substrate such as glass or plastic sheet which is paired with a TFT element substrate.
  • a color filter on array method COA method
  • a black matrix on array method BOA method
  • According to these methods compared with the case where a black matrix is formed on the color filter side, it is not necessary to take an alignment margin with the active element side, so that the aperture ratio can be increased, resulting in higher luminance. Can be achieved.
  • a method of enlarging the light emitting area of each light emitting element itself can be considered.
  • the wiring for driving the element contacts the black matrix or the light shielding wall, or the element driving directly on the black matrix or the light shielding wall. Structures that provide wiring have become mainstream.
  • an insulating material having a volume resistivity of a certain value or more for the black matrix or the like or the light shielding wall in order to prevent a short circuit between the wirings.
  • IPS drive type liquid crystal if the black matrix has conductivity, an electric field is generated in a direction different from the electric field for driving the liquid crystal and induces image disturbance. It is necessary to.
  • carbon black is generally used as a black material for light shielding.
  • carbon black has a high light-shielding property, it has a low electrical resistance value. Therefore, when it is mixed with a resin component to form a black matrix or a light-shielding wall, the carbon black for the resin component has a high light-shielding property.
  • the amount added is increased, carbon black particles are brought into contact with each other to form a conductive path, resulting in a problem that the insulating properties of the black matrix and the light shielding wall cannot be maintained.
  • the thickness of the black matrix and the height of the light-shielding wall are reduced while maintaining the insulating property by suppressing the amount of carbon black added to such an extent that conductivity is not exhibited.
  • the level difference between the substrate and the black matrix or the light-shielding wall is increased, and as a result, the disconnection of the wiring is likely to occur, the uniformity between the liquid crystal elements and the light emitting elements is deteriorated, and the in-plane variation of the elements is reduced.
  • the problem of becoming larger arises. Even when the insulating property can be maintained, the relative dielectric constant of the film is often as high as 200 or more, so that image distortion may be a problem.
  • Patent Document 2 In order to obtain a black matrix and a light-shielding wall that have a high light-shielding property, an insulating property, a reduced thickness, and a low relative dielectric constant, the following methods are disclosed for these problems.
  • Patent Document 2 carbon black is surface-treated with a diazonium compound to increase the dispersibility of carbon black in the resin, thereby increasing the carbon black content ratio in the black matrix resin and increasing the light shielding property.
  • Patent Document 3 discloses a method of obtaining a black matrix having a high insulating property and a relatively low relative dielectric constant by coating the surface of carbon particles with an insulating material.
  • Patent Document 4 uses, as a black material, a powder of titanium oxynitride (TiOxNy: titanium black) whose composition is controlled to improve light shielding properties, and this is combined with an insulating oxide powder.
  • TiOxNy titanium oxynitride
  • Patent Document 5 discloses that a black matrix having high light-shielding properties and insulating properties can be obtained by reducing the carbon black content and adding an organic pigment.
  • a wavelength 950 nm LED is generally used for signals from a wireless remote controller (remote controller), and a fiber 1064 nm band laser or the like is industrially used.
  • a cover using a member that shields visible light and transmits infrared light such as near infrared light from the viewpoint of preventing malfunction due to visible light and appearance. It is.
  • an infrared transmitting black film having sufficient transparency with respect to light having a wavelength from near infrared to infrared used, or an infrared transmitting using the infrared transmitting black film, although the appearance is black.
  • a filter is needed.
  • the COA method and the BOA method are considered to be mainstream, but in these methods, the black coating dry film formed on the array side is patterned to form a black matrix that is a black film. Therefore, it is necessary to align the black matrix pattern directly with respect to the array. Since this alignment uses infrared rays of 850 to 950 nm, a black coating dry film that transmits light in this wavelength region is desired as a black matrix material in order to read the alignment signal.
  • optical density Optical Density
  • T (%) is the transmittance of the membrane.
  • OD ⁇ log (T / 100) (1)
  • an OD value per 1 ⁇ m thickness is often used as a light shielding index.
  • Patent Documents 1 and 6 as black materials, mainly metal materials such as carbon black, titanium black (titanium oxynitride), iron oxide, chromium and silver fine particles, and inorganic materials
  • metal materials such as carbon black, titanium black (titanium oxynitride), iron oxide, chromium and silver fine particles, and inorganic materials
  • a conventional black film which is made of a material and formed using a material obtained by dispersing these black materials in an organic resin or an inorganic resin.
  • an infrared transmission filter using an organic pigment or dye as a black material as described in Patent Documents 7 and 8 has been proposed.
  • the transmittance is lowered in the wavelength region, and the film does not function as an infrared transmissive black film.
  • the organic pigment or dye may be decomposed or deteriorated by sunlight or ultraviolet light from a fluorescent lamp, for example, fading of a filter using these may occur. There are concerns.
  • OD NIR / OD 560 is an infrared transparent black film according to [4], which is 0.40 or less, [6] The infrared transparent black film according to [4] or [5], wherein the volume fraction of the black material is 1.0% by volume or more and 25% by volume or less, [7] The black film according to any one of [1] to [6], wherein the black material is metal fine particles mainly composed of silver and tin.
  • the black film has excellent light shielding properties and is given a volume resistivity of a certain value or more, and has excellent light shielding properties for visible light, and for infrared rays.
  • An infrared transparent black film having a transparency of a certain value or more, a substrate with a black film having the black film, an image display device, and a black resin composition and a black material dispersion for forming the black film can be provided. Accordingly, it is possible to provide an image display device having high brightness and high contrast characteristics.
  • Example B It is an electron microscope observation photograph of the cross section of the infrared light transmissive black film obtained in Example B1. It is an electron microscope observation photograph of the black film section obtained by comparative example B1.
  • the first invention of the present invention comprises at least a resin component and a black material, the volume fraction of the black material is 2% by volume to 30% by volume, and the average dispersed particle size in the film is 1 nm to 200 nm.
  • the present invention relates to a substrate with a black film having a film and an image display device.
  • the second invention of the present invention comprises a black material and a resin component, the average dispersed particle diameter in the film of the black material is 1 nm or more and 100 nm or less, and the transmittance per 1 ⁇ m thickness (T560 at a wavelength of 560 nm).
  • the first black film of this embodiment includes at least a resin component and a black material, the volume fraction of the black material is 2% by volume to 30% by volume, and the average dispersed particle size in the film is 1 nm to 200 nm.
  • the optical density per 1 ⁇ m thickness is 1 or more, and the volume resistivity is 10 11 ⁇ ⁇ cm or more.
  • the first black film of the present embodiment a black material described later is used, but this black material has high blackness and is excellent in dispersibility in the resin. Therefore, by setting the volume fraction in the black film to 2% by volume or more and 30% by volume or less, the optical density per 1 ⁇ m thickness, which is the characteristic of the black film of this embodiment, is 1 or more and the volume resistivity is A black film of 10 11 ⁇ cm or more can be easily obtained. Moreover, since the dispersibility is good, the relative dielectric constant at 1 KHz can be made 15 or less, and the particle size distribution index D90% can be made 600 nm or less.
  • the volume fraction of the black material needs to be 2% by volume or more and 30% by volume or less. If the amount of the black material is less than this range, sufficient light-shielding properties cannot be ensured when the black film is formed. Therefore, since the black film has a low resistance, a desired volume resistivity cannot be obtained.
  • the volume fraction of the black material is preferably 2% by volume or more and 28% by volume or less, and more preferably 2% by volume or more and 25% by volume or less. Note that the volume fraction of the black material in the first black film of the present embodiment is obtained from the mass of the black material and the resin forming component used as raw materials since the specific gravity of each of the black material and the resin component is known. be able to.
  • the black material is stable up to a high temperature because it is a metal.
  • the weight ratio of the resin component in the inside and the black material can be determined.
  • the specific components of the resin component and the black material are specified by component analysis, the specific gravity of both materials can be obtained. The volume fraction of may be obtained.
  • the average dispersed particle size in the black material film needs to be 1 nm or more and 200 nm or less.
  • the average primary particle size of the black material used is preferably 1 nm or more, and therefore it is difficult to exist as particles when the average dispersed particle size is less than 1 nm.
  • the average dispersed particle diameter exceeds 200 nm, a conductive path due to aggregation of the black material fine particles in the black film is likely to occur, so that it is difficult to secure a desired volume resistivity and the black material fine particles are aggregated. If this is significant, the light shielding property also decreases.
  • the average dispersed particle size in the film is preferably 2 nm or more and 200 nm or less, and more preferably 5 nm or more and 200 nm or less. Note that the average dispersed particle size in the black film of the present embodiment is indicated by a particle size (cumulative 50% diameter: median diameter) corresponding to a cumulative value of 50% when the particle size is represented by a cumulative distribution.
  • the particle size distribution index D90% in the black material film in the first black film is preferably 600 nm or less, and more preferably 500 nm or less. If the particle size distribution index D90% in the film is 600 nm or less, it is possible to suppress a large variation in particle diameter, and it is possible to ensure a sufficient light shielding property while maintaining a desired volume resistivity.
  • the particle size distribution index D90% in the film means a particle diameter (cumulative 90% diameter) corresponding to an accumulated value of 90% when the particle size is represented by a cumulative distribution, and the black color existing in the film. This is an index indicating the uniformity of the particle diameter of the material particles.
  • the lower limit of D90% is not specifically defined, since the lower limit of the average particle diameter of the black material to be suitably used is 1 nm, it is difficult in the actual manufacturing process to set D90% to less than 5 nm.
  • the average dispersed particle size in the film of the black material is measured by, for example, cutting a film sample in a cross-sectional direction using a FIB (focused ion beam) to make a slice, and observing the cut surface with a transmission electron microscope. Can do.
  • a certain number of arbitrary particles 50 or more, more preferably 100 or more
  • each particle image is approximated by a circle of the same area, and the diameter of the circle is determined as the diameter of the circle.
  • the cumulative distribution of the particle diameter was determined, and the particle diameter (median diameter) corresponding to the cumulative value of 50% was defined as the average dispersed particle diameter in the film.
  • the particle size distribution index D90% was determined as the cumulative 90% diameter of the particle diameter of the selected particles. The cumulative values are all based on the number.
  • the first black film of the present embodiment needs to have an optical density of 1 or more per 1 ⁇ m thickness. If the optical density per 1 ⁇ m is less than 1, sufficient light shielding properties cannot be obtained when the thickness of the black film is about several ⁇ m. In addition, in order to obtain sufficient light-shielding properties, the film thickness must be increased, and particularly when used as a black matrix or the like, disconnection of wiring, display unevenness, and the like are likely to occur due to the increase in film thickness. Therefore, the optical density per 1 ⁇ m is set to 1 or more as a range in which sufficient light shielding properties can be obtained without making the film thickness unnecessarily thick. Further, the optical density per 1 ⁇ m is preferably 1.2 or more, and more preferably 1.5 or more.
  • the black material in this embodiment has high blackness and is excellent in dispersibility in the resin
  • the amount of the black material is increased. Therefore, it is easy to set the optical density per 1 ⁇ m to 2 or more while maintaining a desired volume resistivity. The higher the optical density per 1 ⁇ m, the better, but the upper limit is about 10 due to the measurement limit.
  • the optical density per 1 ⁇ m of the thickness can be determined as follows.
  • the sample is formed in a film form on a transparent substrate for transmission measurement. While measuring the optical density of this film-like sample with a transmission densitometer, measuring the film thickness using a stylus type surface shape measuring instrument, etc., and dividing the optical density value of the obtained sample by the film thickness, The optical density per 1 ⁇ m thickness can be determined.
  • the optical density of the film-like sample is about 4.0 or less because it can prevent a decrease in measurement accuracy.
  • the volume resistivity of the black film needs to be 10 11 ⁇ ⁇ cm or more. This is because, in a COA type or BOA type liquid crystal display element or a self-luminous display device, the element driving wiring is brought into contact with the black matrix or the light shielding wall or directly on the black matrix or the light shielding wall. Since the structure that provides the mainstream is becoming the mainstream, if the volume resistivity of the black matrix or the light shielding wall formed using the black film is less than 10 11 ⁇ ⁇ cm, it is easy to cause a short circuit between the wirings. As a result, the TFT element malfunctions.
  • the volume resistivity of the black film is preferably 10 12 ⁇ ⁇ cm or more, and more preferably 10 13 ⁇ ⁇ cm or more. The higher the volume resistivity of the black film, the better.
  • the upper limit is not particularly limited, but it is usually 10 18 ⁇ ⁇ cm or less.
  • the volume resistivity can be measured by using a commercially available volume resistivity meter, for example, by a four-probe method.
  • the relative dielectric constant of the first black film of this embodiment is preferably 15 or less at 1 kHz, more preferably 12 or less, still more preferably 6 or less, and particularly preferably 5 or less. If the black film has a relative dielectric constant of 15 or less, when a black matrix or a light shielding wall is formed using the black film, the influence of parasitic capacitance or the like on a switching signal for driving a liquid crystal element or a light emitting element is reduced. By doing so, it is possible to reduce the disturbance of the image or the like to such an extent that there is almost no visual effect.
  • the black film has a relative dielectric constant of 6 or less, a switching signal for driving a liquid crystal element or a light emitting element can be accurately transmitted when a black matrix or a light shielding wall is formed using the black film. And the image is not disturbed.
  • the lower the relative dielectric constant of the black film the better.
  • the lower limit is not particularly limited, but is usually 2.0 or more at 1 kHz.
  • the relative permittivity is proportional to the signal frequency, when the driving frequency of the switching signal in the liquid crystal element or the light emitting element is slow, the relative permittivity does not necessarily need to be low, and the driving frequency is DC level ( 10 Hz or less), the relative permittivity value itself can be ignored.
  • the measurement of the dielectric constant of a black film can be performed using a commercially available LCR meter.
  • the blackness of the silver-tin alloy fine particles which are black materials or the mixed fine particles of silver-tin alloy fine particles and silver fine particles is higher than that of carbon black which is a conventional black material.
  • High blackness means that less amount is required to obtain the same light shielding property, that is, when the optical density per 1 ⁇ m thickness is 1 or more, the volume fraction of the black material in the film is That means less than before. Since the volume fraction of the black material is low in this way, the black material fine particles are not densely packed in the black film. That is, when fine particles are closely packed, a conductive path is formed because the fine particles are in contact with each other, but this does not happen.
  • the dispersibility of the black material is increased.
  • High dispersibility means that the black material has a low degree of aggregation. Even when the volume fraction of the black material is low as described above, if the dispersibility of the black material is low, the conductive material path may be formed by the aggregation of the black material fine particles, particularly in the form of a chain. There is. However, in the first black film of the present embodiment, since the dispersibility of the black material is high and the average dispersed particle size is small, the black material is uniformly dispersed in the black film, and the conductive property due to chain aggregation. No path is formed.
  • the black material in the present embodiment is subjected to a dispersion treatment using a dispersant or a dispersion aid so that the dispersed particle size in the black film is reduced. Reduction and particle size distribution index reduction can be easily achieved.
  • the volume fraction of the black material is 2% by volume to 30% by volume,
  • the average dispersed particle diameter of 1 to 200 nm a volume resistivity of 10 11 ⁇ ⁇ cm or more can be obtained, and the optical density per 1 ⁇ m thickness can be made 1 or more.
  • the relative dielectric constant at 1 kHz can be 15 or less.
  • metal fine particles mainly composed of silver and tin are suitably selected.
  • the above-mentioned “mainly composed of silver and tin” means that the metal fine particles contain at least both silver and tin components, and the total content of silver and tin is based on the whole metal fine particles. It means 50 mass% or more. That is, the component and content are defined for the entire metal fine particles, and do not define the component and content of individual particles themselves.
  • metal fine particles nanometer-sized metal fine particles having a particle diameter of about 1 nm to several hundreds of nanometers exhibit various color tones due to absorption of metal surface plasmons.
  • black metal fine particles it is possible to select metal fine particles mainly composed of silver and tin. it can.
  • the X-ray diffraction data of the ⁇ phase is Ag 3 Sn (IDCC 71-0530), and the X-ray diffraction data of the ⁇ phase is It is considered to correspond to Ag 4 Sn (IDCC 29-1151). Therefore, the silver tin alloy fine particles having the structure of orthorhombic ⁇ phase (Ag 3 Sn) or hexagonal ⁇ phase (Ag 4 Sn) satisfy the chemical stability and blackness. can do.
  • silver phase i.e. as having a crystal structure of silver, although a portion of the silver atoms of the silver in the crystal tin atom becomes substituted, silver-tin alloy formula Ag 1-Y Sn in this case
  • Y the range of Y is 0 ⁇ Y ⁇ 0.115, and is represented by the (Ag) phase (space group represented by the following notation: cubic system) in the above-mentioned document.
  • the average primary particle diameter exceeds 200 nm, the range of electron motion on the particle surface widens, so that the localized surface plasmon absorption of the metal decreases and the blackness decreases. Because there is a case to do.
  • the production of silver tin alloy fine particles by appropriately adjusting reaction conditions (for example, the ratio of tin and silver ions, the pH of the reaction solution, the reaction temperature, the reaction time, the amount of reducing agent, etc.), the production of silver tin alloy fine particles
  • reaction conditions for example, the ratio of tin and silver ions, the pH of the reaction solution, the reaction temperature, the reaction time, the amount of reducing agent, etc.
  • the amount of silver fine particles produced including the case where silver fine particles are not substantially produced, that is, the case where only silver tin alloy fine particles are produced
  • the production ratio of silver tin alloy fine particles and silver fine particles are arbitrarily controlled. can do.
  • the synthesis is completed by reaction in the liquid phase, so that the obtained black material composed of the metal fine particles is dispersed in the aqueous liquid phase, as it is or in a simple process. By passing, it can be used as an aqueous dispersion black material dispersion described later.
  • the dispersion medium of the dispersion liquid may be an organic solvent system in consideration of dispersibility between the black material and the resin forming component.
  • a method of once pulverizing mechanically to obtain a powder and then performing a dispersion treatment in an organic solvent using a wet mixer such as a ball mill or a bead mill can be employed. If possible, the dispersion may be changed by a solvent replacement method while maintaining the state of the dispersion.
  • a resin component that cures in a state where the metal fine particles exhibiting black, which is a black material, are uniformly dispersed, and that is suitable for the characteristics required for the formed black film should be selected. That's fine.
  • this resin component various kinds of ionizing radiation curable resins, thermosetting resins, thermoplastic resins and the like can be used.
  • the ionizing radiation curable resin means a resin that is cured by crosslinking or polymerization reaction by irradiating, for example, ultraviolet rays or electron beams as electromagnetic waves or charged particle beams, and is a radical polymerization type acrylic.
  • resins include unsaturated resins, unsaturated polyester resins, cationic polymerization type epoxy resins, vinyl ether resins, oxetanes, and glycidyl ethers.
  • the acrylic resins include polyester (meth) acrylate resins, epoxy (meth) acrylate resins, urethane (meth) acrylate resins, polyol (meth) acrylate resins, silicone (meth) acrylate resins, and the like. be able to.
  • (meth) acrylate” means “acrylate or methacrylate”. The same applies hereinafter.
  • thermosetting resin examples include phenol resin, phenol-formalin resin, urea resin, urea-formalin resin, melamine resin, polyester-melamine resin, melamine-formalin resin, alkyd resin, epoxy resin, epoxy-melamine resin, Unsaturated polyester resin, polyimide resin, acrylic resin, polysiloxane resin, polyurethane resin, general-purpose two-component curable acrylic resin (acrylic polyol cured product) and the like can be exemplified. Further, as the thermoplastic resin, polyester resin Alkyd resin, polyurethane, polyvinyl pyrrolidone, polyvinyl alcohol and the like are preferably used.
  • the first black film of the present embodiment is a black matrix or the like
  • an alkali-soluble resin is selected as a resin forming component that is a raw material of the resin component, and a resin formed using this resin forming component is selected. It is preferable to use a resin component.
  • the relative dielectric constant of the resin (organic material) is generally low, there is almost no limiting factor in selecting the resin component for setting the relative dielectric constant of the black film to 15 or less. Since some resins have a relative dielectric constant exceeding 10 depending on the composition, etc., attention may be required.
  • the 1st black film of this embodiment is obtained by forming a film body by various well-known coating methods using the below-mentioned black resin composition.
  • the black film is formed by laminating the black resin composition on one main surface of the substrate by various coating methods such as roll coating, spin coating, dip coating, spray coating, and bar coating. It can be easily obtained by forming (coating) to form a coating film, removing the solvent from the coating film by volatilization or the like, and performing a curing treatment if necessary.
  • This curing process is usually a step of reacting a resin-forming component in the coating film by polymerization or the like to form a resin component.
  • an ionizing radiation curable resin is used as the resin-forming component
  • ultraviolet rays, electron beams examples include irradiation with radiation such as X-rays (heat treatment may be performed as necessary after radiation irradiation), and a thermally reactive resin such as a thermoplastic resin raw material to which a thermal polymerization catalyst is added as a resin forming component.
  • heat processing is mentioned.
  • the radiation dose is set to an amount sufficient for the ionizing radiation curable resin to be sufficiently cured, but is usually set to 20 mJ / cm 2 or more and 1000 mJ / cm 2 or less.
  • the temperature of the heat treatment is not particularly limited as long as the heat-reactive resin is sufficiently cured and the resin itself is not denatured or deformed and the substrate can withstand, but for example, 80 ° C. in an air atmosphere.
  • An example of the heat treatment is about 3 to 120 minutes at a temperature in the range of 300 to 300 ° C.
  • the curing process is a step of removing the solvent from the resin component in the coating film, and heating under atmospheric pressure or reduced pressure. Processing. In this case, since the resin component cured by removing the solvent may be swollen and dissolved again by exposure to the same solvent, it is preferable to remove the solvent completely by tightening the heat treatment conditions. .
  • the resin component when an ionizing radiation curable resin is used as the resin component, the resin component may be completely cured by irradiation with radiation such as ultraviolet rays, electron beams, and X-rays after the solvent is removed, and further by heat treatment.
  • radiation such as ultraviolet rays, electron beams, and X-rays
  • the curing reaction may be completed by heat treatment after removing the solvent.
  • the black material dispersion liquid of the present embodiment (hereinafter sometimes simply referred to as “dispersion liquid”) is a dispersion liquid in which the black material of the present embodiment described above is dispersed in a dispersion medium.
  • the average dispersed particle size of the black material is 1 nm or more and 200 nm or less, and the particle size distribution index D90% in the dispersion medium is 600 nm or less.
  • the dispersion medium basically contains one or more of water, an organic solvent, and a resin forming component.
  • the organic solvent include alcohols such as methanol, ethanol, 2-propanol, butanol, octanol; ethyl acetate, butyl acetate, ethyl lactate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ⁇ -butyrolactone Esters such as diethyl ether, ethylene glycol monomethyl ether (methyl cellosolve), ethylene glycol monoethyl ether (ethyl cellosolve), ethylene glycol monobutyl ether (butyl cellosolve), ethers such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether; acetone, Methyl ethyl ketone, methyl isobutyl ketone, acetylacetone
  • the water content in the dispersion when the organic solvent is used is preferably 5% by mass or less, more preferably 3% by mass or less, and still more preferably 2% by mass or less.
  • the water content of the dispersion exceeds 5% by mass, the dispersion is easily separated from the resin component or the resin-forming component when the dispersion in which the black material is dispersed is mixed with the non-aqueous resin component or the resin-forming component. Therefore, it may be difficult to obtain a stable mixture (black resin composition). That is, by setting the water content of the dispersion to 5% by mass or less, it is possible to appropriately select a variety of non-aqueous photosensitive resins that meet desired exposure, development conditions, film properties, and the like. There are no restrictions on the dispersion or coating film, and the degree of freedom in designing these can be expanded.
  • the dispersant is a polymer having a completely different structure from the black material for ensuring the dispersion stability of the black material
  • the dispersion aid is a pigment derivative for enhancing the dispersibility of the black material.
  • a random copolymer and a comb polymer are preferable in consideration of compatibility with an ionizing radiation curable resin, a thermosetting resin, and a thermoplastic resin used as a resin, and compatibility with an organic solvent.
  • the black material dispersion of this embodiment is a dispersion in which the black material of this embodiment is dispersed in a dispersion medium, and the “other components” are added as necessary.
  • the average dispersed particle size of the black material in the dispersion liquid needs to be 1 nm or more and 200 nm or less. That is, since the average primary particle diameter of the suitable black material used in this embodiment is 1 nm or more, it is difficult for the black material fine particles having an average dispersed particle diameter of less than 1 nm to exist.
  • the particle size distribution index D90% (cumulative 90% diameter) of the black material in the dispersion needs to be 600 nm or less.
  • the particle diameter exceeds 600 nm, the dispersion of the particle diameter becomes too large, and it becomes difficult for the contained coarse particles to maintain a stable dispersion state in the dispersion liquid.
  • the particle size distribution index D90% in the dispersion is more preferably 500 nm or less.
  • the lower limit value of D90% is not particularly defined, but since the lower limit value of the average particle diameter of the black material is 1 nm, it is difficult to make D90% less than 5 nm in the actual dispersion process.
  • the particle size distribution of the dispersion was measured using a particle size distribution measuring apparatus by dynamic light scattering method, and the volume average particle size obtained by arithmetic average from the obtained distribution result.
  • (MV value) may be the average dispersed particle size.
  • the particle size distribution index D90% can be obtained as a particle size (cumulative 90% diameter) corresponding to a cumulative value of 90% when the particle size is represented by a cumulative distribution (volume basis). Further, the average dispersed particle size and the particle size distribution index in the black resin composition described later can also be obtained by the same measurement method.
  • the content of the black material in this dispersion is preferably 1% by mass or more and 80% by mass or less, more preferably 5% by mass or more and 50% by mass or less, and further preferably 10% by mass or more and 40% by mass or less.
  • the content of the black material is 1% by mass or more and 80% by mass or less, the black material can take a good dispersion state in the dispersion.
  • the content of the black material is less than 1% by mass, the dispersion medium becomes excessive, and when the black film is formed using this dispersion, it is difficult to obtain the required black film due to the influence of the dispersion medium.
  • the cost for removing the dispersion medium may be high.
  • the content rate of the black material exceeds 80% by mass, the concentration of the black material becomes too high to be in a paste state, and the characteristics as the dispersion may be lost.
  • the black material dispersion of this embodiment can be prepared by mixing and dispersing the black material and, if necessary, components such as a dispersant and a dispersion aid in addition to the dispersion medium.
  • the mixing / dispersing method may be performed by dispersing a mixed liquid obtained by mixing a black material or a resin forming component by selecting a known dispersing machine such as an ultrasonic dispersing machine, a paint shaker, a ball mill, a bead mill, or an Eiger mill. It is preferable to use a bead mill from the viewpoint of improving the properties.
  • a plurality of dispersion methods may be used in combination.
  • the average dispersed particle size of the black material is 1 nm or more and 200 nm or less. That is, since the average primary particle diameter of the suitable black material used in this embodiment is 1 nm or more, it is difficult for the black material fine particles having an average dispersed particle diameter of less than 1 nm to exist. On the other hand, when the average dispersed particle diameter exceeds 200 nm, a conductive path due to aggregation of the black material fine particles is likely to occur in the black film formed using the black resin composition. In addition, when the black material fine particles are significantly aggregated, the light shielding property is also lowered.
  • the particle size distribution index D90% of the black material in the black resin composition is 600 nm or less.
  • the particle size distribution index D90% in the black resin composition is preferably 500 nm or less.
  • the lower limit value of D90% is not particularly defined, but since the lower limit value of the average particle diameter of the black material is 1 nm, it is difficult to make D90% less than 5 nm in the actual dispersion process.
  • index D90% it can obtain
  • the total content of the resin component and the resin-forming component is preferably 5% by mass or more and 70% by mass or less, and preferably 10% by mass or more and 50% by mass. More preferably, it is as follows.
  • the total content of the resin component and the resin-forming component exceeds 70% by mass, the black material existing in the unit volume of the resin component in the black film is insufficient when the black film is formed using the black resin composition. In some cases, sufficient light shielding properties may not be ensured.
  • the total content of the resin component and the resin forming component is less than 5% by mass, a uniform film body is not formed when a black film is formed using the present black resin composition, and the required film thickness is not formed. In some cases, a preferable shape as a black film is not formed.
  • the main components for constituting the black resin composition are the following five types [A] to [E]. Note that [B] and [E] are different.
  • [A] Black material [B] Black material dispersion medium
  • the black resin composition is mainly composed of a combination of these five components, and the combinations are as follows (1) to (7).
  • components other than [A] to [E] that can be added as necessary, that is, dispersants, dispersion aids, and surface treatment agents are omitted here.
  • [A] + [C] This black resin composition is a two-component system that is a minimum combination, and can be regarded as a dispersion of a black material in a liquid resin-forming component. In this case, [C] needs to be liquid.
  • [A] + [B] + [C] This black resin composition is a three-component system, and can be regarded as a mixture of the “black material dispersion” and a resin-forming component.
  • [C] needs to be liquid, but when [C] is soluble in [B], [C] may be solid.
  • [A] + [C] + [E] This black resin composition is a three-component system and can be regarded as a black material dispersed in a resin-forming component dissolved in a solvent. Since [C] is dissolved in [E], it may be liquid or solid.
  • [A] + [D] + [E] This black resin composition is a three-component system, and it can be considered that a black material is dispersed in a resin component dissolved in a solvent. Since [D] is a solid, [E] is indispensable as long as [D] is present.
  • black material [A] black material dispersion medium [B], resin forming component [C], resin component [D], resin forming component or resin component solvent [E], black material, black material dispersion Since the medium and the resin component are described above, the resin-forming component, the resin-forming component, or the solvent of the resin component will be described here.
  • the resin forming component is a component for forming the resin component in the black film, and usually includes a resin component monomer, oligomer or prepolymer. That is, as the resin component, various types of ionizing radiation curable resins, thermosetting resins, thermoplastic resins, and the like can be used, and therefore at least one of monomers, oligomers, and prepolymers of these resins is included.
  • the ionizing radiation polymerizable monomer (monomer) that is the resin forming component is a polyfunctional compound that is a polymerizable monomer having a radical polymerizable functional group in the molecule
  • (Meth) acrylates are preferred, specifically ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) ) Acrylate, caprolactone-modified dipentaerythritol hexa (meth) acrylate, and the like.
  • Examples of the monomer having a cationic polymerizable functional group include alicyclic epoxides such as 3,4-epoxycyclohexenylmethyl-3 ′, 4′-epoxycyclohexenecarboxylate, and glycidyl ethers such as bisphenol A diglycidyl ether. , Vinyl ethers such as 4-hydroxybutyl vinyl ether, and oxetanes such as 3-ethyl-3-hydroxymethyl oxetane. These ionizing radiation polymerizable monomers may be used alone or in combination of two or more, or may be used in combination with the ionizing radiation polymerizable prepolymer.
  • Examples of the ionizing radiation-polymerizable prepolymer include polyester (meth) acrylate, epoxy (meth) acrylate, urethane (meth) acrylate, polyol (meth) acrylate, and silicone (meth) acrylate. Cationic polymerization in a molecule such as a polymerizable oligomer having a radical polymerizable functional group in a molecule such as a polyester or unsaturated polyester, or an epoxy resin such as a novolac epoxy resin prepolymer or an aromatic vinyl ether resin prepolymer And polymerizable oligomers having a functional functional group. These ionizing radiation polymerizable prepolymers may be used singly or in combination of two or more.
  • thermosetting resins such as phenol resin, phenol-formalin resin, urea resin, urea-formalin resin, melamine resin, polyester-melamine resin, melamine-formalin resin, alkyd resin, epoxy resin, epoxy-
  • melamine resin unsaturated polyester resin, polyimide resin, acrylic resin, polysiloxane resin, polyurethane resin, general-purpose two-component curable acrylic resin (acrylic polyol cured product), etc.
  • these resin components are thermoset. Examples thereof include a raw material compound for forming a polymerizable resin, a monomer, an oligomer, and a prepolymer of a polymerizable resin.
  • the resin forming component is a raw material for forming these thermoplastic resins.
  • examples thereof include compounds, monomers, oligomers and prepolymers of polymerizable resins.
  • a reactant, a reaction initiator, a polymerization agent, a polymerization initiator, and the like, which are added to form a resin from these raw material compounds, polymerizable resin monomers, oligomers and prepolymers, are included in the resin forming component. Also good.
  • the said photoinitiator is a compound which can generate the radical which superposes
  • oxime derivatives oxime compounds
  • the said photoinitiator may be used individually by 1 type, and may use 2 or more types together.
  • Examples of the compound having one or more ethylenically unsaturated bonds in the molecule include unsaturated carboxylic acids such as (meth) acrylic acid, crotonic acid, isocrotonic acid, maleic acid, itaconic acid, citraconic acid, and alkyls thereof. Examples thereof include esters, (meth) acrylonitrile, (meth) acrylamide, and styrene. Examples of the compound having two or more ethylenically unsaturated bonds in the molecule include esters of unsaturated carboxylic acids and polyhydroxy compounds, (meth) acryloyloxy group-containing phosphates, and hydroxy (meth) acrylates.
  • unsaturated carboxylic acids such as (meth) acrylic acid, crotonic acid, isocrotonic acid, maleic acid, itaconic acid, citraconic acid, and alkyls thereof. Examples thereof include esters, (meth) acrylonitrile, (meth) acrylamide, and
  • Examples include urethane (meth) acrylates of a compound and a polyisocyanate compound, and epoxy (meth) acrylates of a (meth) acrylic acid or hydroxy (meth) acrylate compound and a polyepoxy compound.
  • the resin-forming component or the solvent for the resin component (hereinafter sometimes referred to as “resin solvent”) is a liquid in which the resin-forming component or the resin component is highly soluble. It is selected from one type or two or more types.
  • resin solvent in addition to the high solubility of the resin-forming component or resin component, the dispersibility of the black material is high, the compatibility with the black material dispersion is high, and when mixed with the black material dispersion In addition, it is necessary to satisfy the condition that the dispersibility of the black material and the solubility of the resin component and the resin forming component do not decrease.
  • the black resin composition is obtained by mixing the two.
  • phase separation, aggregation and sedimentation of the black material, precipitation of the resin-forming component or resin component, etc. occur, and it is not preferable because a good black resin composition cannot be obtained.
  • the same or similar solvent can be selected as the resin solvent and the black material dispersion because such problems can be avoided.
  • the organic solvent used for the above-mentioned black material dispersion liquid can be used similarly.
  • the black resin composition it is preferable to use a dispersant and / or a dispersion aid together in order to improve the dispersibility and dispersion stability of the black material, as with the black material dispersion.
  • a dispersant and / or a dispersion aid it is particularly preferable to use a polymer dispersant as the dispersant because the dispersion stability over time is excellent. Since the dispersant and the dispersion aid are the same as those described in the black material dispersion, the details are omitted.
  • the black material dispersion of the present embodiment when a dispersion containing a dispersant and / or a dispersion aid is selected as the black material dispersion of the present embodiment, and this black material dispersion is used as a raw material for the black resin composition,
  • the dispersants and dispersion aids already contained in may be used as they are.
  • the dispersant or dispersion aid is a substance that modifies the surface of the black material so that the surface of the black material has an affinity for the dispersion medium or solvent. This is because if the properties do not change, it is not necessary to treat with another type of dispersant or dispersion aid.
  • a plurality of dispersion methods may be used in combination.
  • the black material dispersion and the solution in which the resin-forming components are dissolved are sufficiently mixed and stirred without performing the above-described dispersion treatment method when producing the black resin composition. There are cases where it may be sufficient.
  • the base material with a black film of the present embodiment is configured by providing the first black film of the present embodiment described above on a base material.
  • the layer formed as described above using the above-described black resin composition on a light-transmitting substrate is prepared by patterning as necessary.
  • the substrate is not particularly limited, and examples thereof include a glass substrate and a plastic substrate (organic polymer substrate). Moreover, as the shape, a flat plate, a film form, a sheet form, etc. are mentioned. Moreover, as said plastic base material, a plastic sheet, a plastic film, etc. are suitable.
  • the base material with a black film of the present embodiment can be suitably used for producing a color filter as a black matrix substrate provided with a black matrix (light-shielding film).
  • the film thickness of the black film is preferably 0.2 ⁇ m or more and 5.0 ⁇ m or less, and particularly preferably 0.2 ⁇ m or more and 4.0 ⁇ m or less. Further, since the first black film of the present embodiment is used as the black film in the black matrix substrate, even a thin film has a high optical density.
  • the first black film of the present embodiment can be suitably used in various image display devices.
  • the image display device include a self-luminous display device such as a plasma display display device and an EL display device, a CRT display device, a liquid crystal display device, and the like.
  • the effect of the black film in the form is remarkably exhibited.
  • the liquid crystal display device include STN, TN, VA, IPS, OCS, and R-OCB.
  • the thickness of the black matrix can be reduced because the blackness is high.
  • the liquid crystal display device provided with this color filter does not cause cell gap unevenness between the color filter and the substrate, and display defects such as color unevenness. Occurrence is improved.
  • the volume resistivity is high, even when the black matrix and the pixel driving wiring are in contact with each other, such as a COA type or BOA type liquid crystal display element or a self-luminous display device, an element due to a short circuit of the wiring or the like The drive failure is not caused.
  • the second black film having infrared transparency of the present embodiment comprises a black material and a resin component, and the average dispersed particle size in the film of the black material is 1 nm or more and 100 nm or less, and the thickness at a wavelength of 560 nm.
  • the ratio (OD950 / OD560) of the optical density (OD560) based on the transmittance at a wavelength of 560 nm and the optical density based on the transmittance at a wavelength of 950 nm (OD950) is less than 40% transmittance (T560) per 1 ⁇ m.
  • optical density based on transmittance may be simply referred to as “optical density”.
  • the second black film of this embodiment also has sufficient light-shielding properties and high volume resistivity similar to the first black film.
  • the wavelength range of visible light is 380 nm or more and less than 800 nm based on the description of JIS-Z8120 “Short wavelength limit is 360 to 400 nm, Long wavelength limit is 760 to 830 nm”.
  • light with a wavelength of 800 nm to 1 mm is infrared
  • light with a wavelength of 800 nm to 2500 nm is near infrared.
  • the “optical density” is represented by the above formula (1) when the transmittance T (%) is used.
  • the “infrared transparent black film” in the present embodiment means a film that transmits 3.0% or more of the infrared light.
  • the ratio (OD 950 / OD 560 ) of the optical density (OD 560 ) at a wavelength of 560 nm to the optical density (OD 950 ) at a wavelength of 950 nm is 0.35 or less, the wavelength of 950 nm frequently used particularly for a wireless remote controller. Necessary amount of transmitted light can be obtained for this light.
  • OD 950 / OD 560 is preferably 0.32 or less, and more preferably 0.30 or less.
  • the lower limit of OD 950 / OD 560 is about 0.1.
  • the ratio (OD NIR / OD) between OD 560 and the optical density (OD NIR ) at each wavelength in the near infrared (NIR) wavelength region having a wavelength of 800 nm to 2500 nm. 560 ) is preferably 0.40 or less. If OD NIR / OD 560 is 0.40 or less, it has sufficient light intensity for various near-infrared lasers for industrial use, infrared rays for black matrix pattern alignment, etc. while blocking visible light. Therefore, it can be suitably used as an infrared transmissive black film. OD NIR / OD 560 is more preferably 0.37 or less, and further preferably 0.35 or less. The lower limit of OD NIR / OD 560 is about 0.01.
  • the volume fraction of the black material is preferably 1.0% by volume to 25% by volume.
  • the volume fraction within this range, it is possible to secure a sufficient light shielding property in the visible light region when a black film is formed, and to obtain a high transmittance for light in the near infrared region or more. That is, when the volume fraction of the black material is less than 1.0% by volume, the black material is too small, and the light blocking property in the visible light region may be insufficient.
  • the volume fraction of the black material exceeds 25% by volume, the infrared transmitting black film has a metallic luster, so that the transmittance of light in the near infrared region or more may be lowered.
  • the volume fraction of the black material is more preferably 2.0% by volume to 20% by volume, and even more preferably 2.0% by volume to 15% by volume.
  • the volume fraction of the black material is determined from the density of each component constituting the infrared transmitting black film and the weight of each component added when preparing the paint. Can be obtained by calculating the volume of.
  • the resin component since the resin component is volatilized by decomposition and oxidation at a relatively low temperature, the black material is stable up to a high temperature because it is a metal.
  • the black film is determined from the change in the weight of the black film by thermogravimetric analysis (TG).
  • TG thermogravimetric analysis
  • the weight ratio between the resin component and the black material can be obtained.
  • the specific gravity of both the resin component and the black material can be determined by component analysis, so the specific gravity of both substances can be obtained.
  • the specific gravity of each component the volume fraction of the black material in the second black film of the present embodiment may be obtained.
  • the black material in the present embodiment has light transmittance in the infrared region, but the average primary particle diameter of the metal fine particles dispersed in the resin as in the prior art is in the range of 1 nm to 200 nm.
  • the average primary particle diameter of the metal fine particles dispersed in the resin as in the prior art is in the range of 1 nm to 200 nm.
  • Rayleigh scattering and Mie scattering occurring in the infrared region cannot be suppressed, and as a result, sufficient infrared transmission characteristics cannot be obtained.
  • the average dispersed particle diameter in the black film is 100 nm or less as in the present embodiment and Rayleigh scattering and Mie scattering are suppressed, sufficient transmission characteristics can be obtained even in the infrared region.
  • the average dispersed particle diameter of dispersed fine particles is preferably 20 nm or less.
  • the allowable particle diameter is increased in the case of infrared rays having a longer wavelength than visible light, and the infrared rays in the present embodiment
  • the transmittance does not require the same high transparency as the optical element, and some scattering is allowed, so that the average dispersed particle size can be increased to 100 nm.
  • the average dispersed particle diameter in the black material film in the present embodiment is 1 nm or more. The reason is that when the average particle diameter is less than 1 nm, the crystallinity of the particles is lowered, so that the absorption state of visible light becomes unstable and sufficient blackness may not be obtained.
  • the average dispersed particle size of the black material in the infrared transmitting black film in the present embodiment is obtained by cutting the obtained infrared transmitting black film into a thin piece in the cross-sectional direction using FIB (focused ion beam) or the like, and using a transmission electron microscope. It can be determined by observing the particles of black material in the flakes using (TEM). That is, a specific number (usually several tens or more) of particles are randomly selected from the TEM photograph, the particle diameter thereof is measured, and the average value thereof is set as the average dispersed particle diameter.
  • TEM focused ion beam
  • metal fine particles mainly composed of silver and tin are suitably selected.
  • the above-mentioned “mainly composed of silver and tin” means that the metal fine particles contain at least both silver and tin components, and the total content of silver and tin is based on the whole metal fine particles. It means 50 mass% or more. That is, the component and content are defined for the entire metal fine particles, and do not define the component and content of individual particles themselves.
  • metal fine particles nanometer-sized metal fine particles having a particle diameter of about 1 nm to several hundreds of nanometers exhibit various color tones due to surface plasmon absorption of the metal.
  • the (wavelength) varies depending on the composition and particle size of the metal fine particles.
  • the composition and particle diameter by adjusting the composition and particle diameter, it is sufficient to select metal fine particles that exhibit black in the visible light region and exhibit a certain level of transparency in the infrared region, and as such black metal fine particles.
  • fine metal particles mainly composed of silver and tin can be selected.
  • the metal fine particles mainly composed of silver and tin As the metal fine particles mainly composed of silver and tin, silver tin alloy fine particles, or mixed fine particles of silver tin alloy fine particles and silver fine particles can be preferably used.
  • the content of the silver component in the silver tin alloy fine particles that is, the ratio of the silver component to the total amount of silver and tin (silver / (Silver + tin): mass%) is preferably 45 mass% or more and 95 mass% or less, more preferably 50 mass% or more and 95 mass% or less, and further preferably 60 mass% or more and 92 mass% or less. It is.
  • the metal fine particles mainly composed of silver and tin are mixed fine particles of silver tin alloy fine particles and silver fine particles
  • the content of silver component in the mixed fine particles of the silver tin alloy fine particles and silver fine particles that is, silver and tin
  • the ratio of the silver component to the total amount is preferably 45 mass% or more and 95 mass% or less, more preferably 50 mass% or more and 95 mass% or less, More preferably, it is 60 mass% or more and 92 mass% or less.
  • the reason why the content of the silver component is limited to the above range is that when the ratio of the silver component is 45% by mass or more and 95% by mass or less, the reflectance of visible light is not increased and the black has sufficient blackness. This is because a film can be obtained and sufficient light shielding properties can be obtained, and the black film also has infrared transmittance.
  • the preferable content range of the silver component is a preferable content range of the silver component in the entire fine particles when a certain amount of the silver tin alloy fine particles or a mixed fine particle of the silver tin alloy fine particles and silver fine particles is taken. This does not indicate a preferable content range of the silver component in each particle.
  • the silver-tin alloy fine particles may include not only those that can be clearly determined as a silver-tin alloy by having a crystal structure of silver-tin alloy, but also those that have a crystal structure of silver.
  • the silver tin alloy having a crystal structure when the silver tin alloy is represented by the chemical formula Ag 1-X Sn X (X is a real number), the range of X is 0.118 ⁇ X ⁇ 0.2285. ⁇ phase and ⁇ phase of 0.237 ⁇ X ⁇ 0.25 are known (according to Binary Alloy Phase Diagram, p. 94-97).
  • the black material composed of the silver-tin alloy fine particles or the mixed fine particles of the silver-tin alloy fine particles and the silver fine particles contains substantially no tin fine particles.
  • substantially free of tin fine particles means that the presence of a substance having a tin crystal structure is not confirmed in the analysis by the X-ray diffraction method.
  • this black material contains tin fine particles, the light shielding property of the black light-shielding film formed using the black material is significantly lowered.
  • a method of dropping a silver compound solution into a tin colloid dispersion and alloying tin and silver, or silver colloid and tin colloid By adding an oxidizing agent or a reducing agent to the dispersion liquid in which silver coexists, silver tin alloy fine particles and silver fine particles can be generated using a method of alloying silver and tin.
  • the reaction conditions for example, the ratio of tin and silver (silver ions), the pH of the reaction solution, the reaction temperature, the reaction time, the type and amount of the oxidizing agent and reducing agent, etc.
  • the surface of the black material in order to uniformly disperse the black material in the resin component or to increase the affinity between the black material and the resin component, it is preferable to treat the surface of the black material with a surface treatment agent or a dispersant.
  • These surface treatment agents and dispersants may be selected from known materials in accordance with the material of the resin component and the method of dispersing the black material in the resin component.
  • the second black film of the present embodiment can be obtained by adjusting the dispersion method and dispersion conditions together with the type of the dispersant and dispersing the black material in the resin component.
  • the dispersant is preferably a polymer dispersant, for example, urethane dispersant, modified polyester dispersant, polycarboxylate, polyalkyl sulfate, polyvinyl pyrrolidone (PVP), polyvinyl alcohol (PVA), polyacrylamide. Etc. can be mentioned.
  • a polymer having a preferable structure can maintain the dispersibility of a black material when a black film is formed by curing a resin forming component (component for forming a resin component) from a black resin composition described later.
  • a random copolymer, a comb-type copolymer, an ABA-type copolymer, a BAB-type copolymer, a polymer having a hydrophilic group at both ends, a polymer having a hydrophilic group at one end, or the like can be selected.
  • a black material in a solvent having high compatibility with a resin component or a resin-compatible component in other words, a resin component, a resin-forming component, a resin component, and a solvent highly compatible with the resin-forming component.
  • random copolymers and comb copolymers are preferred.
  • dispersant examples include EFKA (manufactured by EFKA Chemicals Beebuy (EFKA)), Disperbyk (manufactured by Big Chemie), Disparon (manufactured by Enomoto Kasei Co., Ltd.), SOLPERSE (manufactured by Geneka), and KP (manufactured by Shin-Etsu Chemical). ), Polyflow (manufactured by Kyoeisha Chemical Co., Ltd.) and the like.
  • EFKA manufactured by EFKA Chemicals Beebuy
  • Disperbyk manufactured by Big Chemie
  • Disparon manufactured by Enomoto Kasei Co., Ltd.
  • SOLPERSE manufactured by Geneka
  • KP manufactured by Shin-Etsu Chemical
  • Polyflow manufactured by Kyoeisha Chemical Co., Ltd.
  • examples of the surface treatment agent include coupling agents such as a silane coupling agent and a titanium coupling agent.
  • This black material has high blackness and excellent light-shielding property for visible light and has infrared transmission properties due to the characteristics of the material itself. And the scattering of the infrared rays resulting from particle
  • the acrylic resin is selected from, for example, polymers based on one or more monomers, oligomers, and prepolymers selected from acrylic resin monomers, oligomers, and prepolymers described in the resin component raw materials described later. be able to.
  • polymers include polymethyl (meth) acrylate, polycyclohexyl (meth) acrylate, polyethylene glycol di (meth) acrylate, poly-trimethylolpropane tri (meth) acrylate, and poly-pentaerythritol tetra (meth) acrylate.
  • poly (meth) acrylic acid ester resins is selected from, for example, polymers based on one or more monomers, oligomers, and prepolymers selected from acrylic resin monomers, oligomers, and prepolymers described in the resin component raw materials described later.
  • examples of such polymers include polymethyl (meth) acrylate, polycyclohexyl (meth) acrylate, polyethylene glycol di
  • Epoxy resins include glycerol polyglycidyl ether, pentaerythritol polyglycidyl ether, diglycerol polyglycidyl ether, polyglycerol diglycidyl ether, phenol novolac epoxy resin, cresol novolac epoxy resin, bisphenol epoxy resin, trisphenol.
  • Normethane type epoxy resin glycidyl (meth) acrylate and styrene copolymer epoxy resin
  • glycidyl (meth) acrylate and cyclohexylmaleimide copolymer A polymer epoxy resin, a fluorene-type epoxy resin, etc. can be mentioned.
  • the polyester resin is not limited as long as it is commonly used in paints.
  • polyvalent carboxylic acids such as adipic acid, sebacic acid, and isophthalic acid
  • polyhydric alcohols such as ethylene glycol and trimethylolpropane.
  • the polyurethane resin is not limited as long as it is generally used in paints.
  • a polyurethane resin obtained by reacting an isocyanate group with a polyol to extend a chain is preferable.
  • the polyol include polyester polyol, polyether polyol, and acrylic polyol.
  • an inorganic oxide having a refractive index comparable to that of the resin component is preferable, and silica (silicon dioxide) fine particles are preferably used from the viewpoint of availability and price.
  • silica silicon dioxide
  • fine particles made of a high refractive index material such as zirconia or titania may be used.
  • low refractive index fine particles having fine voids such as nanoporous silica and hollow silica may be used.
  • the fine particles composed of silver tin alloy fine particles and silver fine particles used as the black material in the second black film of the present embodiment are compared with carbon black and titanium black used as the black material in the conventional black film. Since the blackness is high, as described above, the content in the film can be reduced to a range of 1.0 volume% or more and 25 volume% or less. For this reason, even if a substance other than the black material is added, the film formability and the characteristics of the film itself can be maintained, so that such a filler material can be added.
  • the second black film of the present embodiment is formed by forming a black resin composition described later in layers on a substrate.
  • the black resin composition of the present embodiment is also a resin composition including at least the black material of the present embodiment and a resin forming component or a resin component, and includes a black paint or the like.
  • the substrate to be used may be selected according to the usage method and usage form of the black film, and is not particularly limited. For example, in addition to an inorganic substrate such as glass, a substrate having high hardness such as an acrylic substrate or a polycarbonate substrate is used. If used, a structure having an infrared transmitting black film can be obtained.
  • the coating method (coating film forming method) of the black resin composition is not particularly limited, but spin coating, flow coating, spray coating, dip coating, die coating, gravure coating, knife coating. Method, bar coating method, ink jet method and the like.
  • the second black film can be obtained by curing the applied film or removing the solvent by volatilization.
  • the solvent in the coating film is first removed to form a coating dry film (a solid film shape by removing the solvent).
  • a coating dry film a solid film shape by removing the solvent.
  • the monomer, oligomer, and prepolymer of the resin component raw material may be heated at a temperature at which thermal polymerization starts, and when a reaction initiator is added, heat and light corresponding to the reaction initiator are added.
  • Application may be performed. Moreover, you may use both together.
  • a resist material is used as a resin component raw material, and a complex shape is obtained by exposing and developing a coated dry film to obtain a black matrix described later.
  • the black material dispersion and the black resin composition for forming the second black film of the present embodiment can be obtained, for example, as follows.
  • a black material is prepared.
  • the black material the above-described metal fine particles mainly composed of silver and tin are suitable, and in particular, fine particles composed of silver-tin alloy fine particles and silver fine particles can be more suitably used.
  • the black material is a fine particle having a hydrophilic surface, as can be seen from the fact that the metal is a main component and is preferably produced by a liquid phase reaction method of an aqueous reaction system.
  • the amount of the polymer dispersant or the like to be bonded to the black material surface is preferably 5% by mass or more and 30% by mass or less with respect to the total amount of the black material. Further, there are more suitable ranges depending on the composition of the black material, the primary particle diameter, and the composition of the resin component raw material described later in which the black material is dispersed and mixed. The reason for this is that in the case of forming a coating film from a black resin composition formed using this black material, and further forming an infrared transparent black film, the dispersion of the black material in the coating film or in the black film This is because it is necessary to strictly adjust the addition amount of the polymer dispersant or the like with respect to the black material in order to ensure the property.
  • the black material particles may aggregate from a portion where the coating amount of the polymer dispersant or the like is small after the black material is dispersed in the resin component raw material or the solvent. is there.
  • the amount of the polymer dispersant or the like when the amount of the polymer dispersant or the like is excessive, the dispersant itself may be a factor for reducing the dispersibility.
  • an excessive polymer dispersant or the like when a black film is formed by curing the resin forming component, an excessive polymer dispersant or the like may inhibit curing due to polymerization of the resin forming component, and a sufficient film strength may not be obtained.
  • a photoresist or the like is used for the cured resin, the developability is deteriorated in the development step after exposure with light.
  • the black material particles subjected to the surface treatment are dispersed in a resin component raw material or a solvent highly compatible with the resin component raw material. Later, due to the adsorption / desorption equilibrium of the polymer dispersant and the like on the black material particles, the coating of the polymer dispersant and the like on each particle can be made uniform, so that uniform dispersibility of the black material is also ensured. Become.
  • solvent replacement is performed by extracting and dispersing particles coated with the polymer dispersant as described above directly in a non-aqueous solvent in an aqueous or polar solvent.
  • solvent replacement is performed by extracting and dispersing particles coated with the polymer dispersant as described above directly in a non-aqueous solvent in an aqueous or polar solvent.
  • the coating amount of the polymer dispersant or the like becomes smaller than the designed amount. For this reason, problems such as aggregation of the black material particles as described above may occur.
  • the moisture content in the black material surface-treated with the obtained polymer dispersing agent etc. is 2.0 mass% or less with respect to a process particle. This prevents the aggregation of black material particles and the whitening of the resin when forming a coating film from a black resin composition, which will be described later, and further curing the resin-forming component to form an infrared transparent black film. Because. In other words, if the coating film contains both a solvent and moisture that are highly compatible with the resin component material, drying removes the solvent that is highly compatible with the resin component material and the water content relatively increases. When the value exceeds a certain value, the dissolution parameter in the coating film changes greatly, which may cause phenomena such as aggregation of particles and whitening of the resin.
  • the water content of the black resin composition needs to be kept as small as possible, and the water content of the black material is made as small as possible at the time of surface treatment with a polymer dispersant or the like that is most likely to contain water. It is because it is preferable to keep.
  • a method of reducing the water content of the black material subjected to the surface treatment with such a polymer dispersant a method of removing only the solvent, for example, a method of drying the black material particles using an evaporator or the like. It can be used suitably.
  • a method of removing moisture by heating the black material subjected to the surface treatment for a long time using a dryer at 150 ° C. or more there is a method of removing moisture by heating the black material subjected to the surface treatment for a long time using a dryer at 150 ° C. or more.
  • the low molecular dispersant volatilizes or decomposes. This is not preferable because it causes a change in the processing amount of the dispersant and alteration.
  • a black resin composition containing a black material that has been surface-treated with a polymer dispersant or the like and a resin component raw material is prepared.
  • the resin component raw material is liquid and forms the resin component by curing, solvent distillation, etc., and in addition to monomers, oligomers and prepolymers (resin forming components) that form the resin component, What melt
  • the monomers, oligomers, and prepolymers that form the resin component are in liquid form
  • these monomers, oligomers, and prepolymers are directly used as resin component raw materials, and a black material is mixed and dispersed therein to produce a black resin composition.
  • a black material is mixed and dispersed therein to produce a black resin composition.
  • a black material may be mixed and dispersed therein to produce a black resin composition.
  • the black paint may contain the filler material and additives described later.
  • the black material that has been surface-treated with the polymer dispersant or the like may be mixed and dispersed in the resin component raw material in the form of fine particles to form a black resin composition.
  • a black material dispersion liquid (hereinafter sometimes referred to as “dispersion liquid”) in which a black material is dispersed in a solvent highly compatible with the component raw materials, and mixing the dispersion liquid and the resin component raw materials.
  • a black resin composition may be formed.
  • the filler material may be dispersed in advance, or an additive described later may be dissolved.
  • acrylic resin monomers include methyl (meth) acrylate, cyclohexyl (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di ( (Meth) acrylates such as (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and glycerol (meth) acrylate Acrylic esters; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 2-
  • oligomers and prepolymers include polymethyl (meth) acrylate, polycyclohexyl (meth) acrylate, polyethylene glycol di (meth) acrylate, poly-trimethylolpropane tri (meth) acrylate, and poly-pentaerythritol tetra (meth).
  • examples thereof include poly (meth) acrylic acid ester resins such as acrylate.
  • a baking type acrylic resin such as “Acridick” series manufactured by DIC Corporation may be used as “Acridick” series manufactured by DIC Corporation may be used.
  • Epoxy resin monomers, oligomers and prepolymers include glycerol polyglycidyl ether, pentaerythritol polyglycidyl ether, diglycerol polyglycidyl ether, polyglycerol diglycidyl ether, phenol novolac epoxy resin, cresol novolac epoxy resin, bisphenol.
  • Type epoxy resin fluorene type epoxy resin, trishenol methane type epoxy resin, copolymer epoxy resin of glycidyl (meth) acrylate and styrene, copolymer epoxy resin of glycidyl (meth) acrylate, styrene and methyl (meth) acrylate , Prepolymers before cross-linking network such as glycidyl (meth) acrylate and cyclohexylmaleimide copolymer epoxy resin Rukoto can.
  • the resin-forming component has ultraviolet photosensitivity, and as will be described later, a black film having a complicated design and improved design is formed by exposing and developing the coated and dried film. It is preferable in that it can be performed. Moreover, it can also be used as a black resist for forming a black pattern by using a resin-forming component having ultraviolet sensitivity.
  • resin having ultraviolet photosensitivity there are two types of resin having ultraviolet photosensitivity: a negative type (the photosensitive part remains by development) and a positive type (the photosensitive part is removed by development), but the negative type is preferable.
  • the black film or black material of the present embodiment has a light-shielding property against ultraviolet rays, so that the bottom of the film is not sufficiently exposed even in the exposed portion (ultraviolet irradiation portion), and the positive type In this case, since a residual film is likely to be generated, the negative type is preferable to prevent this effect.
  • the reaction initiator may be any substance that initiates / accelerates polymerization of the resin component by generating radicals by heat or light, but examples of the photoreaction initiator include Darocur Series from Ciba Specialty Chemicals. (For example, 1173) and Irgacure series (for example, 651, 184, 908, 2959, OXE01, OXE02, and the like) and the like may be used alone or in combination of two or more.
  • the resin forming component can be treated as a negative resist by providing the resin forming component with photocurability.
  • the solvent used for the resin component raw material and the solvent used for the black material dispersion are not particularly limited as long as the solubility of the resin component (raw material) used and the dispersibility of the black material can be maintained.
  • methanol, ethanol, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monobutyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether acetate, methyl ethyl ketone, and methyl isobutyl A ketone etc. can be mentioned.
  • an infrared transmissive black film is formed by forming the second black film on a base material.
  • a substrate with a film can be obtained.
  • the base material the substrates mentioned in the above-described formation of the black film can be similarly used.
  • the shape include a flat plate, a film shape, and a sheet shape.
  • the second black film having infrared transparency of the present embodiment can be suitably used as a component constituting a display element or the like in the image forming apparatus. That is, the image display device of the present embodiment only needs to have the black film of the present embodiment in the device, and the aspect may include the substrate with the film of the present embodiment in the device. However, it may be other than that.
  • the image forming apparatus include a plasma display display device, an EL display device, a CRT display device, a liquid crystal display device, and the like. Among these, when used in a liquid crystal display device or an EL display device, the effect of the black film of the present embodiment is achieved. Prominently demonstrated.
  • a black paint as a pigment dispersion resist (black resist) for forming a liquid crystal black matrix or a color filter.
  • the 2nd black film of this embodiment formed by this can be used as a black matrix for image display apparatuses, such as a liquid crystal, and a color filter. That is, after forming a coating and drying film using the black paint on a black matrix substrate, a black matrix pattern is formed by exposure and development, and the black matrix pattern is cured by thermosetting to form a permanent film. For example, a black matrix using the infrared transparent black film of this embodiment can be produced. Furthermore, a color filter can be produced by combining this black matrix pattern and a color filter element / pattern.
  • the second black film of this embodiment has infrared transparency. Furthermore, in principle, the coated and dried film also has infrared transparency, so that an alignment signal using infrared rays in the wavelength range of 850 to 950 nm can be easily read. Therefore, a COA type or BOA type black matrix can be easily produced.
  • the image display device of the present embodiment includes various types such as an electrode substrate, a polarizing film, a retardation film, a backlight, a spacer, a viewing angle compensation film, an antireflection film, a light diffusion film, and an antiglare film.
  • an electrode substrate a polarizing film
  • a retardation film a backlight
  • a spacer a viewing angle compensation film
  • an antireflection film a light diffusion film
  • an antiglare film an antiglare film.
  • the black film of the present embodiment can be applied to these members as necessary.
  • the content ratio of the silver component in the black material is determined by measuring the green powder powder compact with an electron beam microanalyzer (EPMA: XXA8800, manufactured by JEOL Ltd.) And the content ratio (mass ratio) of tin and silver in the powder was determined by qualitative and quantitative analysis using a wavelength dispersion X-ray spectrometer.
  • the particle size distribution of this dispersion is measured using a particle size distribution measuring apparatus (Microtrac 9340-UPA, manufactured by Nikkiso Co., Ltd.) to which a dynamic light scattering method is applied.
  • the volume average particle diameter (MV value) was obtained from the distribution result by arithmetic average, and the value was defined as the average dispersed particle diameter.
  • a cumulative particle size distribution (volume basis) was calculated from the measured particle size distribution, and a particle diameter (cumulative 90% diameter) corresponding to a cumulative value of 90% was obtained and used as a particle size distribution index D90%.
  • the prepared black film sample was cut into thin sections by cutting in the cross-sectional direction using FIB (focused ion beam), and the cut surface was observed with a transmission electron microscope (TEM: JEM-2010, manufactured by JEOL Ltd.). Since 100 arbitrary particles were selected from the observation field and the particle shape was substantially spherical, each particle image was approximated by a circle having the same area, and the diameter of the circle was defined as the particle diameter of the particle.
  • FIB focused ion beam
  • the cumulative distribution of the particle diameter is obtained from the obtained results, and the particle diameter (median diameter) corresponding to the cumulative value of 50% is defined as the average particle diameter of the black material in the film, the particle diameter corresponding to the cumulative value of 90% (cumulative 90%
  • the particle size distribution index D was 90%. Note that the cumulative values in the black film are all based on the number.
  • a glass substrate having an ITO film formed on the surface by sputtering is selected as the film formation substrate, and the dielectric constant of the black film formed on this substrate is insulated with an LCR meter (LCR meter 4284A, manufactured by Agilent).
  • LCR meter 4284A manufactured by Agilent
  • the volume resistivity was measured using an ohmmeter (ultra-high resistance / microammeter R8340A, manufactured by ADC Corporation).
  • the relative dielectric constant was measured at 1 kHz ⁇ 1 V, and the volume resistivity was measured with DC 5 V applied.
  • -Optical density of black film- A glass substrate with an ITO film formed on the surface by sputtering is selected as the film formation substrate, and a transmittance concentration meter (RT-120, TECHKON) is selected using a glass substrate with a black film formed on this substrate as a black film.
  • the optical density of the black film (OD value: Optical Density) was obtained by measuring the transmittance using a glass substrate and using the measured value of the glass substrate alone (without film) as a reference value. Next, the film thickness of the black film was measured using a stylus type surface shape measuring instrument (P-10, manufactured by KLA Tencor), and the OD value of the black film obtained by the above method was measured in film thickness ( ⁇ m unit). ) To obtain an optical density per 1 ⁇ m.
  • Example A1 Preparation of black film- Silver tin colloid liquid (mixed fine particle dispersion of silver tin alloy fine particles and silver fine particles, manufactured by Sumitomo Osaka Cement Co., Ltd., solid content: 30% by mass, average dispersed particle size: 10 nm, particle size distribution index D 90%: 40 nm, containing silver component Resist (dispersion medium: PGMEA, solid content: 1% by mass) with polyfunctional acrylate as a resin-forming component in an amount: 91% by mass, dispersant type: polyurethane / random copolymer, dispersant addition amount: 15 parts by mass) ) was added so that the solid content volume ratio (silver tin colloid: resist) was 3:97 and dispersed by ultrasonic treatment to obtain a black paint.
  • Resist disersion medium: PGMEA, solid content: 1% by mass
  • polyfunctional acrylate as a resin-forming component in an amount: 91% by mass
  • the said solid content volume ratio is a preparation ratio. Subsequently, when the particle size distribution of the black paint was measured by the above method, the average dispersed particle size was 13 nm, and the particle size distribution index D90% was 48 nm.
  • the prepared black paint was applied using a spin coater and vacuum dried for 1 minute. Then, it prebaked at 120 degreeC on the hotplate for 30 second, and obtained the coating film with a dry film thickness of 0.5 micrometer. Thereafter, the entire surface was exposed from the coating film side using 3 kW high-pressure mercury under an exposure condition of 100 mJ / cm 2 . Next, after developing with a 0.1% aqueous solution of potassium hydroxide, development was stopped with pure water, and the glass substrate was post-baked at 200 ° C. for 1 hour to obtain a glass substrate with a black film. The black film thickness at this stage was 0.5 ⁇ m.
  • Example A2 In the production of the black film of Example A1, a substrate with a black film was produced in the same manner as in Example A1, except that a resist was added so that the solid content volume ratio was 7:93, and the same evaluation was performed. It was. The results are summarized in Table 1.
  • Example A3 In the production of the black film of Example A1, a substrate with a black film was produced in the same manner as in Example A1, except that a resist was added so that the solid content volume ratio was 20:80, and the same evaluation was performed. It was. The results are summarized in Table 1.
  • Example A4 In the production of the black film of Example 1, a substrate with a black film was produced in the same manner as in Example 1 except that a resist was added so that the solid content volume ratio was 23:77, and the same evaluation was performed. It was. The results are summarized in Table 1.
  • Example A5 In the production of the black film of Example A1, a substrate with a black film was produced in the same manner as in Example A1, except that a resist was added so that the solid content volume ratio was 25:75, and the same evaluation was performed. It was. The results are summarized in Table 1. In this example, the value was not stable in the measurement of the relative dielectric constant, and the measurement could not be performed. This is not because the volume resistivity of the film material (bulk body) is maintained in a high state, but because the volume fraction of the black material is high, a local conductive path portion is formed in the film. It is thought. This is considered to be the same for Example A5.
  • Example A6 In the production of the black film of Example A1, a substrate with a black film was produced in the same manner as in Example A1, except that a resist was added so that the solid content volume ratio was 30:70, and the same evaluation was performed. It was. The results are summarized in Table 1.
  • Example A7 In production of the black film of Example A1, a silver tin colloid liquid (a mixed fine particle dispersion of silver tin alloy fine particles and silver fine particles, manufactured by Sumitomo Osaka Cement Co., Ltd., solid content: 30% by mass, average dispersed particle size: 180 nm, particle size distribution index D 90%: 500 nm, silver component content: 91% by mass, dispersant type: polyurethane / random copolymer, dispersant addition amount: 15 parts by mass) Then, a base material with a black film was prepared, and the same evaluation was performed. The results are summarized in Table 1.
  • Example A8 In production of the black film of Example A1, a silver tin colloid liquid (a mixed fine particle dispersion of silver tin alloy fine particles and silver fine particles, manufactured by Sumitomo Osaka Cement Co., Ltd., solid content: 30% by mass, average dispersed particle size: 10 nm, particle size distribution index D90%: 40 nm, silver component content: 60% by mass, dispersant type: polyurethane / random copolymer, dispersant addition amount: 15 parts by mass) Then, a base material with a black film was prepared, and the same evaluation was performed. The results are summarized in Table 1.
  • Comparative Example A1 In the production of the black film of Example A1, carbon black (trade name “HA3”, manufactured by Tokai Carbon Co., Ltd.) was used instead of the silver-tin colloid solution, and the volume ratio of carbon black to the resin-forming component was the same as in Example 1. The resist was added so as to be 10:90, and dispersion treatment was performed in the same manner as in Example A1, thereby obtaining a carbon black dispersed paint. In Comparative Example A1, no dispersant is used. Using the carbon black-dispersed paint, a substrate with a black film was prepared in the same manner as in Example A1, and the same evaluation was performed. The results are summarized in Table 1. In addition, since the black film in this comparative example has a low volume resistivity and exhibits conductivity, the relative dielectric constant could not be measured. The same applies to Comparative Examples A4, A5, and A6.
  • Example A2 In production of the black film of Example A1, a silver tin colloid liquid (a mixed fine particle dispersion of silver tin alloy fine particles and silver fine particles, manufactured by Sumitomo Osaka Cement Co., Ltd., solid content: 30% by mass, average dispersed particle size: 220 nm, particle size distribution index D 90%: 550 nm, silver component content: 91% by mass, dispersant type: polyurethane / random copolymer, dispersant addition amount: 15 parts by mass) Then, a base material with a black film was prepared, and the same evaluation was performed. The results are summarized in Table 1.
  • Example A3 In preparation of the black film of Example A1, a silver tin colloid liquid (a mixed fine particle dispersion of silver tin alloy fine particles and silver fine particles, manufactured by Sumitomo Osaka Cement Co., Ltd., solid content: 30% by mass, average dispersed particle size: 170 nm, particle size distribution index D 90%: 650 nm, silver component content: 91% by mass, dispersant type: polyurethane-based random copolymer, dispersant addition amount: 15 parts by mass), the same as in Example A1 Then, a substrate with a black film was prepared and evaluated in the same manner. The results are summarized in Table 1.
  • Example A4 In the production of the black film of Example A1, a substrate with a black film was produced in the same manner as in Example A1, except that a resist was added so that the solid content volume ratio was 30:70, and the same evaluation was performed. It was. The results are summarized in Table 1.
  • Example A5 In the production of the black film of Example A1, a substrate with a black film was produced in the same manner as in Example A1, except that a resist was added so that the solid content volume ratio was 35:65, and the same evaluation was performed. It was. The results are summarized in Table 1.
  • this colloidal solution was stirred for 60 minutes while being kept at 60 ° C., and then irradiated with ultrasonic waves for 5 minutes.
  • this colloidal solution was concentrated by centrifugation to obtain a liquid A having a solid content of 15% by mass.
  • Example A7 In preparation of the black film of Example A1, a silver tin colloid liquid (a mixed fine particle dispersion of silver tin alloy fine particles and silver fine particles, manufactured by Sumitomo Osaka Cement Co., Ltd., solid content: 30% by mass, average dispersed particle size: 10 nm, particle size distribution index D 90%: 40 nm, silver component content: 91% by mass, dispersant type: polyurethane-based random copolymer, dispersant addition amount: 3 parts by mass) Then, a substrate with a black film was prepared and evaluated in the same manner. The results are summarized in Table 1.
  • Example A8 In preparation of the black film of Example A1, a silver tin colloid liquid (a mixed fine particle dispersion of silver tin alloy fine particles and silver fine particles, manufactured by Sumitomo Osaka Cement Co., Ltd., solid content: 30% by mass, average dispersed particle size: 10 nm, particle size distribution index D90%: 40 nm, silver component content: 91% by mass, dispersant type: polyurethane / random copolymer, dispersant addition amount: 70 parts by mass) Then, a substrate with a black film was prepared and evaluated in the same manner. The results are summarized in Table 1.
  • Example A9 In preparation of the black film of Example A1, a silver tin colloid liquid (a mixed fine particle dispersion of silver tin alloy fine particles and silver fine particles, manufactured by Sumitomo Osaka Cement Co., Ltd., solid content: 30% by mass, average dispersed particle size: 10 nm, particle size distribution index D90%: 40 nm, silver component content: 91% by mass, dispersant type: polycarboxylic acid, dispersant addition amount: 70 parts by mass) Then, a base material with a black film was prepared, and the same evaluation was performed. The results are summarized in Table 1.
  • the black film formed by the black paint prepared using the black material dispersion of the present invention has finer particles in the film than the black film shown in the comparative example. It can be seen that the black material fine particles having the same diameter are uniformly dispersed, and the optical density and electric characteristics of the black film are excellent.
  • the color filter using the black film of the present invention as a black matrix exhibited good display characteristics in a liquid crystal display device.
  • each measurement and evaluation method such as the characteristic of a material and a sheet
  • the content ratio of the silver component in the black material is determined by using a green compact powder compact as an electron beam microanalyzer (EPMA, JEOL Ltd., JXA8800 ) And by measuring the content ratio (mass ratio) of tin and silver in the powder by qualitative and quantitative analysis.
  • EPMA electron beam microanalyzer
  • optical density of black film in visible light region The optical density (OD value: Optical Density) of the black film in the visible light region was measured using a transmission densitometer (TECHKON: RT-120) for a glass substrate with a black film, and the glass substrate alone (no film) By using the measured value as a reference value, the OD value of the infrared transmitting black film itself was obtained.
  • the transmittance of the black film is determined by measuring the spectral transmittance of 370 to 2500 nm using a spectrophotometer for the glass substrate with the black film, and using the glass substrate alone (without film) as a reference value for the light at each wavelength of the black film. The transmittance was determined.
  • the spectrophotometer is manufactured by Hitachi, Ltd. U-4100 (measurement wavelength range: 200-2500 nm, detection limit: 0.001%), and Otsuka Electronics MCPC-3700 (depending on the measurement wavelength and measurement light amount). Measurement wavelength range: 300 to 1000 nm, detection limit: 0.000001%) were used in combination.
  • the average dispersed particle size in the black film of the black material was obtained by cutting the obtained black film into a thin piece in the cross-sectional direction using FIB, and using a transmission electron microscope (TEM, JEM-2100F) While observing the particle shape of the black material in the cross section, 50 particles were randomly selected from the TEM photograph, the particle diameter (maximum diameter) was measured, and the average value was defined as the average dispersed particle diameter.
  • TEM transmission electron microscope
  • Example B1 -Formation of black film- To 200 ml of pure water kept at 60 ° C., 15.0 g of a tin (Sn) colloidal dispersion (average primary particle size: 20 nm, solid content: 20% by mass, manufactured by Sumitomo Osaka Cement Co., Ltd.) and silver (Ag) colloid (average) Particle size: 7 nm, solid content: 20% by mass, manufactured by Sumitomo Osaka Cement Co., Ltd. 60.0 g, and 0.75% by mass polyvinylpyrrolidone (PVP, manufactured by Tokyo Chemical Industry Co., Ltd., trade name: K15) aqueous solution 100 g were added, and colloid It was set as the solution.
  • PVP polyvinylpyrrolidone
  • this mixed liquid was reacted by stirring for 10 hours at 60 ° C. using a magnetic stirrer, and then washed and concentrated by centrifugation to obtain a colloid liquid A having a black particle concentration of 15.0 mass%. It was. Thereafter, 7.5 g of a comb-type urethane polymer dispersant (manufactured by BYK Chemie, trade name: Disper Byk161, nonvolatile content: 30% by mass) is added to 100.0 g of the colloid liquid A, and then the solvent is removed by an evaporator. And it was made to dry and the black powder A was obtained. As a result of measuring the water content and the polymer dispersant amount of the obtained black powder A by the above-described method, the water content was 1.5% by mass and the polymer dispersant amount was 13.05% by mass.
  • a comb-type urethane polymer dispersant manufactured by BYK Chemie, trade name: Disper Byk161, nonvolatile content: 30% by mass
  • the ratio of silver component (silver / (silver + tin): mass ratio) was determined from the content ratio of tin and silver. It was 91.3 mass%.
  • Black dispersion A was obtained by adding 82.75 g of propylene glycol monomethyl ether acetate to 17.25 g of the obtained black powder A and irradiating ultrasonic waves for 20 minutes.
  • an acrylic resin solution (KAYARAD ZCR-1569H, manufactured by Nippon Kayaku Co., Ltd., nonvolatile content: 70% by mass) 8.78 g and dipentaerythritol hexaacrylate 1.54 g are added as a resin component raw material.
  • 0.61 g of propylene glycol monomethyl ether acetate was added, followed by treatment with an ultrasonic disperser for 5 minutes, and left for 1 hour to obtain a black paint A.
  • the average dispersed particle size of the black material in the black paint A was measured and found to be 22 nm.
  • the black paint A was applied on a non-alkali glass substrate having a thickness of 0.7 mm by a spin coating method to form a black coating film.
  • the thickness of the coating film was controlled by adjusting the rotational speed of the spin coat so that the thickness of the infrared transmitting black film after heat curing was 1.0 ⁇ m.
  • the glass substrate on which the coating film was formed was heated in the atmosphere at 230 ° C. for 1 hour using a heating device to obtain a glass substrate with an infrared transmitting black film A-1.
  • Table 4 shows values of the ratio (OD NIR / OD 560 ) between the optical density (OD NIR ) at wavelengths of 800 nm to 2500 nm and the optical density (OD 560 ) at wavelength of 560 nm.
  • -Average dispersion particle diameter in black film of black material With respect to the infrared transparent black film A-1, the particle shape of the black material in the film was observed by a transmission electron microscope (TEM) according to the above-described method. A TEM observation photograph of the film cross section is shown in FIG. Further, from this TEM photograph, the particle diameter of the dispersed particles was measured to obtain the average dispersed particle diameter. The results are also shown in Table 4. In addition, the volume fraction of the black material in the film
  • Example B2 Using the black paint A obtained in Example B1, the infrared transmission was carried out in the same manner as in Example B1, except that the spin coating rotation speed was adjusted so that the film thickness after heat curing was 0.5 ⁇ m.
  • a glass substrate with a black film A-2 was obtained.
  • the optical characteristics of the black film, the average dispersed particle diameter of the black material in the film, and the like were evaluated in the same manner as in Example B1. The results are shown in Tables 2-4.
  • Example B3 Using the black paint A obtained in Example B1, the infrared transmission was performed in the same manner as in Example B1, except that the spin coating rotation speed was adjusted so that the film thickness after heat curing was 0.13 ⁇ m. A glass substrate with a black film A-3 was obtained. Using the obtained glass substrate with an infrared transmitting black film A-3, the optical characteristics of the black film, the average dispersed particle diameter of the black material in the film, and the like were evaluated in the same manner as in Example B1. The results are shown in Tables 2-4.
  • Example B5 -Formation of black film- In 200 ml of pure water kept at 60 ° C., 15.0 g of a tin (Sn) colloid dispersion (average primary particle size: 20 nm, solid content: 20% by mass, manufactured by Sumitomo Osaka Cement Co., Ltd.) and silver (Ag) colloid (average) 60.0 g of particle size: 7 nm, solid content: 20% by mass, manufactured by Sumitomo Osaka Cement) and 100 g of 0.75% by mass polyvinylpyrrolidone (PVP: manufactured by Tokyo Chemical Industry Co., Ltd., trade name: K15) aqueous solution, A colloidal solution was obtained.
  • Sn tin
  • Ag silver colloid
  • this mixed liquid was reacted by stirring for 48 hours at 60 ° C. using a magnetic stirrer, and then washed and concentrated by centrifugation to obtain a colloid liquid C having a black particle concentration of 15.0 mass%. It was. Thereafter, 7.5 g of a comb-type urethane polymer dispersant (manufactured by Big Chemie, trade name “Disper Byk161”, nonvolatile content: 30% by mass) is added to 100.0 g of this colloid liquid C, and then the solvent is removed by an evaporator. Removal and drying gave black powder C. As a result of measuring the water content and the polymer dispersant amount of the obtained black powder C by the above-mentioned method, the water content was 1.5% by mass and the polymer dispersant amount was 13.03% by mass.
  • a comb-type urethane polymer dispersant manufactured by Big Chemie, trade name “Disper Byk161”, nonvolatile content: 30% by mass
  • Example B6 Using the black paint C obtained in Example B5, infrared transmission was carried out in the same manner as in Example B5, except that the spin coating rotation speed was adjusted so that the film thickness after heat curing was 0.5 ⁇ m. A glass substrate with a black film C-2 was obtained. Using the obtained glass substrate with an infrared transmitting black film C-2, the optical characteristics of the black film, the average dispersed particle diameter of the black material in the film, and the like were evaluated in the same manner as in Example B1. The results are shown in Tables 2-4.
  • Example B7 Using the black paint C obtained in Example B5, infrared transmission was performed in the same manner as in Example B5, except that the spin coating rotation speed was adjusted so that the film thickness after heat curing was 0.13 ⁇ m. A glass substrate with a black film C-3 was obtained. Using the obtained glass substrate with an infrared transmitting black film C-3, the optical characteristics of the black film, the average dispersed particle diameter of the black material in the film, and the like were evaluated in the same manner as in Example B1. The results are shown in Tables 2-4.
  • Example B8 In addition to 50 g of the black dispersion A obtained in Example B1, 2.05 g of an acrylic resin solution (KAYARAD ZCR-1569H, Nippon Kayaku Co., Ltd., nonvolatile content: 70% by mass) as a resin component raw material and dipentaerythritol hexaacrylate 0 .36 g was added, and 0.61 g of propylene glycol monomethyl ether acetate was further added. The mixture was treated with an ultrasonic disperser for 5 minutes, and left for 1 hour to obtain a black paint D. Next, a glass substrate with an infrared transmitting black film D-1 was obtained in the same manner as in Example B1 except that the black paint D was used.
  • an acrylic resin solution (KAYARAD ZCR-1569H, Nippon Kayaku Co., Ltd., nonvolatile content: 70% by mass) as a resin component raw material and dipentaerythritol hexaacrylate 0 .36 g was added, and
  • Example B9 In the preparation of the black powder A in Example B1, the same as the black powder A except that the comb-type urethane polymer dispersant (manufactured by Big Chemie, trade name Disper Byk161, nonvolatile content: 30% by mass) was 12.5 g.
  • black powder E was prepared.
  • Black dispersion E was obtained by adding 81.25 g of propylene glycol monomethyl ether acetate to 18.75 g of the obtained black powder E and irradiating with ultrasonic waves for 20 minutes.
  • the amount was 0.1% by mass or less. On the other hand, the amount of the polymer dispersant could not be measured because the mass loss of the carbon black itself occurred in the measurement temperature range.
  • 8.86 g of an acrylic resin solution (KAYARAD ZCR-1569H, manufactured by Nippon Kayaku Co., Ltd., nonvolatile content: 70% by mass) and 1.55 g of dipentaerythritol hexaacrylate are added to 50 g of this black dispersion F. Further, 0.61 g of propylene glycol monomethyl ether acetate was added, followed by treatment with an ultrasonic disperser for 5 minutes, and left for 1 hour to obtain black paint F. The average dispersed particle size of carbon black in the black paint F was measured and found to be 145 nm.
  • a glass substrate with a black film F-1 was obtained in the same manner as in Example B1, except that the black paint F was used instead of the black paint A in the formation of the black film of Example B1.
  • the optical characteristics of the black film, the average dispersed particle diameter of the black material in the film, and the like were evaluated in the same manner as in Example B1. The results are shown in Tables 2-4.
  • the obtained black film F-1 was observed by TEM in the same manner as in Example B1.
  • a TEM observation photograph of the film cross section is shown in FIG. From this observation photograph, the average dispersed particle size of the dispersed carbon black was also measured by the same method as in Example B1, but the carbon black particles formed a large aggregate and formed a network in the film. As a result, the particle shape and size of each particle could not be confirmed, and the dispersed particle size could not be calculated.
  • Comparative Example B2 Using the black paint F obtained in Comparative Example B1, the black film was prepared in the same manner as in Comparative Example B1, except that the spin coating rotation speed was adjusted so that the film thickness after heat curing was 0.5 ⁇ m. A glass substrate with F-2 was obtained. Using the obtained glass substrate with the black film F-2, the optical characteristics of the black film, the average dispersed particle diameter of the black material in the film, and the like were evaluated in the same manner as in Example B1. The results are shown in Tables 2-4. The average dispersed particle size of carbon black could not be calculated for the same reason as in Comparative Example B1.
  • Comparative Example B4 In addition to 16 g of the black dispersion F prepared in Comparative Example B1, 16.33 g of an acrylic resin solution (KAYARAD ZCR-1569H, manufactured by Nippon Kayaku Co., Ltd., nonvolatile content: 70% by mass) as a resin component raw material and dipentaerythritol hexaacrylate 2.86 g was added, and 3.68 g of propylene glycol monomethyl ether acetate was further added, followed by treatment with an ultrasonic disperser for 5 minutes. Next, a glass substrate with a black film G-1 was obtained in the same manner as in Example B1, except that the black paint G was used.
  • an acrylic resin solution (KAYARAD ZCR-1569H, manufactured by Nippon Kayaku Co., Ltd., nonvolatile content: 70% by mass) as a resin component raw material and dipentaerythritol hexaacrylate 2.86 g was added, and 3.68 g of propylene glycol monomethyl ether acetate
  • Example B5 In the preparation of the black powder A in Example B1, the black powder was used except that the amount of addition of the comb-type urethane-based polymer dispersant (manufactured by Big Chemie, trade name Disper Byk161, nonvolatile content: 30% by mass) was 1.5 g.
  • Black powder H was obtained by the same method as A. Using this black powder H, an attempt was made to produce a black dispersion in the same manner as in Example B1, but a sufficient dispersion state could not be obtained and a dispersion could not be produced. The results are shown in Table 2 (Comparative Examples B5 to B8 are not evaluated for optical density and the like because they cannot form a film and have poor film properties).
  • Example B6 In the preparation of black powder A in Example B1, black powder A was used except that the amount of comb urethane polymer dispersant (Bik Chemie, trade name Disper Byk161, nonvolatile content: 30% by mass) was 25 g. Black powder I was obtained by the same method. A glass substrate with a black film I-1 was produced in the same manner as in Example B1 except that this black powder I was used. However, many agglomerates existed on the film surface and many pinholes were generated. It was confirmed that it was not suitable for the measurement of film properties. The results are shown in Table 2.
  • Example B7 In the preparation of the black powder A in Example B1, a polycarboxylic acid polymer dispersant (Kao Co., Ltd.) was used instead of the comb-type urethane polymer dispersant (manufactured by Big Chemie, trade name Disper Byk161, nonvolatile content 30% by mass).
  • a black powder J was obtained in the same manner as the black powder A except that 7.5 g was used. Using this black powder J, an attempt was made to produce a black dispersion in the same manner as in Example B1, but a sufficient dispersion state could not be obtained and a dispersion could not be produced. The results are shown in Table 2.
  • Example B8 In the preparation of the black powder A in Example B1, the black powder K was treated in the same manner as the black powder A except that the drying with the evaporator after the treatment with the polymer dispersant was interrupted and the water content was changed to 5.2% by mass. Was prepared. A glass substrate with a black film K-1 was produced in the same manner as in Example B1 except that this black powder K was used. However, aggregation occurred in the coating film during the solvent evaporation process after spin coating. It was confirmed that the coating surface became white and cloudy. The results are shown in Table 2.
  • Comparative Examples B1 to B4 there was no significant change in the transmittance in the visible light region and the infrared region, and there was no transparency in the infrared region. Further, in Comparative Example B5, the amount of the polymer dispersant added was too small, so that the black powder was not sufficiently dispersed and a dispersion could not be prepared. Further, in Comparative Example B6, since the amount of the polymer dispersant added was too large and the dispersion state was not stable, the black powder aggregated during the formation of the black film, and a good black film could not be obtained. In Comparative Example B7, the affinity between the black powder and the polymer dispersant is poor, and the black powder is not sufficiently covered with the polymer dispersant. could not.
  • the transfer type photosensitive resin film described in paragraphs 0158 to 0170 of JP-A No. 2006-251237 is used for the black matrix (light-shielded image) having the black film of Examples B1 to B9 obtained above.
  • a colored pattern having a predetermined size and shape of red, green, and blue was formed by the conventional color filter manufacturing method, and a color filter was manufactured on the TFT element substrate.
  • a counter electrode substrate provided with a transparent common electrode was disposed at a position facing the color filter on the TFT element substrate, and a liquid crystal material was sealed between the color filter and the counter electrode substrate to form a liquid crystal cell.
  • Polarizing plates were attached to both surfaces of the obtained liquid crystal cell, and white LEDs as a backlight were disposed on the back side of the TFT element substrate.
  • the display characteristics of the thus manufactured COA type liquid crystal display device were evaluated. As a result, it was confirmed that a liquid crystal display device provided with a color filter using each of the black matrices exhibits good display characteristics. In particular, since the alignment between the TFT element and the black matrix was good, color mixing between R, G, and B colors was well prevented.
  • the black film of the present invention and the substrate with the black film using the black film can be suitably used in a display element typified by a liquid crystal display element and an organic EL element and an image display apparatus using the same.
  • the infrared transmissive black film of the present invention has excellent light shielding properties for visible light and has a certain value or more for infrared rays, the light emitting part of the infrared wireless remote controller And various black protective covers including a protective cover for the light receiving unit.
  • it can be applied to a black matrix of COA type or BOA type, it can be suitably used for various image display devices.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Nonlinear Science (AREA)
  • Mathematical Physics (AREA)
  • Chemical & Material Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Optical Filters (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne un film noir, etc. qui a des propriétés supérieures de blocage de la lumière, est doté d'une résistivité volumique spécifique fixe et contient une matière noire et un composant résine, le pourcentage volumique de la matière noire étant 2 % en volume à 30 % en volume inclus, la dimension moyenne des particules dispersées dans le film étant 1 nm à 200 nm inclus, la densité optique pour chaque 1 µm d'épaisseur étant au moins 1, et la résistivité volumique spécifique étant d'au moins 1011 Ω.cm. L'invention concerne également un film noir transmettant le rayonnement infrarouge, etc. qui a des propriétés supérieures de blocage de la lumière par rapport au rayonnement de lumière visible, et au moins une certaine valeur de transmittance par rapport au rayonnement infrarouge, la dimension moyenne des particules dispersées de la matière noire dans le film étant 1 nm à 50 nm inclus, la transmittance (T560) à une longueur d'onde de 560 nm pour chaque 1 µm d'épaisseur étant de moins de 40 %, et le rapport (DO950/DO560) de la densité optique (DO950) sur la base de la transmittance à une longueur d'onde de 950 nm à la densité optique (DO560) sur la base de la transmittance à une longueur d'onde de 560 nm n'étant pas supérieur à 0,35.
PCT/JP2011/069286 2010-08-26 2011-08-26 Film noir, substrat doté d'un film noir, dispositif d'affichage d'images, composition de résine noire, et liquide de dispersion de matière noire WO2012026577A1 (fr)

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CN201180041475.XA CN103069316B (zh) 2010-08-26 2011-08-26 黑色膜、带黑色膜的基材和图像显示装置以及黑色树脂组合物和黑色材料分散液
KR1020137004842A KR101800344B1 (ko) 2010-08-26 2011-08-26 흑색막, 흑색막이 있는 기재 및 화상 표시 장치, 및 흑색 수지 조성물 및 흑색 재료 분산액

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JP2010189650A JP5429114B2 (ja) 2010-08-26 2010-08-26 赤外線透過黒色膜、赤外線透過黒色膜を用いた膜付き基材及び画像表示装置
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JP2013257493A (ja) * 2012-06-14 2013-12-26 Sumitomo Osaka Cement Co Ltd 黒色材料、黒色材料分散液、黒色樹脂組成物、黒色膜及び黒色膜付き基材
JP2015525371A (ja) * 2012-05-30 2015-09-03 エルジー・ケム・リミテッド 感光性樹脂組成物および前記感光性樹脂組成物から製造されたベゼルパターンを含むタッチパネルまたはディスプレイ装置
EP3951447A4 (fr) * 2019-03-29 2022-07-06 FUJIFILM Corporation Composition, film de protection contre la lumière, filtre coloré, élément optique, capteur, élément d'imagerie à semi-conducteurs et unité de phare
WO2023022199A1 (fr) 2021-08-18 2023-02-23 積水化学工業株式会社 Particules noires transmettant la lumière proche infrarouge

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KR101616775B1 (ko) * 2013-06-18 2016-04-29 디아이씨 가부시끼가이샤 액정 표시 장치
EP3054343B1 (fr) 2013-11-29 2018-05-30 DIC Corporation Dispositif d'affichage à cristaux liquides (lcd)
EP3045961B1 (fr) 2013-12-24 2018-05-02 DIC Corporation Dispositif d'affichage à cristaux liquides
JP6730006B2 (ja) * 2015-05-21 2020-07-29 株式会社きもと 光学機器用遮光部材、及びその製造方法
KR101776430B1 (ko) * 2015-12-14 2017-09-07 현대자동차주식회사 차세대 연료펌프 일체형 디젤 연료필터
CN105448825B (zh) * 2016-01-07 2018-12-11 京东方科技集团股份有限公司 显示基板的制备方法及显示基板、显示装置
JP7114844B2 (ja) * 2017-08-18 2022-08-09 エルジー・ケム・リミテッド 基板
KR102630401B1 (ko) * 2018-09-20 2024-01-30 후지필름 가부시키가이샤 차광성 조성물, 경화막, 컬러 필터, 차광막, 광학 소자, 고체 촬상 소자, 헤드라이트 유닛

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JP2009008740A (ja) * 2007-06-26 2009-01-15 Fujifilm Corp 隔壁、カラーフィルタ及び表示装置
JP2009069822A (ja) * 2007-08-22 2009-04-02 Mitsubishi Chemicals Corp 樹脂ブラックマトリックス、遮光性感光性樹脂組成物、ｔｆｔ素子基板及び液晶表示装置

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JP2015525371A (ja) * 2012-05-30 2015-09-03 エルジー・ケム・リミテッド 感光性樹脂組成物および前記感光性樹脂組成物から製造されたベゼルパターンを含むタッチパネルまたはディスプレイ装置
JP2013257493A (ja) * 2012-06-14 2013-12-26 Sumitomo Osaka Cement Co Ltd 黒色材料、黒色材料分散液、黒色樹脂組成物、黒色膜及び黒色膜付き基材
EP3951447A4 (fr) * 2019-03-29 2022-07-06 FUJIFILM Corporation Composition, film de protection contre la lumière, filtre coloré, élément optique, capteur, élément d'imagerie à semi-conducteurs et unité de phare
WO2023022199A1 (fr) 2021-08-18 2023-02-23 積水化学工業株式会社 Particules noires transmettant la lumière proche infrarouge
KR20240046713A (ko) 2021-08-18 2024-04-09 세키스이가가쿠 고교가부시키가이샤 근적외선 투과 흑색 입자

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KR20140006767A (ko) 2014-01-16
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