JP4738214B2 - Colorant for pixel formation and use thereof - Google Patents

Description

  The present invention relates to a colorant for forming a pixel and a color filter.

  With the recent development of information-oriented devices, LCD color displays are used as information display members for personal computers, mobile information devices, televisions, projectors, monitors, car navigation systems, mobile phones, electronic calculators and electronic dictionaries. It is used in a wide variety of information display related devices such as bulletin boards, information bulletin boards, displays of function display boards, sign boards, etc., and shooting screens of digital cameras and video cameras. Accordingly, color filters mounted on liquid crystal color displays are required to have better quality in terms of image characteristics such as fineness, color density, light transmission, and contrast.

  The color tones of the three primary color pixels of the color filter used in the liquid crystal color display, that is, red (hereinafter referred to as “R”), green (hereinafter referred to as “G”), and blue (hereinafter referred to as “B”) pixels, For example, a color tone that matches a corresponding maximum emission wavelength (for example, R: 610 nm, G: 545 nm, B: 435 nm) in the energy distribution of a three-wavelength fluorescent lamp used as a backlight is required. The transmission wavelength of the G color pixel needs to match the maximum emission wavelength of 545 nm of the G color of the three-wavelength fluorescent lamp, have high transmittance with respect to the maximum emission wavelength, and shield the R and B emission. .

  Green pigments generally used in colorants such as paints, synthetic resins and printing inks include C.I. I. Pigment Green (hereinafter abbreviated as “PG”) 7 (polychloro copper phthalocyanine pigment) and PG 36 (polybromo polychlor copper phthalocyanine pigment). As a green pigment for forming a G color pixel of a color filter, PG36 exhibiting yellowish green is mainly used. However, PG36 is obtained by bromination and chlorination of unsubstituted copper phthalocyanine. Therefore, as will be described later, the number of substituted bromine atoms and chlorine atoms is not constant for each production batch. Therefore, there is a problem that the color tone is not fixed to yellowish green suitable for color filters, and many green pigments with insufficient yellowness are generated.

  Further, in order to effectively bring out the optical characteristics of the G color pixel, 20 to 100% by mass of a yellow pigment is added to PG 36 in order to block the transmission of light in the short wavelength portion of PG 36. However, as described above, since the color tone (yellowish green) of PG 36 is likely to be blurred for each production lot, the maximum transmission wavelength of the formed G color pixel is corrected to 545 nm. A mass% of yellow pigment is added. As a result, there is a problem in that the transmittance of the G color pixel is sacrificed, and a portion where the hue and chromaticity expected on the chromaticity diagram do not appear due to the large amount of yellow pigment added.

  Accordingly, an object of the present invention is to provide a pixel forming colorant useful for forming G color pixels of the three primary color pixels of a color filter.

  As for the green pigment used in the G color pixel of the color filter, the inventors of the present invention have a polybromide copper phthalocyanine green pigment having a bromine atom substitution number of 14 or more and exhibiting a deep yellowish green color, and in particular, hexadecabromine finely divided into particles. It has been found that the maximum transmission wavelength of the transmission spectrum of a thin film containing copper phthalocyanine green pigment is 530 to 545 nm, and for the adjustment of the yellowish green hue blur and the transmission wavelength of the pigment which is a defect of the above-mentioned commercially available PG36 The present invention has been completed by finding that the disadvantages such as a decrease in pixel density and transmittance and a decrease in hue and chromaticity range due to the addition of a yellow pigment are solved.

That is, the present invention is a colorant for forming a green pixel of a color filter containing at least one of the following pigments (A) and (B) , which comprises a yellow pigment containing the pigment (A) or (B): The maximum transmission wavelength of the transmission spectrum of the thin film not included is approximately 527 to 530 nm, and the pigment is kneaded and ground together with a water-soluble salt in a kneader to reduce the average particle size to 10 to 150 nm. A pixel forming colorant is provided.
(A) An average of 14 to 16 bromine atoms obtained by reacting a copper salt with at least one component of phthalic acid substituted with an average of 3.5 to 4.0 bromine atoms and derivatives thereof is substituted. Copper phthalocyanine green pigment not substituted with chlorine atoms (hereinafter sometimes referred to as “green pigment A”)
(B) an average of at least one component with an average 1.0 to 2.0 chlorine atoms and an average of 3.0 to 4.0 amino phthalate bromine atom is substituted and derivatives thereof from 2.0 to 3 An average of 12 to less than 16 bromine atoms and an average of 4 or less obtained by reacting a mixture of at least one component of phthalic acid substituted with 0 bromine atoms and derivatives thereof with a copper salt Copper phthalocyanine green pigment substituted with more than 0 chlorine atoms (hereinafter sometimes referred to as “green pigment B” ).

In the present invention, the phthalic acid derivative as a reactive substance for the copper phthalocyanine green pigment (A) is a phthalic anhydride, phthalodinitrile, or phthalimide in which a bromine atom having an average of 3.5 to 4.0 is substituted. At least one selected from the group consisting of phthalamide, phthalamide acid and salts thereof; at least one of phthalic acid substituted with an average of 3.0 to 4.0 bromine atoms and derivatives thereof component, bets Riburomufutaru acid, tetrabromophthalic acid, their acid anhydrides, there in their dinitrile, acid imide, acid amides and amide acid derivative, and at least one compound selected from the group consisting of salts Phthalic acid substituted with an average of 1.0 to 2.0 chlorine atoms and an average of 2.0 to 3.0 bromine atoms, and At least one component of the derivatives of at least one selected from the group consisting of tribromo-monochlorophthalic acid, acid anhydrides thereof, dinitriles, acid imides, acid amides and amide acid derivatives, and salts thereof A compound selected from the group consisting of anionic, cationic and nonionic groups on a copper phthalocyanine green pigment having one or more substitution positions and 14 or more substituted with bromine atoms A green pigment derivative (C) having at least one group introduced therein; and the green pigment is at least one of hexadecabromo copper phthalocyanine green pigment and tetradecabromo-dichloro copper phthalocyanine green pigment, C) is, of penta decabromodiphenyl copper phthalocyanine sulfonated or Tet Decabrome - it is preferably a sulfonated product of monochloroacetic copper phthalocyanine.

Further, in the above invention, the average particle diameter of the green pigment, 10～130Nm Dearuko and are preferred.

In the present invention, the green pigment is dispersed in at least one of an organic liquid medium, an organic liquid-water mixed medium, an aqueous medium, and a solid resin medium; and further contains a yellow pigment It is preferable that the film-forming material further contains at least one of a polymer, an oligomer and a monomer.

  In addition, the present invention provides a pixel forming ink comprising the pixel forming colorant of the present invention as a coloring component; a color filter obtained using the pixel forming ink To do.

  At least selected from the group consisting of the green pigment A, the green pigment B, and the green pigment derivative C whose maximum transmission wavelength is longer than that of the conventional green pigment as the green colorant in the G color pixel of the three primary color pixels of the color filter. By using one kind, excellent optical characteristics such as high optical density, high light transmittance, and high contrast can be imparted to the G color pixel.

  The undesirable use of PG36 as a colorant for forming a G color pixel in a color filter is due to the influence of the particle size of the pigment and is not entirely attributable to the structure of the pigment. This is because the total number of bromine atoms and chlorine atoms introduced into the benzene ring of the phthalocyanine skeleton, particularly the number of bromine atoms introduced is large. PG36 is produced industrially by, for example, a method in which copper phthalocyanine is dissolved using a molten mixture of anhydrous aluminum chloride and sodium chloride as a solvent, and bromine and chlorine atoms are introduced using bromine and chlorine gas, so-called “post bromine”. And post-chlorination method ”.

  Purchasing and purifying a commercial product of PG36, making it fine particles, and analyzing the bromine and chlorine content in the commercial product. Table 1 shows the results and G color pixels of color filters using those pigments. Evaluation of maximum transmission wavelength and color tone was shown. Nine lots of PG36 were taken as test pigments. In order to purify the pigment of each lot, the powder pigment is dissolved in 100% by mass sulfuric acid, the solution is poured into a large amount of water to precipitate the pigment, and the precipitate is washed with an alkaline aqueous solution, dimethylformamide (DMF), ethanol. Washed. Looking at the results of elemental analysis in Table 1, the bromine content is 66.6% by mass to 60.4% by mass (average 64.6% by mass), which is the difference between the upper and lower limits of the above range 6.2. The mass% corresponds to about 9 mass% with respect to the average value. The chlorine content is also 8.08% to 5.74% by mass (average 6.51% by mass), and 2.34% by mass of the difference between the upper and lower limits of the above range is about 36% by mass of the average value. Equivalent to. Thus, the bromine and chlorine contents of commercially available PG36 vary greatly.

  Comparison of the analysis results of bromine and chlorine with the evaluation of green pigments for G color pixels in the color filters of each pigment commercial product does not necessarily indicate that there is a direct relationship between them. PG36, in which the number of introductions is sufficiently large and chlorine atoms are sufficiently introduced at the remaining substitution positions, shows a yellowish green color tone. However, when the number of bromine atoms introduced is small and chlorine atoms are introduced, the PG36 becomes bluish in tone, and even when the number of bromine atoms is reduced and the bromine atom content increases, Is insufficient, and the present green pigment for color filters is rejected.

  The reason why the bromine and chlorine contents greatly change is that the production method of PG36 is based on “post-bromination and post-chlorination method” of copper phthalocyanine, and halogen substitution of industrially produced PG36. Variations in the types of groups and their substitution numbers are inevitable. Therefore, it is necessary to select and use only an acceptable production lot for the commercially available PG 36, and the above-mentioned types of halogen substituents and fluctuations in the number of substitutions are determined by the G color pixel ink of an appropriate color filter, and by extension. It is difficult to produce the above-described high-quality color filter industrially and stably. The present invention solves the above problems.

  Next, the present invention will be described in more detail with reference to the best mode for carrying out the invention. The green pigment A used in the present invention is obtained by reacting a phthalic acid and / or derivative thereof having an average bromine atom substitution number of 3.5 to 4.0 with a copper salt, and an average of 14 to 16 It has 1 bromine atom and no chlorine atom. Examples of the phthalic acid derivatives include, for example, phthalic anhydrides having an average number of bromine atoms per molecule of 3.5 to 4.0, phthalodinitrile, phthalimide, phthalamide, phthalamic acid and sodium thereof, Examples thereof include alkali metal salts such as potassium.

  The green pigment A used in the present invention can be obtained by mixing urea, cupric chloride, a condensation catalyst and the like with one of the above polybromphthalic acids and reacting them according to a conventional method. Examples of the condensation catalyst include ammonium molybdate, titanium tetrachloride, and zirconium tetrachloride. As the reaction solvent, for example, nitrobenzene, trichlorobenzene, 1-chloronaphthalene and the like can be used. The reaction conditions are 175 to 200 ° C. and 2 to 4 hours. In the reaction, there is no significant difference in the reactivity of the polybromophthalic acids. After the reaction, the solvent is removed to obtain a crude pigment (pigment before pigmentation). The crude pigment is dissolved 7 to 20 times in 100% by mass sulfuric acid or fuming sulfuric acid, and the solution is poured into ice water to precipitate the pigment, whereby the green pigment A used in the present invention is obtained. Next, it is more preferable that the precipitate is washed with an aqueous alkaline solution and further purified with a solvent such as alcohol or DMF.

  It is preferable to further control the particle size of the obtained pigment. The pigment particle size is controlled by crystallizing the purified pigment by the solvent finish method or the like and then kneading and grinding it with a water-soluble salt and, if necessary, a water-soluble organic solvent in a kneader such as a kneader. Is called. The average particle size of the pigment whose particle size is controlled is generally 10 to 150 nm, preferably 20 to 110 nm. The pigment agglomerates obtained in the particle size control are suspended in a dilute sulfuric acid aqueous solution to dissolve and remove salts and water-soluble organic solvents. The precipitate is collected by filtration, washed with water, and used as an aqueous filter cake, or a finer pigment obtained by drying and grinding it, or a processed pigment co-precipitated or kneaded with an easily dispersible polymer.

  The green pigment A used in the present invention has a maximum transmission wavelength on the longer wavelength side than PG36 generally used, and gives a strong yellowish green color. Moreover, since the green pigment A is synthesized using polybromphthalic acids, it can be synthesized using the material by determining the bromine atom content at the time of selection of the raw material. As a result, the number of bromine atoms substituted in the green pigment A thus obtained is substantially constant, and has the feature that the G color pixel can constantly reproduce the color when manufacturing a color filter.

  The green pigment B used in the present invention includes, as a raw material for the pigment, at least one of phthalic acid having at least one bromine atom and derivatives thereof and phthalic acid having at least one chlorine atom and derivatives thereof. Except that the average number of bromine atoms in the green pigment obtained is 12 or more and less than 16 and the average number of chlorine atoms is 4 or more and more than 0. Same as A. That is, the production method for the green pigment B, the method for controlling the particle size of the pigment, the substituents other than bromine and chlorine atoms, the method for introducing them, and the effects thereof are the same as in the case of the green pigment A.

  In addition, as at least one of the phthalic acid having at least one bromine atom and a derivative thereof, dibromophthalic acid, tribromophthalic acid, tetrabromophthalic acid, their acid anhydrides, their dinitriles, acid imides, At least one compound selected from the group consisting of acid amides and amide acid derivatives, and salts thereof, and at least one of the phthalic acid having at least one chlorine atom and derivatives thereof is tribromo -At least one compound selected from the group consisting of monochlorophthalic acid, acid anhydrides thereof, dinitriles, acid imides, acid amides and amide acid derivatives, and salts thereof, and the bromine atom of the resulting pigment The number and the number of chlorine atoms are as described above.

  In the pigment A or B, a number corresponding to a substituent that suppresses excessive crystallization of the pigment at one or two positions of one or more benzene rings in which the bromine atom and the chlorine atom are not substituted. The green pigment derivative C it has can also be used. Substituents other than bromine and chlorine atoms in these pigments will be described later.

  The pigment derivative C having one or two substituents other than the bromine atom and chlorine atom is a method of using the phthalic acid having one or two substituents in the polybromophthalic acid as a part of the raw material, It is obtained by a method of introducing the above substituent into a 14-15 brominated copper phthalocyanine compound, a method of substituting a bromine atom with one or two other substituents, and the like. Since the pigment derivative C having one or two substituents other than bromine and chlorine atoms behaves like an amorphous or oil-soluble dye, it has a high backlight transmittance as a color filter pigment. , Light scattering is low, and thus the contrast of the color filter is improved. The pigment derivative C having an ionic group other than the bromine atom contributes to the dispersibility and dispersion stability of the green pigment A when used in combination with a polymer dispersant having a counter ion (counter ion).

  Examples of the substituent other than the bromine atom and the chlorine atom include, for example, a hydrocarbon group having 1 to 25 carbon atoms, more specifically, an alkyl group, an aryl group, an alkylaryl group, an arylalkyl group, an alkoxyalkyl group, Examples thereof include a hydrophobic hydrocarbon group such as a polyalkylene oxide group, a hydrophobic low-molecular group containing these hydrophobic hydrocarbon groups, an addition polymer residue, and an addition condensate residue. Examples of the ionic or water-soluble substituent include an anionic, cationic and / or nonionic water-soluble group or a hydrophilic low-molecular group containing them, more specifically, a sulfone group and a carboxyl group. An ionic or water-soluble group selected from the group consisting of sulfate group, phosphate group, amino group, quaternary amino group, pyridinium group and salts thereof, polyalkylene oxide group and glyceryl group, Examples thereof include hydrophilic addition polymer residues and addition condensate residues. A particularly preferred group is a sulfone group.

Each of the above substituents may be directly or carboxylic acid ester group, carboamide group, sulfoamide group, sulfate ester group, phosphate ester group, ether group, tertiary amino group, (mono or di) -iminotriazi. Substituted at one of the positions of the benzene ring of the phthalocyanine skeleton in which the bromine and chlorine atoms are not substituted through a linking group selected from the group consisting of a nylamino group and a (mono or di) -iminotriazinyloxy group Can do.
The “green pigment A”, “green pigment B”, and “green pigment derivative C” may be collectively referred to as “green pigment”.

  The colorant for forming a pixel of the present invention preferably contains 10 to 50% by mass of the above green pigment. The colorant is useful as a raw material for ink used to form G color pixels of a color filter. The production of the ink is performed in accordance with the production of a conventionally known ink. The pixel forming ink of the present invention including the pixel forming colorant contains the green pigment as an essential component, and further includes a pigment dispersant, a dispersion stabilizer, a film forming material, and a film forming aid as necessary. An agent etc. can be contained. In order to produce the pixel forming ink containing the green pigment finely dispersed in a stable and economical manner, the green pigment is used rather than the green pigment is directly used to produce the pixel forming ink. It is preferable to produce the ink via a colorant contained at a high concentration.

  The colorant for forming a pixel of the present invention has a high pigment content by applying optimum conditions for pigment dispersion, and it is desirable to use a material that is stable to physical factors such as heat and light as its component. For example, even when preparing a photoresist (photosensitive) ink, the coloring component is used as a high-density pixel-forming colorant, and the ink is directly produced without going through a high-density pixel-forming colorant. In addition, the pigment can be finely dispersed at a high concentration, and the pixel forming colorant of the present invention is safe and easy to handle for work, and the amount to be produced as long as it is a high concentration pixel forming colorant. Has the advantage of requiring a small amount.

  The green pigment is contained at a higher concentration in at least one of an organic liquid medium, an organic liquid-water mixed medium, an aqueous medium, and a solid resin medium rather than an ink medium that is actually used for pixel formation. It is preferable to disperse the pigment at a high concentration by this method. At that time, if necessary, an ionic pigment derivative as a pigment dispersant and an ionic polymer having a counterionic group thereof, a resin as a film-forming polymer, a surfactant, an antifoaming agent, a smoothing agent, an adhesion It is preferable to appropriately add various additives such as a oxidant and a silane coupling agent. The pigment concentration in the pixel forming colorant is not particularly limited, but is usually 10 to 50% by mass. The “ionic pigment derivative” is a compound in which an ionic group such as a sulfone group is introduced into a pigment molecule, and is a substance used as a pigment dispersant or dispersion stabilizer.

  The ionic pigment derivative is often added in the case of a solvent-based pigment dispersion. The blending ratio of the ionic pigment derivative called a so-called synergist to the pigment is preferably 0.05 to 40 parts by mass, more preferably 0.1 to 20 parts by mass per 100 parts by mass of the pigment. Moreover, the ionic polymer which has the said counterionic group is also used as a dispersing agent of a pigment, and the ratio of this ionic polymer type | system | group dispersing agent is 1-50 mass parts per 100 mass parts of pigments.

  In the case of producing a liquid colorant for forming a pixel, a group and / or molecular chain having affinity for the pigment in the molecule and a group and / or molecular chain having affinity for the solvent are used. It is preferred to use random, block and / or graft copolymers having a binder and dispersant, these copolymers being 10 to 200% by weight of the total amount of pigment and ionic pigment derivative, preferably It is preferable to use it in a total ratio of 20 to 100% by mass.

  Examples of the pigment disperser used in the production of the colorant for forming a pixel of the present invention include a known disperser, for example, a vertical medium disperser such as a ball mill, a sand mill and a bead mill, a horizontal medium disperser such as a dyno mill and a horizontal bead mill, Examples thereof include a roll mill, an ultrasonic mill, and a high-pressure collision disperser. The pigment is dispersed in the medium by a method of dispersing a plurality of times using one kind of the above-mentioned dispersing machines or a method of combining two or more kinds of dispersing machines.

  In the present invention, the desirable dispersed particle size of the pigment is, when it is made into an ink, the sedimentation property of the pigment in the ink, the aggregation property during storage, and the like, and the optical density, saturation, sharpness, transparency, and contrast properties of the pixel. In consideration of pixel characteristics that determine the quality of the display image, the average particle diameter is 10 to 130 nm, preferably 20 to 110 nm. As a method for obtaining a pigment dispersion having a desired particle size distribution, the size of the pulverizing media of the disperser is reduced, the filling rate of the pulverizing media is increased, the processing time is increased, and the discharge speed is decreased. Methods such as classification and separation with a filter or ultracentrifuge after pulverization are used. Or the combination of those methods is mentioned.

  As described above, the transmission spectrum of the green pigment used for forming the G color pixel for the color filter is matched with the transmission spectrum of the set G color pixel, for example, the maximum transmission wavelength is adjusted to 545 nm and shielded. In order to lower the transmittance of 400 nm to 500 nm, a yellow pigment exhibiting a preferable transmission spectrum may be added. In preparing such a pigment dispersion, the green pigment and the yellow pigment are each dispersed alone to form a colorant for pixel formation, and then mixed at a predetermined ratio, or the green pigment and the yellow pigment are mixed in a predetermined manner. There is a method of dispersing the compounded in the ratio at a time. Examples of the yellow pigment for complementary color include pigment yellow (PY) 62, 74, 83, 138, 139, 150, 155, 185, and the like.

  As the pigment forming the R and B color pixels used together with the G color pixel formed of the above green pigment, many conventionally known pigments are used. For example, azo pigments such as insoluble azo, soluble azo and high molecular weight azo, quinacridone red and quinacridone magenta quinacridone pigments, diketopyrrolopyrrole pigments, anthraquinone pigments, perylene pigments, phthalocyanines Blue-based phthalocyanine pigments, isoindolinone pigments, dioxazine pigments such as dioxazine violet, quinophthalone yellow pigments, complex pigments such as nickel azo yellow, and the like are used.

  Specific examples of pigments representative for R and B color pixels include pigment red (PR) 177, 242, and 254 as red pigments, and pigment yellow (PY) 83, 138, and 139 as yellow pigments for complementary colors. 150, 185, etc., pigment blue (PB) 15: 6, 60, etc. as a blue pigment, pigment violet (PV) 23, etc. as a violet pigment for complementary color, and the above-mentioned red pigment and yellow pigment And coprecipitated pigments of blue and purple pigments, solid solution pigments and mixed crystal pigments.

  The colorant or ink of the present invention preferably further contains a film forming material. As the film forming material, any of the known film forming materials conventionally used for coloring compositions for color filters can be used and is not particularly limited. When the pixel forming ink is a photolithographic development type (photosensitive type), an energy ray curable film forming material is used as the film forming material. In addition, in the case of addition polymerization or addition crosslinkable ink, heating or energy ray curable film forming materials such as thermal polymerization type, laser heat ray polymerization type, ultraviolet ray polymerization type, photocationic polymerization type, and electron beam polymerization type are used. The

  The film-forming material as described above is a conventionally known addition polymerization or monomer, oligomer and / or polymer having an unsaturated double bond or a polymerizable cyclic ether group having addition crosslinkability, and polymerization added as required. It is an addition polymerization or addition crosslinkable fixing agent comprising an initiator and a liquid medium.

  Specific examples of the film forming material include, as monomers, pentaerythritol di (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, bisphenol A type epoxy resin-di (meth) acrylate. And (meth) acrylic acid esters such as bisphenol F-type epoxy resin-di (meth) acrylate and bisphenolfluorene-type epoxy resin-di (meth) acrylate.

  Moreover, as a polymer, (meth) acrylic acid (co) polymer, (meth) acrylic acid ester type (co) polymer, styrene type (co) polymer, (meth) acrylic acid ester-styrene type copolymer Polyester acrylate resin, polyepoxy acrylate resin, polyurethane acrylate resin, polyether acrylate resin, polyol acrylate resin, etc .; photosensitive cyclized rubber resin, photosensitive phenol resin, photosensitive polyacrylate resin , Photosensitive polyamide resins, photosensitive polyimide resins, unsaturated polyester resins, and the like. These may be used alone or in combination of two or more. These resins preferably have an alkali-soluble substituent such as a carboxyl group or a phenolic hydroxyl group in the side chain for the purpose of improving developability after pattern exposure.

  Examples of the polymerization initiator include known photopolymerization initiators such as 1-hydroxy-cyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2,2-diethoxyacetophenone, 2-Methyl-1- (4- (methylthio) phenyl) -2-morpholinopropan-1-one, 2-benzyl-2- (N, N-dimethylamino) -1- (4-morpholinophenyl) butanone -1 etc. can be mentioned. These may be used alone or in combination of two or more.

  The color filter of the present invention can be obtained by forming G color pixels using the above photosensitive pixel forming ink in combination with pixels of other colors. The pixel formation method is not particularly limited, and a known color filter pixel formation method is used. For example, when forming color filter pixels on a substrate, the photosensitive pixel forming ink is coated on the substrate using, for example, a spin coater, a roll coater, a slit coater, a printing machine, and the like, After preliminary drying, a photomask is brought into close contact, and exposure is performed using an ultra-high pressure mercury lamp to form a pixel pattern. Next, development and washing are performed, and post-baking is performed as necessary, whereby a pixel pattern of a color filter can be formed.

  In addition, as a method of forming a color filter pixel using non-photosensitive pixel forming ink, for example, relief printing ink and flexographic printing plate as proposed in Japanese Patent Application Nos. 2004-209788 and 2005-011333. Pixels can be printed directly on the substrate as pixel forming printing inks such as ink, lithographic ink, intaglio gravure ink, stencil screen ink. Furthermore, inkjet printing, dispenser injection methods, pixel formation methods using electronic printing or electrostatic printing, and colored pixel formation methods by electrodeposition coating can also be used.

  Then, according to a conventional method, baking is performed as necessary, polishing for smoothing the surface, or top coating for protecting the surface is performed. In addition, a color filter having RGB pixels can be obtained by forming a black matrix according to a conventional method. In addition, a method of forming three primary color pixels on a transfer or pasting film and then transferring or pasting the three primary color pixels on a color filter substrate is also performed. The method for forming these color filter pixels is known, and the method for forming the color filter pixels is not particularly limited in the present invention.

  As the film forming material of these pixel forming inks, conventionally known dry-fixing type film forming materials can also be used, which can be used in the form of a solvent solution, an aqueous solution, an emulsion, a latex or a solid heat-meltable resin, As the film-forming polymer, random, block and / or graft copolymers with or without reactive groups can also be used. These film-forming materials can further contain a crosslinking agent as required.

  Specific examples of resin varnishes for inks that are dried to form a film include (meth) acrylic acid ester (co) polymers, styrene-maleic acid ester (co) polymers, and (meth) acrylic acid. Ester-styrene copolymer, epoxy resin, amino alkyd resin, polyester resin, amino resin modified polyester resin, polyurethane resin, acrylic polyol urethane resin, soluble polyamide resin, soluble polyimide resin, soluble polyamideimide Resin, soluble polyesterimide resin, etc .; water-soluble salt of (meth) acrylic acid ester-based (co) polymer, water-soluble salt of styrene-maleic acid ester-based copolymer, water-soluble aminoalkyd resin, water-soluble Examples include aminopolyester resins, which are used alone or in combination of two or more. It is used in combination.

  As a monomer having a group that reacts with a crosslinking agent, (meth) acrylic acid, maleic acid, 2-hydroxyalkyl (2 to 6 carbon atoms) (meth) acrylate, polyethylene glycol (meth) acrylate, glycidyl (meth) Examples thereof include acrylate, N-methylol (meth) acrylamide, and isocyanate ethyl (meth) acrylate. Examples of the crosslinking agent include trimethylolpropane polyglycidyl ether, pentaerythritol polyglycidyl ether, methoxymethylolated melamine, butoxymethylol melamine, polyhexamethylene carbodiimide, trimethylolpropane-tris (tolylene diisocyanate) adduct, trimethylolpropane-tris ( Hexamethylene diisocyanate) adduct and the like.

  Examples of the pigment dispersion medium of the pixel forming ink include alcohols such as propanol; (mono-poly) alkylene glycols such as (mono-poly) ethylene glycol and (mono-poly) propylene glycol, and monoalkyl ethers thereof. , Dialkyl ethers, monoalkyl ether monoacylates; esters such as ethyl acetate, butyl acetate, ethyl lactate and γ-butyrolactone; ketones such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; decane, “Isopar” (trademark) Name, manufactured by Exxon Chemical Japan Co., Ltd.), aliphatic hydrocarbon solvents such as “Shellsol” (trade name, manufactured by Shell Japan Co., Ltd.); alicyclic hydrocarbon solvents such as cyclohexane and methylcyclohexane; aromatics such as xylol hydrocarbon Agent; DMF, dimethylacetamide, N- methyl-2-pyrrolidone, 2-pyrrolidone, and a nitrogen-containing solvent such as 1,3-dimethyl-2-imidazolidinone.

  When the pixel forming ink is a water-based ink, the aqueous medium is water or a mixed solvent of water and a water-soluble organic solvent, and it is preferable to use ion-exchanged water, distilled water or the like as water. Examples of the water-soluble organic solvent used in the aqueous mixed solvent include conventionally known water-soluble organic solvents, specifically, lower alcohols such as ethyl alcohol and propanol, (mono-poly) ethylene glycol, (mono- Poly) propylene glycol, polyhydric alcohols such as (mono-poly) glycerin and their lower alkyl ethers such as methyl ether, ethyl ether and propyl ether: nitrogen-containing solvents such as N-methyl-2-pyrrolidone and 2-pyrrolidone Is mentioned.

  The color filter formed using the colorant or ink of the present invention is equipped in an image display device such as a liquid crystal color display, and is used for personal computers, mobile information devices, televisions, projectors, monitors, car navigation systems, mobile phones, electronic devices. It can be incorporated in various information display related devices such as a display screen of a computer or an electronic dictionary, an information bulletin board, a guidance bulletin board, a display such as a function display board and a sign board, and a photographing screen of a digital camera or video camera.

  In addition, the pixel formation of the color filter has been mainly described above. However, the colorant for forming a pixel of the present invention can be used in various other applications such as a synthetic or natural resin, a colorant for paint, a plastic film, Suitable as printing ink for paper, synthetic paper, paper colorant, textile printing agent printing ink, color copier toner, ink jet printer ink, thermal transfer ribbon ink green pigment colorant Yes, each giving an excellent green colored article.

  Next, the present invention will be described in more detail with specific examples. In the text, “part” and “%” are based on mass unless otherwise specified. Further, the number of bromine atoms and chlorine atoms substituted in the following copper phthalocyanine green pigment is the number calculated from the charging ratio of the raw materials used.

[Examples and Comparative Examples for Green Pigment A]
Example A-1 (Production of hexadecabromo copper phthalocyanine green pigment)
(1) Synthesis of hexadecabromo copper phthalocyanine A synthesis reactor having a stirrer, a reverse flow cooler, a reaction vessel equipped with a thermometer, and a heating device was prepared. The content of bromine atoms in the raw material tetrabromophthalic anhydride is 69.0%, and the number of bromine atoms substituted per molecule is 4.0. A reaction vessel was charged with 172.8 parts of trichlorobenzene, 40.0 parts of the above tetrabromophthalic anhydride, 23.3 parts of urea, 6.36 parts of titanium tetrachloride and 3.0 parts of cupric chloride and heated. The reaction was performed. The temperature was gradually raised from 100 ° C. to 175 ° C., and the mixture was stirred as it was for 3 hours to continue the reaction. The reaction temperature immediately before completion of the reaction was 195 ° C.

  The yield of the obtained crude pigment was 38.6 parts, and the crude pigment yield was 97.4%. 98% sulfuric acid and 20% fuming sulfuric acid were blended to prepare 100% sulfuric acid. After dissolving 20 parts of the obtained crude pigment in 140 parts of the above-mentioned 100% sulfuric acid and stirring at 70 ° C. for 1 hour, the solution was poured into 10 times ice water to precipitate the pigment, and the precipitate was filtered. The filter cake was washed with water. Subsequently, the filter cake was washed successively with a dilute aqueous sodium hydroxide solution, ethanol and DMF, and the filter cake was further treated with xylol to obtain a purified pigment. The yield of purified pigment was 93.9%.

  According to elemental analysis, the copper content of the purified pigment was 3.44% (theoretical value: 3.456%), and the bromine atom content was 69.8% (theoretical value: 69.52%) ( The content of chlorine atoms is 0%). The average number of bromine atoms substituted per molecule calculated from the analytical value of the obtained hexadecabromocopper phthalocyanine green pigment was 16.1, indicating that the phthalocyanine skeleton was substituted with 16 bromine atoms.

(2) Preparation of fine particle green pigment 100 parts of the purified pigment obtained in the above (1) was charged into a kneader equipped with a pressure lid together with 600 parts of sodium chloride powder and 110 parts of diethylene glycol. Premixing was performed until a uniformly moist mass was formed in the kneader, and then kneading and grinding were performed while the pressure lid was closed and the contents were pressed at a pressure of 6 kg / cm ² . Kneading and grinding were performed for 2 hours while controlling the temperature so that the contents were 92 to 98 ° C.

  The obtained ground product was stirred in 3,000 parts of 2% sulfuric acid heated to 80 ° C. for 1 hour, and then collected by precipitation filtration and washed with water to remove sodium chloride and diethylene glycol. A filter cake of fine green pigment was obtained. In order to measure the particle diameter of the obtained pigment, 200% of a nonionic active agent is added to the pigment filter cake with respect to the pigment, diluted with water, ultrasonically dispersed to prepare a pigment dispersion, and a particle size measuring instrument When measured with “Model N-4” (trade name; manufactured by Coulter, Inc.), the average particle diameter was about 40 nm. The filter cake was dried and pulverized to obtain a fine powder pigment “(16 bromo) green pigment A-1”.

Example A-2 (Production of sulfonated product of pentadecabromo copper phthalocyanine)
(1) Synthesis of pentadecabromo copper phthalocyanine In the same synthesis reaction apparatus as Example A-1 (1), 172.8 parts of trichlorobenzene, 30.00 parts of tetrabromophthalic anhydride, 8.23 parts of tribromophthalic anhydride, urea 23.3 parts, 6.36 parts of titanium tetrachloride and 3.0 parts of cupric chloride were charged and synthesized in the same manner as in Example A-1 (1) to obtain a crude pigment. The yield of crude pigment was 36.6 parts, and the yield of crude pigment was 96.5%. The pigment was purified in the same manner as in Example A-1. The yield of the coarse particle pigment obtained by purification was 94.1%. Hereinafter, the pigment is abbreviated as “15BrCuPc”.

(2) Synthesis of sulfonated product of 15BrCuPc 20 parts of 15BrCuPc obtained in the above (1) was dissolved in 140 parts of 20% fuming sulfuric acid and stirred at 110 ° C. for 2 hours to perform a sulfonation reaction of the pigment. The reaction solution was poured into 10-fold ice water to precipitate a sulfonated product. The precipitate was collected by filtration, and then the filter cake was sufficiently washed with water to obtain a sulfonated product of 15BrCuPc. Hereinafter, this is referred to as “PG sulfonic acid A-1.”

Example A-3 (evaluation of green pigment)
(1) Preparation of Green Pigment Dispersion As a pigment dispersant, a butyl acrylate-styrene-hydroxyethyl acrylate-methacrylic acid (mass ratio = 50/15/10/25) copolymer (average molecular weight: 12,000). ) Solution of 30% propylene glycol monomethyl ether acetate (hereinafter abbreviated as “PGMA”) (hereinafter referred to as “resin dispersant PGMA solution A-1”).

  19 parts of “(16 bromo) green pigment A-1” obtained in Example A-1 (2), 1 part of “PG sulfonic acid A-1” obtained in Example A-2 (2), high cationic property Blend 12 parts of molecular dispersant (polyester amidated polyethyleneimine, 50% solution), 50 parts of the above “resin dispersant PGMA solution A-1” and 18 parts of PGMA, and stir with a dissolver for 2 hours. After confirming the disappearance, a zirconia bead (diameter: 0.65 mm) was used in a horizontal annular bead mill disperser, and a dispersion treatment was performed at a peripheral speed of 14 m / s. Green pigment colorant A-1 ").

(2) Preparation and application of G color pixel forming ink 100 parts of “(16 bromo) green pigment colorant A-1” 50 parts of photosensitive acrylic resin varnish, 10 parts of trimethylolpropane triacrylate, 2-hydroxyethyl 2-methylpropan-1-one, 2 parts of 2,2-diethoxyacetophenone and 37 parts of PGMA were added to form a photosensitive green pigment dispersion (hereinafter referred to as “(16 bromo) green pigment photosensitive dispersion A-1”. Obtained). A glass substrate treated with a silane coupling agent is set on a spin coater, and the above-mentioned “(16 bromo) green pigment photosensitive dispersion A-1” is first spin-coated at 300 rpm for 5 seconds and then at 1,200 rpm for 5 seconds. did. Subsequently, prebaking was performed at 80 ° C. for 10 minutes, and exposure was performed with an ultrahigh pressure mercury lamp at a light amount of 100 mJ / cm ² to obtain a green glass substrate (hereinafter referred to as “(16 brom) green glass substrate A-1”).

Comparative Example 1
(1) Preparation of Green Fine Particle Pigment As a result of chemical analysis of bromine atom and chlorine atom for commercially available PG36 yellowish green pigment, bromine atom content is 66.6%, chlorine atom content is It was 6.95%. When the total number of halogen substitutions was calculated as 16, the number of substituted bromine atoms was 13 and the number of chlorine atoms was 3. The green pigment powder was charged into a kneader equipped with a pressure lid together with sodium chloride powder and diethylene glycol according to the pigment refinement process of Example A-1 (2), and kneaded and ground. Similarly, the salt and solvent were dissolved and removed from the obtained ground product, and the precipitate was collected by filtration and then washed with water to obtain a filter cake of a fine pigment. The average particle diameter of the pigment was about 40 nm. The filter cake was dried and pulverized to obtain a fine powder pigment “PG36A-1”.

(2) Preparation of Pigment Dispersion In the same manner as in Example A-3 (1), instead of “(16 bromo) green pigment A-1” and “PGsulfonic acid A-1”, the above “PG36A-1” ”, A cationic polymer dispersant, an acrylic resin and PGMA are blended, stirred and peptized with a dissolver, and dispersed with a horizontal medium disperser to obtain“ PG36 Colorant A-1. ” It was.

(3) Preparation and application of G color pixel forming ink In place of “(16 bromo) green pigment colorant A-1” in Example A-3 (1), “PG36 colorant obtained in (2) above” A-1 ”was used to add a photosensitive acrylic resin varnish, a photosensitive monomer, a photopolymerization initiator, and PGMA to obtain a photosensitive green pigment dispersion“ PG36 photosensitive dispersion A-1. ”

  In the same manner as in the spin coating operation of Example A-3 (2), a glass substrate treated with a silane coupling agent was set on a spin coater, and the above “PG36 photosensitive dispersion A-1” was applied and exposed. Then, curing was performed to obtain a green glass substrate (hereinafter referred to as “PG36 green glass substrate A-1”).

Example A-4 (Evaluation of color characteristics of green glass substrate)
Color as a color filter color of “(16 bromo) green glass substrate A-1” prepared in Example A-3 (2) and “PG36 green glass substrate A-1” prepared in Comparative Example 1 (3) The characteristics were evaluated. Each chromaticity (x value, y value) and brightness (Y value) of the substrate was measured using a chromaticity meter (trade name: Color Analyzer TC-1800MK2 manufactured by Tokyo Denshoku Co., Ltd.). The light for colorimetry was auxiliary standard illuminant C. Further, each green glass substrate was sandwiched between two polarizing plates, and a contrast value was obtained from a ratio of transmitted light amounts in a parallel Nicol state and a crossed Nicol state.

  Table 2 shows the chromaticity, brightness, and contrast value of the green glass substrates prepared in Example A-3 (2) and Comparative Example 1 (3), respectively. The spectral characteristic of “(16 bromo) green glass substrate A-1” is a high level capable of effectively transmitting the green light emission of the three-wavelength fluorescent lamp and effectively blocking the red and blue light emission. It showed the lightness and saturation.

Example A-5 (Preparation of color filter)
(1) Preparation of R and B fine-particle pigments Using “(16 bromo) green pigment A-1” of Example A-1 as a green pigment for a color filter, PR254 as a red pigment and a blue pigment, PY138, PB15: 6 and PV23 were prepared. In accordance with the pigment refinement process of Example A-1 (2), each pigment powder was charged into a kneader equipped with a pressure lid together with sodium chloride powder and diethylene glycol, and kneaded and ground. Similarly, the salt and solvent were dissolved and removed from the obtained ground product, and the precipitate was collected by filtration and washed with water. Thus, the filter cake of each refined pigment was obtained. The average particle size of the fine pigments of each color was 40 to 60 nm. The filter cake was dried and pulverized to obtain fine powder powder pigments.

(2) Preparation of pigment colorant Fine particles of PR254, PY138, PB15: 6 and PV23 obtained in (1) above instead of “(16 bromo) green pigment A-1” and “PG sulfonic acid A-1” In the same manner as in Example A-3 (1), these fine particle pigments were respectively mixed with a cationic polymer dispersant, an acrylic resin and PGMA, and stirred and peptized with a dissolver, and an annular type. Dispersion treatment was performed with a bead mill disperser to obtain a colorant for each pigment (hereinafter referred to as “red, yellow, blue and purple colorant A-1”).

(3) Preparation of pixel forming ink In order to form RGB pixels on the glass substrate of the color filter, “(16 bromo) green pigment photosensitive dispersion A-2”, “red pigment” according to the composition shown in Table 3 below. Photosensitive dispersion liquid A-1 "and" blue pigment photosensitive dispersion liquid A-1 "were obtained.

(4) Preparation of color filter A glass substrate treated with a silane coupling agent was set on a spin coater, and the “red pigment photosensitive dispersion A-1” of (3) above was first treated at 300 rpm for 5 seconds, then 1, Spin-coated at 200 rpm for 5 seconds. Next, prebaking was performed at 80 ° C. for 10 minutes, a photomask having a mosaic pattern was brought into close contact with the coated surface of the glass substrate, and exposure was performed with an ultrahigh pressure mercury lamp at a light amount of 100 mJ / cm ² . Next, development and washing were performed with a dedicated developer and a dedicated rinse to form a red mosaic pattern on the glass substrate.

  Subsequently, the green mosaic pattern and the blue mosaic pattern were subjected to the above method using “(16 bromo) green pigment photosensitive dispersion A-2” and “blue pigment photosensitive dispersion A-1” in Table 3. Thus, an RGB color filter was obtained by coating and baking. The obtained color filter has excellent spectral curve characteristics, excellent fastness such as light resistance and heat resistance, and excellent light transmission properties, and is excellent as a color filter for liquid crystal color displays. Showed the nature.

[Example for Green Pigment B]
Example B-1 (Production of tetradecabromo-dichlorocopper phthalocyanine green pigment)
(1) Synthesis of tetradecabromo-dichlorocopper phthalocyanine In the same synthesis reaction apparatus as Example A-1, 172.8 parts of trichlorobenzene, 18.08 parts of tribromo-monochlorophthalic anhydride, 20.00 parts of tetrabromophthalic anhydride 23.3 parts of urea, 6.36 parts of titanium tetrachloride and 3.0 parts of cupric chloride were charged. The reaction was performed under the same reaction conditions as in Example A-1 to obtain a crude pigment. The yield of crude pigment was 36.5 parts, and the crude pigment yield was 96.7%. The crude pigment was purified as in Example A-1. The yield of the purified pigment obtained by purification was 94.4%. According to elemental analysis, the bromine content was 64.3% (theoretical value: 63.94%), and the chlorine content was 4.1% (theoretical value: 4.053%). The average bromine substitution number per molecule calculated from the analysis value of the obtained tetradecabromo-dichlorocopper phthalocyanine green pigment (hereinafter abbreviated as “14Br2ClCuPc”) was 14.1, and the average chlorine substitution number was 2.0. It was shown that all benzene rings of the phthalocyanine skeleton were completely substituted with 14 bromine atoms and 2 chlorine atoms.

(2) Preparation of Green Fine Particle Pigment by Fine Treatment A green pigment filter cake was obtained in the same manner as in Example A-1 using 100 parts of 14Br2ClCuPc obtained in (1) above. When the average particle size was measured in the same manner as in Example A-1, the average particle size was about 40 nm. Thereafter, a fine powder pigment (hereinafter referred to as “green pigment B-1”) was obtained in the same manner as in Example A-1.

Example B-2 (Production of sulfonated product of tetradecabromo-monochloro copper phthalocyanine)
(1) Synthesis of tetradecabromo-monochloro copper phthalocyanine 172.8 parts of trichlorobenzene, 9.04 parts of tribromo-monochloro phthalic anhydride, 20.00 parts of tetrabromo phthalic anhydride in the same synthesis reaction apparatus as in Example A-1. , 8.23 parts of tribromophthalic anhydride, 23.3 parts of urea, 6.36 parts of titanium tetrachloride and 3.0 parts of cupric chloride were charged. The reaction was carried out in the same manner as in Example A-1. The yield of crude pigment was 35.5 parts, and the yield of crude pigment was 96.0%. The pigment was purified in the same manner as in Example A-1. The yield of tetradecabromo-monochloro copper phthalocyanine coarse particle pigment (hereinafter abbreviated as “14BrClCuPc”) obtained by purification was 94.6%.

(2) Synthesis of sulfonated product of 14BrClCuPc 20 parts of 14BrClCuPc obtained in (1) above was sulfonated in the same manner as in Example A-2, and a sulfonated product of 14BrClCuPc (hereinafter referred to as “PG sulfonic acid B-1”). Obtained.

Example B-3 (evaluation of green pigment B-1)
(1) Preparation of Green Pigment Dispersion 19 parts of “Green Pigment B-1”, 1 part of “PG Sulfonic Acid B-1”, Cationic Polymer Dispersant (Polyester Amidated Polyethyleneimine, 50% Solution) 12 parts, 50 parts of the same “resin dispersant PGMA solution A-1” as in Example A-3 and 18 parts of PGMA were blended, and a green pigment dispersion (hereinafter referred to as “green pigment coloring”) was prepared in the same manner as in Example A-3. Referred to as “agent B-1”).

(2) Preparation and application of green pixel forming ink A photosensitive green pigment dispersion (ie, ink) was prepared in the same manner as in Example A-3 except that 100 parts of the above-mentioned “green pigment colorant B-1” was used. Further, a green glass substrate (hereinafter referred to as “green glass substrate B-1”) was obtained.

(3) Evaluation of color characteristics of green glass substrate The color characteristics of the “green glass substrate B-1” as a color filter color were evaluated in the same manner as in Example A-4. Table 4 shows the chromaticity, lightness, and contrast value of the green glass substrate obtained in Example B-3 (2). The spectral characteristics of the “green glass substrate B-1” are high-level brightness that can effectively transmit the green light emission of the three-wavelength fluorescent lamp and effectively block the red and blue light emission. It showed sex.

Example B-4 (Preparation of color filter)
(1) Preparation of fine color pigments by refining R and B pigments Using “green pigment B-1” of Example B-1 as a green pigment for a color filter, and as a red pigment and a blue pigment, Using the same pigment as in Example A-5, filter cakes of the respective refined pigments were obtained according to the refinement process of the pigment in Example A-1 (2). The average particle size of the fine pigments of each color was 40 to 60 nm. The filter cake was dried and pulverized to obtain fine powder powder pigments.

(2) Preparation of pigment colorant In place of “green pigment B-1” and “PG sulfonic acid B-1”, the PR254, PY138, PB15: 6 and PV23 particulate pigments obtained in (1) above are used. Except for the above, in the same manner as in Example A-3 (1), these fine particle pigments were respectively mixed with a cationic polymer dispersant, an acrylic resin and PGMA, stirred with a dissolver and peptized, and an annular type bead mill dispersing machine. The pigment was subjected to dispersion treatment to obtain colorants for the respective pigments (hereinafter referred to as “red, yellow, blue and purple colorants B-1”).

(3) Preparation of pixel forming ink In order to form RGB pixels on the glass substrate of the color filter, the green pigment photosensitive dispersion B-2 and the red pigment photosensitive dispersion B-1 are prepared according to the formulation shown in Table 5 below. And blue pigment photosensitive dispersion B-1.

(4) Preparation of color filter In the same manner as in Example A-5, “red pigment photosensitive dispersion B-1”, “green pigment photosensitive dispersion B-2” and “blue pigment photosensitive” in (3) above. Color dispersion filter B-1 "was used to obtain an RGB color filter. The resulting color filter has excellent spectral curve characteristics, excellent fastness such as light resistance and heat resistance, and excellent light transmission properties, and is excellent as a color filter for liquid crystal color displays. Showed the properties.

According to the present invention, the green pigment A, the green pigment B, or the green pigment whose maximum transmission wavelength is longer than that of the conventional green pigment is used as a green pigment for the G color pixel of the three primary color pixels of the color filter. By using the derivative C, a G color pixel of a color filter excellent in optical characteristics such as optical density, light transmittance, and contrast is formed.

Claims (11)

A colorant for forming a green pixel of a color filter containing at least one of the following pigments (A) and (B) , and a transmission spectrum of a thin film containing the pigment (A) or (B) and no yellow pigment The maximum transmission wavelength is approximately 527 to 530 nm, and the pigment is kneaded and ground together with a water-soluble salt in a kneader to reduce the average particle size to 10 to 150 nm. Coloring agent.
(A) An average of 14 to 16 bromine atoms obtained by reacting a copper salt with at least one component of phthalic acid substituted with an average of 3.5 to 4.0 bromine atoms and derivatives thereof is substituted. Copper phthalocyanine green pigment (B) not substituted with chlorine atoms (B) An average of 1.0 to 2. and at least one component of phthalic acid substituted with 3.0 to 4.0 bromine atoms on average and derivatives thereof. An average of 12 obtained by reacting a mixture of at least one component of phthalic acid substituted with 0 chlorine atoms and an average of 2.0 to 3.0 bromine atoms and derivatives thereof with a copper salt copper phthalocyanine green Pigments chlorine atoms are substituted more than zero and the average 4 or less less than 16 bromine atoms or more.   The phthalic acid derivative as the reactive material for the copper phthalocyanine green pigment (A) is a phthalic anhydride, phthalodinitrile, phthalimide, phthalamide, phthalamic acid in which 3.5 to 4.0 bromine atoms are substituted on average. The colorant for forming a pixel according to claim 1, which is at least one selected from the group consisting of salts thereof. Wherein said at least one component of the average 3.0 to 4.0 amino phthalate bromine atom is substituted and derivatives thereof, bets Riburomufutaru acid, tetrabromophthalic acid, their anhydrides, their dinitrile, acid At least one compound selected from the group consisting of imides, acid amides and amide acid derivatives, and salts thereof, and said average of 1.0 to 2.0 chlorine atoms and average of 2.0 to 3. At least one component of phthalic acid substituted with 0 bromine atoms and derivatives thereof is tribromo-monochlorophthalic acid, its anhydride, their dinitrile, acid imide, acid amide and amido acid derivatives, and their The colorant for forming a pixel according to claim 1, which is at least one compound selected from the group consisting of salts. Further, the copper phthalocyanine green pigment having one or more substitution positions and 14 or more substituted with bromine atoms has at least one substituent selected from the group consisting of anionic, cationic and nonionic groups The colorant for pixel formation according to claim 1, comprising the introduced green pigment derivative (C). The green pigment is at least one of hexadecabromo copper phthalocyanine green pigment and tetradecabromo-dichloro copper phthalocyanine green pigment, and the green pigment derivative (C) is a sulfonated product of tetradecabromo copper phthalocyanine or tetradecabromo-monochloro. pixel-forming colorant of claim 4 which is a sulfonated product of copper phthalocyanine. The colorant for forming a pixel according to claim 1, wherein the green pigment has an average particle diameter of 10 to 130 nm. The colorant for forming a pixel according to claim 1, wherein the green pigment is dispersed in at least one of an organic liquid medium, an organic liquid-water mixed medium, an aqueous medium, and a solid resin medium.   Furthermore, the coloring agent for pixel formation of Claim 1 containing the yellow pigment.   Furthermore, the coloring agent for pixel formation of Claim 1 which contains at least 1 sort (s) of a polymer, an oligomer, and a monomer as a film formation material.   A pixel forming ink comprising the pixel forming colorant according to claim 1 as a coloring component. A color filter obtained using the pixel forming ink according to claim 10 .