Classifications

• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
  • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
  • C09B67/0033—Blends of pigments; Mixtured crystals; Solid solutions
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
  • C09B29/00—Monoazo dyes prepared by diazotising and coupling
  • C09B29/0003—Monoazo dyes prepared by diazotising and coupling from diazotized anilines
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
  • C09B29/00—Monoazo dyes prepared by diazotising and coupling
  • C09B29/34—Monoazo dyes prepared by diazotising and coupling from other coupling components
  • C09B29/36—Monoazo dyes prepared by diazotising and coupling from other coupling components from heterocyclic compounds
  • C09B29/3695—Monoazo dyes prepared by diazotising and coupling from other coupling components from heterocyclic compounds containing other heterocyclic compounds
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
  • C09B31/00—Disazo and polyazo dyes of the type A->B->C, A->B->C->D, or the like, prepared by diazotising and coupling
  • C09B31/02—Disazo dyes
  • C09B31/12—Disazo dyes from other coupling components "C"
  • C09B31/14—Heterocyclic components
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
  • C09B33/00—Disazo and polyazo dyes of the types A->K<-B, A->B->K<-C, or the like, prepared by diazotising and coupling
  • C09B33/02—Disazo dyes
  • C09B33/12—Disazo dyes in which the coupling component is a heterocyclic compound
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
  • C09B35/00—Disazo and polyazo dyes of the type A<-D->B prepared by diazotising and coupling
  • C09B35/02—Disazo dyes
  • C09B35/021—Disazo dyes characterised by two coupling components of the same type
  • C09B35/03—Disazo dyes characterised by two coupling components of the same type in which the coupling component is a heterocyclic compound
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
  • C09B35/00—Disazo and polyazo dyes of the type A<-D->B prepared by diazotising and coupling
  • C09B35/02—Disazo dyes
  • C09B35/039—Disazo dyes characterised by the tetrazo component
  • C09B35/04—Disazo dyes characterised by the tetrazo component the tetrazo component being a benzene derivative
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
  • C09B35/00—Disazo and polyazo dyes of the type A<-D->B prepared by diazotising and coupling
  • C09B35/02—Disazo dyes
  • C09B35/039—Disazo dyes characterised by the tetrazo component
  • C09B35/08—Disazo dyes characterised by the tetrazo component the tetrazo component being a derivative of biphenyl
  • C09B35/10—Disazo dyes characterised by the tetrazo component the tetrazo component being a derivative of biphenyl from two coupling components of the same type
  • C09B35/18—Disazo dyes characterised by the tetrazo component the tetrazo component being a derivative of biphenyl from two coupling components of the same type from heterocyclic compounds
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
  • C09B35/00—Disazo and polyazo dyes of the type A<-D->B prepared by diazotising and coupling
  • C09B35/02—Disazo dyes
  • C09B35/039—Disazo dyes characterised by the tetrazo component
  • C09B35/08—Disazo dyes characterised by the tetrazo component the tetrazo component being a derivative of biphenyl
  • C09B35/20—Disazo dyes characterised by the tetrazo component the tetrazo component being a derivative of biphenyl from two coupling compounds of different types
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
  • C09B35/00—Disazo and polyazo dyes of the type A<-D->B prepared by diazotising and coupling
  • C09B35/02—Disazo dyes
  • C09B35/039—Disazo dyes characterised by the tetrazo component
  • C09B35/28—Disazo dyes characterised by the tetrazo component the tetrazo component containing two aryl nuclei linked by at least one of the groups —CON<, —SO2N<, —SO2—, or —SO2—O—
  • C09B35/30—Disazo dyes characterised by the tetrazo component the tetrazo component containing two aryl nuclei linked by at least one of the groups —CON<, —SO2N<, —SO2—, or —SO2—O— from two identical coupling components
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
  • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
  • C09B67/0001—Post-treatment of organic pigments or dyes
  • C09B67/0002—Grinding; Milling with solid grinding or milling assistants
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
  • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
  • C09B67/0071—Process features in the making of dyestuff preparations; Dehydrating agents; Dispersing agents; Dustfree compositions
  • C09B67/0084—Dispersions of dyes
  • C09B67/0085—Non common dispersing agents
  • C09B67/009—Non common dispersing agents polymeric dispersing agent
• • G—PHYSICS
  • G02—OPTICS
  • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
  • G02B5/00—Optical elements other than lenses
  • G02B5/20—Filters
  • G02B5/22—Absorbing filters
  • G02B5/223—Absorbing filters containing organic substances, e.g. dyes, inks or pigments

Definitions

• the present invention relates to a highly electrically insulating azo black pigment, a method for producing the same, a coloring composition, a coloring method, and colored articles. More particularly, the need to be a highly insulating, applications utilizing to absorb covers visible light region, more useful in applications using infrared, visible light shielding properties and infrared transmissive optical
• the present invention relates to a composition, a coloring method using the composition, and colored articles. Examples of the colored article include a color display panel and a back sheet of a solar power generation module.
• LCD liquid crystal color displays
• LCD liquid crystal color displays
• CF color filters
• R (red), G (green), and B (blue) pixels are arranged in a stripe, mosaic, triangle, etc. on a transparent substrate made of glass, etc. Color is generated by additive mixing of transmitted light of R, G, and B pixels to form an image. Further, a black matrix (hereinafter abbreviated as “BM”) is formed around each pixel in a lattice shape to shield the light from the backlight and prevent color light from leaking from adjacent pixels, and R, Color is generated by additive mixing of the transmitted light of the G and B pixels to form an image.
• BM black matrix
• the conventional method of forming BM was a method of vapor-depositing chromium or the like, but there were various problems listed below. That is, the chromium vapor deposition method requires a metal sputtering apparatus for production, and is difficult to adapt to the increase in the size of the glass substrate, is expensive, has a high reflectance, and has environmental problems due to chromium compounds. In contrast, the realization of cost reduction and higher definition of the CF, the elimination of environmental problems, a method of forming a BM using a resin composition containing a black pigment such as carbon black pigment and titanium black pigment is proposed Carbon black pigment has been used as a main component.
• a black pigment such as carbon black pigment and titanium black pigment
• liquid crystal color displays are also moving toward larger size, while the development of small size such as medium size, mobile size and pocket size is remarkable.
• CF pixel display method improvement of ink for pixel formation to improve color sharpness and color reproducibility, and further improvement of color development, sharpness, and contrast of chromatic pigments used for it High performance has been achieved.
• a black matrix on array method in which a BM is formed on a thin film transistor (TFT), and a color filter on array method (COA method) in which pixels are also stacked on the substrate side are: Since the aperture ratio increases and the pixel area can be increased, the viewing angle, which was a weak point of conventional LCDs, can be widened. Also, alignment with the counter substrate is not necessary in the work process, and the bonding process work is improved. Can be streamlined.
• lateral electric field drive system in the displaying pixels to convert the liquid crystal layer by applying an electric field parallel to the substrate - plane switching mode (IPS mode) and a wide viewing angle
• VA method which is a vertical alignment method for liquid crystals that enables high contrast
• MVA method multi-domain vertical alignment method using distributed light distribution that creates different orientations within the pixel ) Etc.
• the methods such as the BOA method, the COA method, and the IPS method mentioned above are a method of forming a BM on an active element such as a TFT or a method of forming an active element on a spacing support member resin such as a thickened BM.
• a material such as BM may cause malfunction of the TFT unless the electrical insulation is high.
• carbon black pigments that are generally used as BM light-shielding black pigments are inherently low in electrical resistance, so they are not suitable as light-shielding black pigments used in these systems.
• a light-shielding material having high electrical resistance characteristics is desirable.
• Patent Document 1 a carbon black pigment in which a carbon black pigment defined by an oxygen amount is coated with a highly insulating resin film to improve electrical resistance has been proposed.
• Patent Document 2 an insulating BM is formed by using a carbon black pigment whose surface is covered with an organic carbon-treated insulating carbon black pigment or resin to improve electrical resistance, and a proposal for applying this to a COA system.
• Patent Document 2 carbon black pigments are inherently conductive materials, and it is difficult to achieve complete insulation even with resin coating.
• the photovoltaic power generation module constituting the photovoltaic power generation system is attached to a place that is directly irradiated with sunlight, in particular, on the rooftop of an outdoor building, on the roof, or in an outdoor open space.
• the back sheet is colored black with a carbon black pigment so that the gap between the silicon cells of the power generation module is black and the entire surface looks black for the purpose of making the appearance beautiful and unobtrusive. Has been done.
• the backsheet absorbs heat, causing the power generation module to rise in temperature, resulting in a decrease in the output of the power generation cell. May end up. Therefore, a coloring system that can suppress the temperature rise of the power generation module as much as possible even when the back sheet is colored black or dark chromatic in a solar power generation system is expected.
• the electrical insulation of a pigment is evaluated by measuring the volume resistivity and surface resistance of a coating film containing the pigment.
• the insulation of a coating film is a film forming material that forms the coating film. Since it depends largely on the electrical insulation of the polymer binder material, it may not be said that the electrical insulation of the pigment itself is shown correctly.
• BM of a color display is required to have sufficient light-shielding properties for a backlight, an attempt is made to solve this problem by increasing the black pigment content in the BM coating as much as possible.
• the above-described solar cell backsheet has the same demand as described above. That is, carbon black, which has a low electrical resistance, is used for coating many electronic circuits and conductive wires, such as solar cell backsheets, and when black pigments are used to color black or dark colors. It is not preferable to use a pigment or a titanium oxide black pigment.
• a technique using a pigment that can be easily synthesized, such as an azo pigment, rather than the condensed pigment proposed in Citations 3 and 4 that require a multi-step advanced synthesis process Development is demanded.
• the object of the present invention is to exhibit sufficient insulation as the black pigment itself, and by using this, it is possible to give visible light blocking properties and infrared transmission optical characteristics, and to provide a color display BM or the like.
• An object of the present invention is to provide a novel azo black pigment that can be used in a wide range of applications such as a back sheet for a solar cell and can be synthesized by a simpler method than a condensed pigment.
• the inventors of the present invention have earnestly studied to achieve the development of a black pigment that can be used with high reliability in the formation of the CF insulating BM as described above and the coloring of the backsheet of the photovoltaic power generation panel. As a result, the present invention was reached. More specifically, as a function of the black pigment itself, even if BM is formed on an active element such as TFT, the TFT does not cause malfunction due to short circuit, its volume resistivity is at least an index of an insulator.
• a black pigment having an electric resistance of 10 8 ⁇ ⁇ cm or more and having an average particle size of about 10 nm to 200 nm in order to satisfy optical properties as a pigment and performance requirements as a colorant As a result of endeavoring to develop, the present invention has been completed.
• the present invention is an azo black pigment that exhibits high electrical insulation properties and that can be used to give visible light blocking properties and infrared transmission optical properties, and is one in a molecule. It has a molecular structure having the above azo group and at least one 2-hydroxy-11H-benzo [a] -carbazole-3-carboxylic acid amide residue introduced from a coupling component, and has a volume resistivity of the pigment itself. Is 10 10 ⁇ ⁇ cm or more, and an average particle size thereof is 10 nm to 200 nm.
• a preferred embodiment of the present invention includes an azo black pigment having the molecular structure having at least one of the following structures (1) to (6).
• a compound having one amino group (representative formula: Ar—NH 2 ) as a diazo component and diazotized to a diazonium salt, and 2-hydroxy-11H-benzo [a] — as a coupling component
• HBC carbazole-3-carboxylic acid arylamide
• Compound having two or more amino groups as a diazo component ( Representative formula: H 2 N—Ar—NH 2 ) and diazotized to diazonium salt, and 2-hydroxy-11H-benzo [a] -carbazole-3-carboxylic acid arylamide (HBC) as a coupling component Abbreviation) is an azo-coupled structure represented by [HBC
• a coupling component (indicated as HBC-Cp) having a group (abbreviated as HBC-) and another coupling component residue (indicated as Cp-) other than the compound has one amino group as a diazo component
• a diazo component a diazonium salt obtained by diazotization using a compound having one or more azo groups and one or more amino groups (representative formula: Ar—N ⁇ N—Ar—NH 2 ) is used.
• aryl residue and “Ar” indicates or without residues having a substituent group of the aromatic compounds and heterocyclic compounds, be the same if there more than wherein also be different Good.
• “Ar—N ⁇ N—” and “—N ⁇ N—Ar—N ⁇ N—” in the formula mean an “arylazo residue” coupled with a diazonium salt of a diazo component. The same applies to the following.
• Another embodiment of the present invention is a method for producing an azo black pigment for obtaining the above azo black pigment, which is selected from any of the following (I-1) to (I-6):
• the synthesis method (I) of an azo black pigment using a synthesis method is provided and the azo black pigment synthesized in the synthesis step (I) is coarse
• the following (II-1) or (II-) is a method for producing an azo black pigment, characterized in that the step (II) is carried out to refine the pigment so that the average particle diameter of the pigment becomes 10 nm to 200 nm by the method 2).
• a method for synthesizing the pigment in the synthesis step (I) of the azo-based black pigment (I-1) To a diazonium salt obtained by diazotizing a compound having one amino group (representative formula: Ar—NH 2 ), 2-hydroxy-11H-benzo [a] -carbazole-3-carboxylic acid arylamide ( Synthesis method for azo coupling of HBC) (I-2) A diazonium salt formed by diazotizing a compound having two or more amino groups (representative formula: H 2 N—Ar—NH 2 ) is converted into 2-hydroxy-11H —Synthesis Method for Azo Coupling of Benzo [a] -carbazole-3-carboxylic Acid Arylamide (HBC) (I-3) Compound Having Two or More Amino Groups (Representative Formula: H 2 N—Ar—NH 2 Diazotized) to 2-hydroxy-11H-benzo [a] -carbazole-3-carboxylic acid aryl
• a diazonium salt obtained by diazotizing a compound having one amino group (indicated as Ar—NH 2 ) to droxy-11H-benzo [a] -carbazole-3-carboxylic acid is azo-coupled, and then obtained.
• the present invention includes, as separate embodiments, formed by dispersing a pigment component containing azo black pigment obtained by the production method of the azo black pigment or above in a liquid dispersion medium or in a solid dispersion medium A coloring composition is provided.
• the article when the article is colored black or dark by coloring the surface of the article or coloring the article itself, the colored composition described in any of the above is used.
• a feature coloring method is provided.
• the present invention provides, as another embodiment, a colored article characterized by being subjected to the above-described method for coloring an article.
• the present invention provides a color display panel having a black matrix (BM) formed on a color filter (CF) substrate or an organic EL light emitting substrate, wherein one or more BMs are present in the molecule.
• BM black matrix
• CF color filter
• organic EL light emitting substrate wherein one or more BMs are present in the molecule.
• a molecular structure having at least one 2-hydroxy-11H-benzo [a] -carbazole-3-carboxylic acid amide residue introduced from a coupling component, the volume resistivity of the pigment itself is Provided is a color display panel characterized by containing an azo black pigment having an average particle size of 10 nm to 200 nm and having an average particle diameter of 10 10 ⁇ ⁇ cm or more.
• the present invention provides, as another embodiment, on a light reflective sheet provided with a light reflective base, at least one azo group in the molecule and at least one introduced from a coupling component. It has a molecular structure having 2-hydroxy-11H-benzo [a] -carbazole-3-carboxylic acid amide residue, the volume resistivity of the pigment itself is 10 10 ⁇ ⁇ cm or more, and its average particle diameter
• a coloring composition containing a highly electrically insulating azo black pigment having a thickness of 10 nm to 200 nm is coated, applied, stuck, welded, stacked, printed, inkjet printed, electrophotographic printed or electrostatic printed.
• a method for producing a back sheet for a photovoltaic module characterized by providing a reflective color in the infrared region, and multilayering a black or dark infrared transmissive layer on the light reflective sheet Subjected to. Furthermore, the back sheet
• the colored film containing the azo black pigment has a black color, and the light beam of the backlight in the visible light range is almost completely absorbed on the CF transparent substrate as described above. Therefore, it is suitable as a BM forming material. Furthermore, the volume resistivity value is 10 8 ⁇ ⁇ cm or more which is an index of an insulator when the black pigment itself is measured as a powder sample by sufficiently washing to remove the influence of contaminating ions and the like.
• various CF improvement methods for forming a BM on an active element such as a TFT such as a BOA method, an IPS method, a COA method, a columnar spacer, etc. It is also suitable as a material for forming a light-shielding black film for forming a CF BM.
• the azo black pigment provided by the present invention in addition to the above-described high electrical insulation, in addition to the above-described CF constitution method, in addition to providing optical characteristics that absorb up to a high wavelength region of visible light, It is suitable for the form used for the liquid crystal panel etc. which employ
• the azo black pigment of the present invention is highly electrically insulating, it can be suitably used as a light-shielding black pigment for BM in organic EL displays. Further, azo black pigment provided by the present invention, since the possible BM to infrared transparent black film, the alignment in the case of laminating the multilayer on the CF substrate, the infrared absorbing point or crosshairs If printing is performed, position adjustment using an infrared laser can be easily performed.
• the azo black pigment of the present invention sufficiently transmits infrared rays, the light in the infrared region transmitted through the black coating film formed using the pigment is a white pigment added to the base or coating material. It shows the function of being reflected by extender pigments, etc., and re-transmitted through the black coating. Furthermore, since the azo black pigment of the present invention has a high electric resistance value, it is suitable for applications for coating electric circuits and electric wires. For example, a back sheet of a photovoltaic power generation panel is an application that can utilize both of these functions. The back sheet in which the azo black pigment of the present invention is used to form a black or dark infrared transmissive layer in multiple layers on the reflective base layer reflects the heat rays of sunlight, thereby The temperature rise can be suppressed.
• the azo black pigment of the present invention can be used as a dye for an infrared filter by utilizing infrared transparency as described above in other general-purpose applications.
• the azo black pigment of the present invention is in a form combined with a white pigment and the like, from the viewpoint of improvement of living environment, comfort and energy saving in recent years, painting on houses and buildings, road paving, and more It can be used as a temperature rise prevention material due to direct sunlight when painting a ship's deck or exterior.
• the azo black pigment of the present invention can be used for coloring materials for counterfeiting of military equipment or forgery prevention.
• the azo black pigment of the present invention can be expanded to the various functions and applications listed above, and is a condensation pigment that requires a multi-step advanced synthesis process such as the perylene pigment described above. As compared with the above, since it can be easily synthesized in a short process at normal pressure and in the atmosphere, it is useful that the azo black pigment of the present invention can be used from the economical viewpoint.
• the azo black pigment of the present invention itself exhibits high electrical insulation, and by using this, it is possible to provide visible light blocking properties and infrared transmission optical characteristics.
• the feature is a molecular structure having one or more azo groups in the molecule and at least one 2-hydroxy-11H-benzo [a] -carbazole-3-carboxylic acid amide residue introduced from a coupling component
• the volume resistivity of the pigment itself is about 10 10 ⁇ ⁇ cm or more, and the average particle size is about 10 nm to 200 nm.
• the average particle diameter is preferably 10 nm to 50 nm.
• the azo black pigment of the present invention optically absorbs light in the visible light region and transmits light in the infrared light region due to its chemical structure, and physically has pigment particles. Since it is fine, pigment particles can be filled with high density in the coating film. By their effects, azo black pigment of the present invention, the formation can be sufficiently shield light in the visible region, moreover, since the pigment particles are fine, for example, a light-shielding coating film such as BM In the colorant composition for making it disperse
• the azo black pigment of the present invention needs to exhibit a high electric resistance characteristic of a volume resistivity of 10 10 ⁇ ⁇ cm or more when the black pigment itself is measured as a powder, Even in the process, it is sufficiently washed so as to eliminate the influence of contaminating ions and the like.
• the present inventors have at least one 2-hydroxy-11H-benzoic acid having at least one azo group in the molecule and introduced from the coupling component.
• a chemical structure having an [a] -carbazole-3-carboxamide residue was found.
• the production method of the azo-based black pigment needs to provide one or more azo bonds (azo groups) in the molecular structure, for example, as a diazo component, one or two amino groups that change to a diazonium group are used.
• a method of azo coupling using a compound having the above, a method of azo coupling using a compound having at least one coupling position as a coupling component, or an intermediate having the same pigment structure And a method of synthesizing an azo dye having a carboxyl group and then amide-bonding with a polyamine to form an azo pigment. This point will be described in detail.
• the azo black pigment of the present invention preferably has one of the following structures (1) to (2g).
• an azo pigment having one azo group in the molecule is called a “monoazo black pigment”, and a black disazo pigment or black trisazo pigment having two or more azo groups in the molecule.
• polyazo black pigments are sometimes collectively referred to as “polyazo black pigments”.
• polyazo black pigment having the structure examples include polyazo black pigments having the following structure depending on the intermediate of the azo pigment used and the synthesis method. Examples of their synthesis methods include the following.
• benzidine is exemplified as a compound having two or more amino groups by the above synthesis method. Examples of structures when phenylenediamine or diaminobenzanilide is used for each are given.
• benzidine or an amino group as a compound having two or more
• An example of a structure in which phenylenediamine is used and 2-hydroxy-3-naphthoic acid arylamide is used as another coupling component Cp will be given.
• HBC-HBC 2-hydroxy-11H-benzo [a] -carbazole-3-carboxamide residues
• HBC- 2-hydroxy-11H-benzo [a] -carbazole-3-carboxamide residues
• the above-mentioned residue can be obtained via phenylene or biphenylene by the above synthesis method.
• An example of a structure in which aniline is used as a compound having one amino group in a coupling component in which two “HBC-” are bonded is given.
• a compound (Ar—NH 2 ) having one amino group as a diazo component is used for 2-hydroxy-11H-benzo [a] -carbazole-3-carboxylic acid, and the diazonium salt is converted to azo Synthesis is performed by coupling to a carboxylic acid of a monoazo
• the above-mentioned residue can be obtained via phenylene or biphenylene by the above synthesis method.
• An aniline as a compound having one amino group is bonded to the coupling component in which the residue of 2-hydroxy-3-naphthoic acid arylamide, which is another coupling component other than the compound, is bonded to “HBC-”.
• An example of the structure when used is given.
• the diazonium salt is azo-coupled to form a carboxylic acid of a monoazo dye, and then the carboxylic acid of both azo dyes is condensed with an aryl polyamine to form a carboxamide bond. To be synthesized.
• one or more azo compounds may be added to the “HBC” by the synthesis method described below.
• An example of a structure in the case of coupling using an aniline that binds a phenylazo residue as a compound having a group and one or more amino groups is given.
• the method for producing an azo black pigment of the present invention includes an azo black pigment synthesis step (I) using a synthesis method selected from the following, and the azo black pigment synthesized in the synthesis step (I):
• the pigment particle size is adjusted by refining the pigment so that the average particle size of the pigment is 10 nm to 200 nm by the following method (II-1) or (II-2).
• Process (II) is performed. Below, a synthetic
• the method for synthesizing the azo black pigment of the present invention is selected from the following synthesis methods (1) to (4).
• the method of (1) has one amino group as a diazo component or having two or more compounds (representative formula: Ar-NH 2, H 2 N-Ar-NH 2) with, formed by diazotizing this diazonium salt Alternatively, a compound having an azo group and an amino group (representative formula: Ar—N ⁇ N—Ar—NH 2 ) and diazotized to a diazonium salt to give 2-hydroxy-11H-benzo [a]
• This is a synthesis method in which carbazole-3-carboxylic acid arylamide (HBC) is azo-coupled.
• HBC carbazole-3-carboxylic acid arylamide
• the method (2) uses a compound having two or more amino groups (representative formula: H 2 N—Ar—NH 2 ) as a diazo component, and diazotizes this to a 2-hydroxy-11H—
• This is a method for synthesizing a polyazo black pigment having a structure in which benzo [a] -carbazole-3-carboxylic acid arylamide (HBC) and other coupling components (denoted as Cp) other than the compound are azo-coupled.
• HBC benzo [a] -carbazole-3-carboxylic acid arylamide
• Cp coupling components
• the polyazo black pigment obtained by the synthesis method (2) has a structure represented by [HBC—N ⁇ N—Ar—N ⁇ N—Cp] described above.
• the method (3) is the following method (3-1) or (3-2).
• the polyazo black pigment obtained by the synthesis methods of (3-1) and (3-2) is represented by [Ar—N ⁇ N—HBC—HBC—N ⁇ N—Ar] described above. It will have a structure.
• the method (4) is the following method (4-1) or (4-2).
• the polyazo black pigments obtained by the synthesis methods (4-1) and (4-2) are represented by [Ar—N ⁇ N—HBC—Cp—N ⁇ N—Ar] described above. It will have a structure.
• the coupling component and diazo component used in the above synthesis method will be described.
• the coupling component is specifically exemplified.
• Examples of the coupling component (HBC) include 2-hydroxy-11H-benzo [a] -carbazole-3-anilide, 2-hydroxy-11H-benzo [a] -carbazole-3-naphthylamide, and the like. Their derivatives. Examples of the derivative include a substituent such as an alkyl (carbon number: 1 to 10) group, an alkoxy (carbon number; 1 to 10) group, a trifluoromethyl group, a halogen group; a nitro group, an alkyloxycarbonyl group, an alkyl group.
• Sulfonyl group aminosulfonyl group, alkylsulfamide group, phenylsulfamide group, alkylaminosulfonyl group, anilinosulfonyl group, aminocarbonyl group, benzamide group, alkylaminocarbonyl group, anilinocarbonyl group, cyclic dicarboimide group, cyclic ureylene
• a coupling component having one or more groups introduced therein.
• Examples of the coupling component (HBC-HBC) include phenylene-bis (2-hydroxy-11H-benzo [a] -carbazole-3-carboxamide), biphenyl-bis (2-hydroxy-11H-benzo [a ] -Carbazole-3-carboxamide), naphthalene-bis (2-hydroxy-11H-benzo [a] -carbazole-3-carboxamide) and the like and derivatives thereof.
• a substituent of the derivative a known substituent such as an alkyl (carbon number: 1 to 10) group, an alkoxy (carbon number: 1 to 10) group, a trifluoromethyl group, a halogen group, etc. Coupling components introduced individually or more.
• Examples of the coupling component (Cp) include 2-hydroxy-3-naphthoic acid arylamide, 2-hydroxy-6-naphthoic acid arylamide, 2-hydroxy-3-anthracenecarboxylic acid arylamide, 2 -Hydroxy-3-dibenzofurancarboxylic acid arylamide, 2-hydroxy-1-carbazolecarboxylic acid arylamide, acetoacetic arylamide and the like and their derivatives.
• Azoic coupling components 2 4, 6, 7, 8, 10, 11, 12, 14, 17, 18, 19, 20, 21, 22, 23, 24, 27, 28, 29, 31, 32, 41 46, 111, 112, 113, 45, 16, 37, 36, 15, acetoacetic-N-benzimidazolone-5-amide and the like.
• the diazo component is specifically exemplified.
• Examples of the compound (a) having one amino group are aniline, naphthylamine, aminoanthraquinone, phenoxyaniline, phenyliminoaniline, and the like, and derivatives thereof.
• a known substituent for the aryl group for example, an alkyl (carbon number: 1 to 10) group, an alkoxy (carbon number; 1 to 10) group, a trifluoromethyl group, a halogen group, a nitro group
• 2-methoxy-5-N-phenylcarbamoyl-aniline, 2'-chloro-2-methoxy-5-N-phenylcarbamoyl-aniline, 3'-chloro-2-methoxy-2'methyl-5-N-phenylcarbamoyl -Examples include aniline.
• Examples of the compound having two amino groups include phenylenediamine, diaminobiphenyl, diaminonaphthalene, diaminoanthraquinone, diamino-benzophenone, diaminopyridine, diaminodiphenylamine , Diaminodiphenyl ether, diaminobenzanilide and the like and their derivatives.
• a substituent of the derivative a known substituent such as an alkyl (carbon number: 1 to 10) group, an alkoxy (carbon number: 1 to 10) group, a trifluoromethyl group, a halogen group, etc.
• a diazo component introduced individually or more.
• the diazo component having an azo group is specifically exemplified.
• Examples of the compound having one azo group and one amino group include (phenylazo) -aniline, (naphthylazo) -aniline, (phenylazo) -naphthylamine, (naphthylazo) ) -Naphthylamine and the like and their derivatives.
• a substituent of the derivative a known substituent such as an alkyl (carbon number: 1 to 10) group, an alkoxy (carbon number: 1 to 10) group, a trifluoromethyl group, a halogen group, etc.
• a diazo component introduced individually or more. Specifically, for example, C.I. I. Azoic diazo components 4, 21, 23, 27, 38, 39, 45, 51 and the like.
• the step (II) of making the pigment fine and adjusting the particle size of the pigment particles, which constitutes the azo black pigment production method of the present invention will be described.
• the particle size of the azo pigment obtained by the synthesis method as described above is coarse
• the azo black pigment of the present invention is either the following method (1) or (2):
• the average particle diameter of the pigment is reduced to about 10 nm to 200 nm.
• the pigment in order to sufficiently shield the light of the backlight with a light-shielding coating film such as a BM coating film of CF, for example, using the azo black pigment obtained by the synthesis method described above, It is necessary to physically eliminate light leakage, and the pigment needs to be fine particles in order to fill the pigment, which is a fine particle solid, with high density in the coating film.
• the high-concentration pigment black coloring composition and black colorant which are pigment dispersions used for forming a coating film, the pigment is stably dispersed and has high long-term storage stability.
• the pigment particles are fine, and the average particle diameter is about 10 nm to 200 nm. Therefore, the azo black pigment of the present invention is known in the following manner in order to adjust the average particle size of the pigment to the required particle size when the pigment synthesized by the above method is coarse. It is necessary to carry out a pigment refinement step and produce a refined pigment.
• Pigment grinders or pigment dispersers such as ball mills, sand mills, attritors, horizontal continuous media dispersers, kneaders, continuous uniaxial kneaders, continuous biaxial kneaders, three rolls, open roll continuous kneaders Miniaturization method to use and miniaturization
• a pigment refining step selected from known methods such as a salt milling method in which a water-soluble salt and, if necessary, a water-soluble organic solvent are kneaded and ground in a kneading machine, and the average particle size is about 10 nm.
• a salt milling method in which a water-soluble salt and, if necessary, a water-soluble organic solvent are kneaded and ground in a kneading machine, and the average particle size is about 10 nm.
• the particle diameter of the pigment is adjusted in accordance with the intended use. When a higher infrared transmittance is desired, it is
• the particle diameter of the pigment is adjusted according to the intended use.
• the adjustment of the particle size is mainly controlled by the amount ratio of the salt to the pigment and the kneading time.
• the pigment particles be smaller, for example, a fine pigment particle of 10 to 50 nm is preferable, and a dispersion state of ultrafine pigment particles of 10 to 30 nm is preferable. .
• the base is preferably reflective, but the pigment particles may be relatively large and may be used at 100 nm to 200 nm.
• the above-mentioned salt milling method is a method in which a water-soluble inorganic salt powder as a grinding aid is added to the pigment several times, specifically 2 to 20 times the amount of the pigment to be ground according to the desired pigment particle size. Add about 3 to 10 times the amount, add a viscous water-soluble organic solvent such as ethylene glycol, diethylene glycol, polyethylene glycol, and knead and grind.
• a viscous water-soluble organic solvent such as ethylene glycol, diethylene glycol, polyethylene glycol, and knead and grind.
• As the water-soluble inorganic salt used for the grinding aid sodium chloride, sodium sulfate and the like are used. After milling, it is added dilute sulfuric acid, etc. in water, dissolve the grinding aid, and filtered to give a pigment filtration paste (presscake) and washed with water.
• the washing water further has a conductivity of 50 ⁇ S / cm or less, preferably 10 ⁇ S / cm or less, preferably ion-exchanged water, reverse osmosis membrane Thoroughly washing in a washing step of washing using purified water or distilled water to prepare a highly insulating fine pigment.
• the evaluation of the degree of washing of the pigment presscake is preferably determined by measuring the conductivity of the filtrate.
• the attached waste water is mixed in the drainage path of the filter and it may not always be shown correctly, as a guideline, it is washed until it shows a value of 500 ⁇ S / cm or less, preferably 200 ⁇ S / cm or less.
• a value of 10 10 ⁇ ⁇ cm or more is achieved as the volume resistivity.
• the pigment presscake is dried with hot air by a conventional method, and then pulverized with a dry pulverizer or redispersed in water, and the pigment dispersion is formed into a powder pigment by spray drying.
• the powder pigment is dispersed by the above-described various wet dispersers and kneaders to obtain a high-concentration pigment black coloring composition or black coloring agent.
• the press cake can be dispersed with a wet disperser as it is or processed into an oily colorant or a resin dispersion colorant by a flushing method. Processing is performed. It is also preferable to treat the resin in water to make an easily dispersible processed pigment or processed pigment.
• a powder pigment compression-molded tablet was prepared, and the volume resistivity in a state where the pigments were in close contact with each other without a polymer binder was measured. While the amount may vary depending on the pigment, the powder pigment an aluminum ring of about 1 g ⁇ 1.5 g (inner diameter 3.3 cm, height 5 mm, thickness 1mm) bloom in the manual compression molding machine (Riken Seiki Co., compressed by Ltd.) to 200 kg / cm 2, the thickness was formed approximately into 2mm-shaped tablets.
• HIRESTA-UP high resistivity meter
• the measurement result of the azo black pigment showed 10 14 ⁇ ⁇ cm or more, indicating that the electrical insulation was very high.
• the above measurement method is referred to as “pigment tablet electrical resistance measurement method”.
• the black colorant used for forming the coating film includes a method for producing a colorant by sufficiently dispersing the black pigment directly with other materials, and a processed pigment by sufficiently dispersing the black pigment in advance at a high concentration.
• a high concentration pigment black coloring composition is manufactured, and then a necessary material is added to form a colorant.
• the azo black pigment of the present invention is a coloring composition that, when used, is colored black or an achromatic dark color, or a dark chromatic color, depending on the purpose, application, usage, etc.
• the pigment component containing can be used in various forms as a liquid coloring composition containing a pigment component in a liquid dispersion medium or a solid coloring composition containing a pigment component in a solid dispersion medium.
• the azo black pigment of the present invention is a pigment component, an azo black pigment alone, or a chromatic color pigment, a white pigment, another black pigment and an extender pigment as one of a plurality of pigment components.
• One type or two or more types can be selected according to the color and used in combination.
• the mixing ratio of the chromatic color pigment, white pigment, other black pigment or extender pigment used in combination with the azo black pigment of the present invention to correct the color of the azo black pigment is not particularly limited, but it is computer color matching It is also a preferable mode to decide by a method that is optimized using a toning system of a system, for example, “Karacom System” (Daiichi Seika Kogyo Co., Ltd.).
• a known pigment can be used and is not particularly limited.
• anthraquinone pigment, quinacridone pigment, diketopyrrolopyrrole pigment, indigo / thioindigo pigment, perinone pigment, perylene pigment, phthalocyanine pigment, indoline pigment, isoindoline pigment, isoindolinone pigment Choose from dioxazine pigments, quinophthalone pigments, nickel azo pigments, metal complex pigments, insoluble azo pigments, high molecular weight azo pigments, organic pigments such as aniline black pigments, complex oxide pigments, and inorganic pigments such as iron oxide pigments At least one pigment, or a mixture of two or more pigments, a mixed crystal pigment, or a stacking (laminated) pigment.
• Organic pigments include, for example, yellow pigments and C.I.
• Pigment Red (abbreviated as PR) 4, 5, 23, 48: 2, 48: 4, 57: 1, 112, 122, 144, 146, 147, 150, 166, 170, 177, 184, 185, 202, 207, 214, 220, 221, 242, 254, 255, 264, 272 and the like; and mixed crystal pigments and stacking pigments thereof.
• C.I. I. Pigment blue (abbreviated as PB) 15: 1, 15: 2, 15: 3, 15: 4, 15: 5, 15: 6, 16, 17: 1, 60, 80, aluminum phthalocyanine blue, etc .
• C.I. I. Pigment Green (abbreviated as PG) 7, 36, 58, poly (13-16) bromocopper phthalocyanine, poly (13-16) bromozinc phthalocyanine, etc .
• I. Pigment violet (abbreviated as PV) 19, 23, 37 and the like; and mixed crystal pigments and stacking pigments thereof.
• black pigments include complex oxide black pigments, perylene black pigments, and aniline black pigments.
• the azo black pigment of the present invention as a colorant, especially in the liquid pigment dispersion, it is preferable to add an anionic and cationic pigment derivative azo black pigment.
• a method of introducing a diazo component or coupling component having an ionic group by an accessory coupling method, or a separately synthesized pigment derivative having an ionic group at the time of a fine particle production process or pigment dispersion It is carried out by a known method such as a method of adding at the time of preparing the liquid.
• the pigment derivative chromatic pigment derivatives such as yellow, blue, and red are appropriately used in addition to the black pigment derivative, including the adjustment of the color tone.
• the above-described known color pigments are also used for the red, green, blue, yellow, and purple pigments used for the chromatic color pixels of CF R, G, and B. Since the pixels are required to be clear and have high transmittance, the pigment particles are desirably ultrafine, and the average particle diameter is about 10 nm to 100 nm, preferably about 15 nm to 50 nm. In order to make the pigment ultrafine, it is preferable to use the above-described salt milling method, and to sufficiently wash and wash with water similarly to the black pigment.
• the chromatic color pigment When the chromatic color pixel is also formed in a state where it is in contact with or close to the electrode together with the BM, the chromatic color pigment similarly has a volume specific resistance of 10 10 ⁇ ⁇ cm or more, preferably It preferably exhibits a high electric resistance characteristic of 10 12 ⁇ ⁇ cm or more.
• a black coating film such as CF BM
• a liquid black colorant As the pigment dispersant used in the liquid colorant, a pigment- or solvophilic copolymer or oligomer, a low-molecular surfactant or the like is used.
• the film-forming material is selected according to the method of forming a coating film such as CF BM, for example, a heat drying method, a heat curing method, an energy ray curing method, etc., and is used as a polymer, oligomer or monomer. Are selected and used in combination.
• the pigment dispersant or film-forming material itself is liquid, or contains a liquid medium comprising an organic solvent system, an aqueous system, or a water-hydrophilic organic solvent mixed solvent system as a dilution medium, If necessary, it further contains additives such as a curing catalyst, a polymerization catalyst, a leveling agent, and an antifoaming agent.
• the pigment to be used is prepared in advance as a high-concentration pigment processed product in which the pigment to be used is finely dispersed in a dispersion medium, Manufacturing can be facilitated.
• the liquid high-concentration pigment dispersion is called “base color” or “base ink” and is used.
• the solid or wet type resin dispersion colorant containing the azo black pigment of the present invention is a colorant mainly used for internal coloration of plastics and synthetic fibers. It is used in known product shapes such as master powder, master batch, moisturizing master batch, etc., which are pigment dispersions, and colored pellets colored throughout.
• the solid dispersion medium at least one selected from thermoplastic resins, thermosetting resins, waxes, fatty acid amides, fatty acid metal soaps, and the like can be used.
• a pigment-philic or amphiphilic copolymer is used as a pigment dispersant.
• a graft copolymer or a block copolymer in which both functions are separated is preferable.
• the resin binder as a coating forming material, baking-type resin binder and radiation-curable resin binder having air drying or a reactive group in a non-reactive no known reactive groups are employed.
• room temperature drying type or baking type resin binders include, for example, acrylic resins, vinyl resins such as styrene (co) polymers, amino resin-modified polyester resins, polyurethane resins, acrylic polyol urethane resins, and soluble resins.
• Polyamide resin soluble polyimide resin, soluble polyamideimide resin, soluble polyesterimide resin, alkyd resin, aminoalkyd resin, epoxy resin, chlorinated rubber resin, silicon resin, fluororesin, cellulose acetate resin, nitrocellulose Resin, hydroxyethyl cellulose, water-soluble salt of styrene-maleic acid ester copolymer, water-soluble salt of (meth) acrylic acid ester (co) polymer, water-soluble aminoalkyd resin, water-soluble aminopolyester resin And water soluble Such as polyamide resin and the like, which are used in combination or alone or in combination.
• Examples of the reactive group possessed by the reactive film forming material include a methylol group, an alkylmethylol group, an isocyanate group, a masked isocyanate group, and an epoxy group.
• oligomers and monomers can be used depending on the application, and a crosslinking agent may be used.
• a crosslinking agent for example, methylolmelamine-based, isocyanate-based, and epoxy-based crosslinking agents are also used in combination.
• energy ray curable coating material such as ultraviolet (light) curable resin and electron beam curable resin
• ultraviolet (light) curable resin and electron beam curable resin include photocurable cyclized rubber resin, photocurable phenolic resin, light Curable polyacrylate resins, photocurable polyamide resins, photocurable polyimide resins, etc., and unsaturated polyester resins, polyester acrylate resins, polyepoxy acrylate resins, polyurethane acrylate resins, polyether acrylate resins And binders such as polyol acrylate resins, or binders to which monomers are further added as reactive diluents.
• optical density optical density: “OD value”
• OD value optical density: “OD value”
• the film thickness of the BM that brings about it is usually 0.8 ⁇ m to 3 ⁇ m.
• the BM itself is thickened, pixels are stacked on the BM, or a colorless resin film is stacked, and 5 ⁇ m to 10 ⁇ m is preferable.
• the OD value per 1 ⁇ m thickness is not generally determined by the thickness of the BM to be applied, it is set to 1.0 / ⁇ m or more, preferably 1.5 / ⁇ m or more. It is required that when the film thickness is thin to increase the pigment content in the coating film, if thick may be low pigment content, the range is about 60 to 20% in mass%, preferably from 55 to 30%.
• the black colorant containing the azo black pigment of the present invention for example, the pigment content of resist ink and ink-jet ink is set to a relatively low pigment content of about 5 to 15%, preferably about 5% to 10%. It is preferable that the pigment is stably dispersed, has high storage stability, maintains a viscosity suitable for coating, and forms a uniform colored film.
• the azo black pigment of the present invention has a high electrical insulation property with a volume specific resistance of 10 10 ⁇ ⁇ cm or more. Therefore, even when the pigment content is increased in order to provide the high OD value as described above, there is no decrease in the electrical resistance value due to the pigment as seen in the pigment having a low electrical insulation value. For this reason, by using the azo black pigment of the present invention, the formulation of a sufficiently high light-shielding coating film can be studied, and the quality of CF and organic EL parts can be guaranteed.
• BM formation method and pixel formation method are performed in accordance with conventional methods.
• the CF substrate known glass CF substrates, plastic CF substrates, and plastic films for transfer or pasting can be used.
• it is formed by one or more forming methods selected from an inkjet printing method, a printing method, a transfer method, a pasting method, and the like.
• a chromatic color pixel is formed on the CF substrate on which the BM is formed by a known pixel forming method using a known chromatic color pixel forming colorant.
• a chromatic color pixel is formed on the CF substrate on which the BM is formed by a known pixel forming method using a known chromatic color pixel forming colorant.
• it is formed by one or two or more forming methods selected from a photolithography method, a laser ablation method, an ink jet printing method, a printing method, a transfer method, a pasting method, and the like.
• black backsheets for photovoltaic modules is carried out according to conventional methods.
• a colorant a pigment obtained by coating a light reflective pigment with a black pigment, or a method of using a mixture of both, or a light reflective sheet as a base, the azo black pigment of the present invention is used.
• the colorant composition is coated, applied, stuck, welded, stacked, printed, ink jet printed, electrophotographic printed or electrostatically printed to give a reflective color in the infrared region and light reflective.
• a back sheet for a photovoltaic power generation module is formed, wherein a black or dark infrared transmissive layer is laminated on the sheet.
• a color filter substrate or an organic EL light-emitting substrate formed in such a manner that an electrode such as a TFT and a BM or a pixel that is substantially highly electrically insulating are in contact with or close to each other, and those A color display device equipped with a color display panel is provided with high reliability.
• Production Examples 1 to 12 are production methods for obtaining the azo black pigments of the examples of the present invention, and the obtained pigments are all black pigments of the examples of the present invention.
• a compound having one or more amino groups which is a starting material for obtaining a diazonium salt used for azo coupling, is referred to as a “diazo component”.
• Coupled component-1 2-hydroxy-11H-benzo [a] carbazole-3-carboxy- (2′-methyl) -p-anisidide
• the solution of the coupling component-1 was kept at 0 to 10 ° C., and the diazonium salt solution obtained above was added dropwise thereto. Subsequently, the solution was kept at 15 ° C. or lower, and the pH was adjusted to 6.5 to 7.0 using sodium acetate to perform a coupling reaction.
• the mixture was filtered, washed with methanol and washed with water to obtain a pigment press cake.
• the obtained pigment press cake was dried and pulverized to obtain a crude pigment (crude, coarse particle pigment).
• the yield was 10.36 g, and the yield was 95%.
• the obtained ground product was stirred for 1 hour in 3,000 parts of warm water heated to 80 ° C., and then filtered and washed to remove sodium chloride and diethylene glycol. Further, it was washed with ion-exchanged water having a conductivity of 2 ⁇ S / cm or less until the conductivity of the washing filtrate was about 100 ⁇ S / cm or less to obtain a miniaturized azo black pigment presscake.
• the obtained pigment press cake was dried and pulverized to obtain an azo-based black pigment refined powder pigment.
• black pigment-1 black pigment-1
• the average particle size of the black pigment-1 obtained above was measured by the following method. Take a transmission electron micrograph (60,000 times) of the black pigment-1 obtained, and measure the particle size distribution using the image analysis type particle size distribution software, Mac-View (manufactured by Mountec). did. As a result, the average particle size of Black Pigment-1 was about 80 nm. This method is referred to as “image analysis type particle size distribution measurement method”.
• a black pigment-1 compression-molded tablet was prepared by the following method, and the volume resistivity of the powder pigment itself was measured by the above-mentioned “pigment tablet electrical resistance measurement method”.
• black pigment-1 powder pigment
• a tablet was formed.
• the volume resistivity of the pigment tablet formed as above was measured using a high resistivity meter Hiresta UP. The measurement result showed 10 14 ⁇ ⁇ cm or more, and it was found that Black Pigment-1 itself has very high electrical resistance characteristics.
• the average particle diameter of the pigment was measured by “image analysis type particle size distribution measurement method”, and the volume resistivity of the pigment itself was measured by “pigment tablet electrical resistance measurement method”.
• Tables 1 and 2 collectively show the names, compound names, and molecular weights of diazo components and coupling components used in Production Example 2-11 described later.
• the obtained press cake was dried and pulverized to obtain fine powder powder pigments of the respective azo black pigments.
• the obtained pigments were designated as “black pigments 2 to -11”, respectively.
• the average particle diameter of the obtained black pigments was measured, as shown in Table 4, all were in the range of 80 to 90 nm.
• the volume resistivity of each of the black pigments -2 to -11 was measured, as shown in Table 4, all were 10 14 ⁇ ⁇ cm or more, and it was confirmed that the pigments themselves showed high insulation properties. It was.
• Example 1 Evaluation of spectral transmittance of coating film containing black pigment-1 of Production Example 1
• a black film-formed polyethylene terephthalate (PET) film was prepared.
• a 50% xylene-butanol mixed solvent solution of an acrylic resin having a carboxyl group (acid value is 10 mgKOH / g) and a 50% xylene-butanol mixed solvent solution of a butylated methylolmelamine resin are blended at a ratio of 80:20,
• the varnish used below was prepared (hereinafter simply referred to as “varnish”).
• As the diluent solvent a mixed solvent of xylene-butanol (4: 1) was used (hereinafter referred to as “diluted solvent”).
• the black coating film containing black pigment-1 has a spectral transmittance of 0% over the entire wavelength region of 400 to 750 nm in the visible light region. It was confirmed that almost no transmission occurred. In the near-infrared region, the transmittance increases rapidly in the near-infrared region near 800 nm, the transmittance in the near-infrared region of 900 nm is 36%, and further increases gently on the longer wavelength side. It was confirmed that
• Example 2 Evaluation of light reflection characteristics of coating film containing black pigment-1 of Production Example 1
• the black pigment-1 was evaluated as follows in order to see the reflection characteristics on the reflection surface of the white plate. Formation of the black PET film obtained in Example 1 (1) With a white plate applied to the back surface without the coating film, a visible part and a near red color were measured using a Hitachi spectrophotometer (U-4100, manufactured by Hitachi, Ltd.). External spectral reflectance was measured. Table 6 shows the measurement results.
• the spectral reflectance of the white plate back obtained by applying a white plate to the back surface of the black PET film prepared using the black pigment-1 (hereinafter referred to as the spectral reflectance of the white plate back).
• the reflection of the light of the black PET film by the white plate back is reflected from the surface of the black pigment particles constituting the black coating film, and the light transmitted through the black coating film is reflected by the underlying white plate. It is considered that the light is added to form reflected light, which is considered to be a factor that increases the spectral reflectance in the near infrared region.
• These facts indicate that near-infrared light can be reflected more efficiently if the light transmittance of the black pigment is made higher and a base using a highly reflective base is used.
• the reflectance is not 0% up to about 700 nm but a value of 5% because of the relationship with the measuring apparatus.
• Example 3 (1) In the same manner as in Example 1, black PET films were prepared using the black pigments 2 to -12 obtained in Production Examples 2 to 12, respectively. The dry film thickness of the black coating was about 30 to 40 nm, respectively. Subsequently, using the obtained black PET films, the spectral transmittances of the visible part (visible region) and the near infrared part (infrared region) were measured in the same manner as in Example 1. Table 7 shows the results. As shown in Table 7, although there was a slight difference depending on the structure of the pigment, the same tendency as that of the black PET film produced using the black pigment-1 was shown.
• Example 4 (Formation of CF BM) (1) Preparation of black pigment dispersion 40 parts of 25 parts of black pigment-1 and benzyl methacrylate-2-hydroxyethyl methacrylate-methacrylic acid copolymer (molar ratio: 60:20:20, mass average molecular weight 30,000) 25 parts of a propylene glycol monomethyl ether acetate (hereinafter abbreviated as PGMA) solution (hereinafter referred to as “acrylic copolymer solution-1”) and 50 parts of PGMA were sufficiently premixed.
• PGMA propylene glycol monomethyl ether acetate
• black pigment dispersion-1 a black coloring composition containing a pigment at a high concentration.
• black pigment dispersion-1 a black coloring composition containing a pigment at a high concentration.
• acrylated acrylic polyol solution 50% PGMA solution of acrylated acrylic polyol photocurable resin (hereinafter referred to as “acrylated acrylic polyol solution”). 6 parts), 2 parts dipentaerythritol hexaacrylate (hereinafter abbreviated as DPEHA), and ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole as a photopolymerization initiator 1 part of -3-yl]-, 1- (O-acetyloxime) (“Irgacure OXE02”, manufactured by BASF) and 51 parts of PGMA were blended and sufficiently stirred with a high-speed stirrer. Thereafter, the mixture was filtered through a filter having a pore size of 3 ⁇ m to prepare a black resist ink containing black pigment-1. Hereinafter, this is referred to as “photocurable black resist ink-1”.
• DPEHA dipentaerythritol hexaacryl
• the volume resistivity of the black coating film on the glass substrate obtained above was measured using a high resistivity meter Hiresta UP.
• the measurement result was 10 14 ⁇ ⁇ cm or more, and it was confirmed that this black coating film exhibits high insulation.
• Example 5 (Preparation and evaluation of photocurable black resist ink-2 to -12)
• black pigment dispersions 2 to -12 were prepared using the black pigments 2 to -12 obtained in Production Examples 2 to 12 instead of the black pigment 1, respectively.
• photocurable black resist inks 2 to -12 were respectively prepared.
• the ink was applied onto a glass substrate with a spin coater, pre-dried, pre-baked, and an ultrahigh pressure mercury lamp The film was exposed to light and post-baked to obtain black coating films each having a thickness of 3 ⁇ m.
• any black coating film has a volume specific resistance of 10 14 ⁇ ⁇ cm or more and exhibits high insulation.
• Example 6 (Optimization of light absorption in the visible light region of the BM film) As shown in Table 10, the spectral transmittance in the visible light region of the BM film prepared using the black pigment-6 in the same manner as in Example 5 was found to be slightly transmitted on the low wavelength side. It was. Therefore, in order to maximize the light absorptivity in the visible light region as the BM film, the black pigment-6 was complemented with a chromatic pigment and the color was adjusted and optimized. Regarding the blending ratio of the colored pigments, a color matching system of Karacom System (Daiichi Seika Kogyo Co., Ltd.) was used as a computer color matching system.
• a yellow pigment as a pigment suitable for toning.
• a photocurable yellow resist ink-1 was prepared in the same manner as in Example 4 except that PY138 was used as a yellow pigment.
• a coating film was formed on the glass substrate so as to have a film thickness of 1 ⁇ m.
• the light absorption in the visible light region as the BM film was optimized using the color adjustment system of the Karakom system. As a result, it was found that the mass ratio of black pigment-6 and PY138 was corrected with a color ratio of about 100: 5 to 25.
• the photocurable black resist ink-6 and the photocurable yellow resist ink-1 are blended in an amount such that the mass contrast is 87:13 in terms of pigment, and “photocurable black resist ink-13” is prepared. It was.
• the obtained photocurable black resist ink-13 was applied on a glass substrate to form a BM film having a thickness of 3 ⁇ m. As shown in Table 11, the BM film was confirmed to exhibit sufficient absorbability over the entire visible light region. Further, since the long wavelength side of the visible light region is sufficiently absorbed and shielded, it is suitable for a system using a backlight of an LED light source.
• Example 7 (Formation of insulating BM on array substrate)
• an array substrate including an array electrode composed of a source electrode, a drain electrode, and a gate electrode and a switching active element that activates a pixel electrode is set on a spin coater, and the photocurability obtained in Examples 4 to 6 is obtained.
• Black resist inks 1 to -13 were each spin-coated and prebaked at 80 ° C. for 10 minutes. After that, using a photomask having a mosaic pattern in which the width of the BM covering the electric circuit is 20 ⁇ m and the openings for the pixels are 280 ⁇ m long and 80 ⁇ m wide, a proximity exposure machine is applied to the coated surface of the array substrate.
• insulating BM formation array substrates-1 to -13 Using the ultra high pressure mercury lamp, exposure was performed with a light amount of 100 mJ / cm 2 . Next, development, washing and drying were performed with a dedicated developer and a dedicated rinse, and a highly insulating BM pattern having a thickness of about 3 ⁇ m was formed on each array substrate. These are respectively referred to as “insulating BM formation array substrates-1 to -13”.
• Example 8 (Formation of pixel pattern) (1) Refinement treatment of used pigments As chromatic pigments for pixels, PR254 (diketopyrrolopyrrole red pigment), PR177 (anthraquinone red pigment), PG36 (copper phthalocyanine green pigment), PB15: 6 ( ⁇ type) Copper phthalocyanine blue pigment), PY138 (yellow pigment) and PV23 (dioxazine violet pigment) were prepared.
• 100 parts of each pigment and 700 parts of sodium chloride powder were charged into a kneader, refined, dissolved in salt and solubles, filtered, washed with water, A chromatic pigment press cake was obtained.
• each pigment presscake was 35-45%.
• the press cake was dried and pulverized to obtain a fine powder pigment.
• the average particle size of each pigment was measured in the same manner as in Production Example 1, it was about 25 nm.
• the volume specific resistance of each refined powder pigment was measured, it was 10 14 ⁇ ⁇ cm or more, and it was confirmed that these chromatic pigments also showed high insulation properties.
• Pigment Dispersion Liquid pigment dispersions of red, green, blue, yellow and purple were prepared in the same manner as in Example 4 (1). 1 part of a pigment derivative having a known tertiary amino group was blended with 19 parts of each of the finely-divided chromatic pigments obtained in the above (1), and 15.2 parts of acrylic copolymer solution-1 was mixed therewith. And PGMA 64.8 parts. Next, these were sufficiently premixed and then dispersed with a continuous horizontal medium disperser “Dynomill ECM-Pilot 1.5 liters” to obtain a pigment dispersion of each color. When the average particle diameter of the pigment dispersion of each color was measured with a particle size measuring instrument N-4, it was about 40 to 45 nm.
• each pixel was adjusted using each of the chromatic pigment dispersions obtained above.
• PR254 and PR177 pigment dispersions were blended at 8: 2 to obtain “Red Pigment Dispersion-1”.
• a pigment dispersion of PG36 and PY138 was blended at a ratio of 5: 5 to obtain “Green Pigment Dispersion-1”.
• a pigment dispersion of PB15: 6 and PV23 was blended at 8: 2 to obtain “Blue Pigment Dispersion-1”.
• the “green resist ink-1” for the green pixel and the “blue resist for the blue pixel are used by using the green pigment dispersion-1 and the blue pigment dispersion-1, respectively, instead of the red pigment dispersion-1.
• Ink-1 "was prepared.
• the red resist ink-1, the green resist ink-1, and the blue resist ink-1 are respectively applied to the insulating BM formation array substrates -2 to -13 obtained in Example 7. Each was coated, exposed, developed, washed, and dried to form a red, green, and blue mosaic pattern on the array substrate to obtain a CF with BM and RGB pixels.
• Example 9 (Preparation of color filter with aqueous IJ ink) (1) Preparation of aqueous pigment resin dispersion (aqueous color base) 20 parts of each of the red, green, blue, yellow and purple pigment presscakes refined in Example 8 (1) in pure pigment content 16 parts of aqueous resin pigment dispersant-2 described below was added thereto. And ion-exchange water was added so that it might become a total of 100 parts. This was stirred with a dissolver for 2 hours, and after confirming that there were no pigment lumps, dispersion treatment was performed with “Dynomill ECM-Pilot 1.5 liters” to obtain an aqueous color (pigment dispersion) of each color. It was.
• the average particle size of each of the water-based color dispersed pigments was about 40 to 45 nm.
• the resin pigment dispersant-2 used above is benzyl methacrylate-ethyl methacrylate-2-ethylhexyl methacrylate-2-hydroxyethyl methacrylate-methacrylic acid copolymer (mass ratio; 30: 20: 20: 20: 10).
• Ammonium salt aqueous solution having a solid content of 50%, and using butyl carbitol: isopropanol: water 35: 35: 30 as a solution medium.
• the color of the pixel was adjusted using the pigment dispersion of each color obtained above.
• PR254 and PR177 pigment dispersions were blended at 8: 2 to obtain “Red Pigment Dispersion-2”.
• a pigment dispersion of PG36 and PY138 was blended at a ratio of 5: 5 to obtain “Green Pigment Dispersion-2”.
• a pigment dispersion of PB15: 6 and PV23 was blended at 8: 2 to obtain “blue pigment dispersion-2”.
• pixels are formed with IJ ink on “insulating BM formation array substrate-1” obtained in Example 7.
• a hole was formed.
• the positive resist composition was applied to the surface of the substrate with a coater so that the total thickness from the dried glass substrate was 8 ⁇ m, and air-dried at 50 ° C. or less.
• the positive resist film was exposed to ultraviolet light from the back surface of the substrate, developed with a 3% aqueous solution of phosphoric acid and 3% soda, washed with water, neutralized with a 1% aqueous solution of phosphoric acid, washed with water and dried.
• a CF substrate having an opening surrounded by a partition wall having a height of about 8 ⁇ m and having a hole with a length of 280 ⁇ m and a width of 80 ⁇ m was prepared.
• the positive resist composition used above is composed of 4 parts of ester obtained by reacting 1,2-naphthoquinone-2-diazide-5-sulfonyl chloride with o-chlorophenol-formaldehyde resin, and 2 parts of novolak resin.
• a 20% solid content resin composition comprising 2 parts of an oil-soluble phenol resin, 2 parts of a water-swellable resin comprising an acrylic acid-polystyrene macromonomer (6: 4) copolymer, and 90 parts of ethylene glycol monomethyl ether. is there.
• each color was printed, it was dried and pre-baked.
• the surface of the substrate was irradiated with ultraviolet rays, the partition made of a positive resist was photodecomposed, immersed in a 4% trisodium phosphate aqueous solution, washed and removed, and neutralized with dilute acid. Thereafter, it is washed with water, dried, and further baked at 180 ° C. to cure the coating film to form a red, green, and blue mosaic pattern, and to form RGB pixels on the insulating BM formation array substrate.
• CF was obtained.
• the film thickness of each pixel is about 2 ⁇ m, and the pixel film on the formed CF substrate is independent of color mixing, has no uneven color density, has a smooth surface, and has a clear mosaic pattern 3. Color pixels are shown.
• an IJ printer is formed in the hole for pixel formation.
• Each color ink of R, G, B was ejected from the head and filled. After each color was printed, it was dried and pre-baked. Next, ultraviolet rays are irradiated to photolyze the partition walls, the partition walls are removed with an alkaline aqueous solution, neutralized, washed with water, dried, baked at 180 ° C. and cured to form RGB pixels on the insulating BM formation array substrate. Each of the obtained substrates was obtained.
• the substrate on which the RGB pixels are formed on the insulating BM formation array substrate obtained in Examples 8 and 9 is coated with an overcoat layer on the entire surface according to a conventional method, and an ITO transparent electrode film is formed by sputtering deposition. Then, an alignment film was formed, and a CF substrate was manufactured. Further, a counter substrate and a spacer were assembled according to a conventional method, and a liquid crystal was loaded to produce a liquid crystal display. These CFs are manufactured using a manufacturing method that is rational, economical, high-definition, and capable of handling wide apertures, so for large-sized liquid crystal displays, medium-sized monitor liquid crystal displays, and small-sized mobile TVs. Can be provided at low cost.
• Example 10 Heat-shielding back sheet for photovoltaic module
• a horizontal type in which 15 parts of black pigment-1, 15 parts of an acrylic polyol (hydroxyl value: 100) butyl acetate solution (solid content 50%) and 50 parts of butyl acetate are sufficiently premixed and glass beads are used as a dispersion medium.
• the pigment was dispersed with a continuous medium disperser to prepare a black pigment high-concentration dispersion containing the pigment at a high concentration.
• the black coating liquid prepared in (1) above was applied to the surface of a PET substrate sheet (film thickness: 100 ⁇ m) and dried to form a black coating film (dry film thickness: 5 ⁇ m). Furthermore, the white coating liquid obtained in (2) above is applied to the back surface and dried to form a white coating film (dry film thickness: 5 ⁇ m), with the black coating film on the front and the white coating film on the back surface.
• a multilayered PET sheet was obtained. Hereinafter, this is referred to as a “black white multilayer PET sheet”.
• a silica / alumina-deposited polyester film (film thickness: 12 ⁇ m) was laminated.
• the adhesive used here was 70 parts of the acrylic polyol butyl acetate solution used in (1) above, 15 parts of hexamethylene diisocyanate trimer, and 15 parts of butyl acetate (hereinafter referred to as acrylic polyol). (Referred to as hexamethylene diisocyanate adhesive).
• further PET base sheet film thickness: 100 [mu] m
• PET back sheet for photovoltaic module
• the appearance of the PET back sheet coated with a multi-layered black coating and white coating obtained above was black and excellent in aesthetics due to the properties of black pigment-1. Further, due to the optical properties of Black Pigment-1, the PET backsheet transmits light in the infrared region of sunlight through the black coating layer on the surface, reflected by the underlying white layer, and again through the black layer. And radiated to the outside, so that it absorbs less sunlight and exhibits excellent heat shielding properties.
• Such a PET back sheet is suitable as a back sheet for a photovoltaic power generation module that is desired to avoid a temperature rise.
• a photovoltaic power generation module was produced according to a conventional method.
• a surface sealing sheet is pasted on the light-receiving surface side surface of the photovoltaic cell, and the light-shielding back sheet is pasted as a protective sheet on the non-light-receiving surface side of the back surface, with the black surface facing the light-receiving side, Equipped with a transparent glass substrate, these were sandwiched and sealed with a sealing material made of ethylene vinyl acetate resin, to obtain a photovoltaic power generation module.
• the obtained photovoltaic power generation module has excellent power generation efficiency.
• Example 11 Heat-shielding backsheet for photovoltaic module
• 40 parts of black pigment-1 and 60 parts of polyester resin powder were mixed with a Henschel mixer to obtain a powdery colorant.
• 12.5 parts of the obtained powdery colorant was blended in 87.5 parts of PET resin pellets, mixed with a Henschel mixer, then kneaded with a twin screw extruder, and made into black resin pellets with a pelletizer.
• a black PET film having a thickness of 50 ⁇ m was prepared by a T-die extruder.
• a white PET sheet (film thickness: 180 ⁇ m) kneaded and colored with a titanium oxide pigment was prepared. After applying the acrylic polyol-hexamethylene diisocyanate-based adhesive used in Example 10 (4) to the surface, the black PET film obtained in (1) above was pasted thereon, and the black film was laminated. A white PET sheet was prepared.
• the appearance of the black-white multi-layer PET back sheet obtained by laminating a black film and a white PET sheet was black and excellent in aesthetic appearance. Further, due to the optical properties of black pigment-1, sunlight in the infrared region passes through the black film layer on the surface, is reflected by the white PET sheet below, and is again transmitted through the black film to the outside. Therefore, the solar light is hardly absorbed and excellent heat shielding properties are exhibited. Therefore, the black-white multi-layer PET backsheet can be suitably used as a backsheet for a photovoltaic power generation module that wants to avoid a temperature rise.
• a photovoltaic power generation module was produced according to a conventional method.
• a solar cell is attached to the surface on the light-receiving surface side with a surface sealing sheet, the light-shielding back sheet as a protective sheet on the non-light-receiving surface side on the back surface, the black surface facing the light-receiving side, and the light-receiving surface
• a solar power generation module was prepared by sandwiching a glass substrate equipped with a transparent glass substrate with a sealing material made of ethylene vinyl acetate resin. The obtained photovoltaic power generation module has excellent power generation efficiency.

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