JP2007023266A - Pigment composition and use thereof - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a pigment composition for color filter prevented from foreign matter generation, increase in viscosity and decline in storage stability even in the case of high pigment content and capable of producing color filters with high transparency and color grade. <P>SOLUTION: The pigment composition comprises a pigment, a pigment modifier and a resin varnish; wherein the pigment modifier is a pigment composite of a sulfone group-containing pigment molecular component and a sulfone group-free pigment molecular component, and the the number of average sulfone group introductions per molecule in terms of total pigment molecule in the pigment composite is 0.05-0.5. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a pigment composition (hereinafter sometimes simply referred to as “pigment ink”), a method for producing a color filter, and a color filter, which are particularly useful for producing a color filter used for a liquid crystal color display, an imaging device, and the like. More specifically, the present invention relates to a pigment ink excellent in transparency, fluidity and storage stability, which is useful for forming a pixel pattern of a color filter, a method for producing a color filter, and a color filter.

  Color filters used in liquid crystal displays, etc. are currently applied to a substrate with a pigment ink in which a pigment is dispersed in a photoresist by spin coating, coating, or transfer, and then exposed and developed through a photomask. It is mainly manufactured by a pigment dispersion method in which pixels are formed by patterning. At that time, simply dispersing the pigment, resin, solvent, etc. with a normal disperser does not sufficiently disperse the pigment, so the pixel pattern to be formed lacks transparency, and the light transmittance is insufficient for color filters. Met.

  Further, as a resin generally used for a photoresist, an acrylic polymer having a high acid value is mainly employed because an alkaline aqueous solution can be used as a patterning developer. However, in pigment inks composed of pigments and high acid value acrylic resins, pigment agglomeration occurs and the viscosity of the pigment ink tends to increase, and the pigment ink thickens over time, and the storage stability of the pigment ink is improved. Often gets worse.

  When producing a color filter with the pigment ink with the above difficulties, the pigment ink to be used is applied to the substrate by a spin coating method and then patterned, but the pigment ink has a high viscosity, When the pigment is agglomerated and exhibits a thixotropic viscosity, the central portion of the coating surface before patterning made of pigment ink rises, so when making a large screen color filter, The pixel pattern and the pixel pattern in the peripheral part cause unevenness in hue and density difference.

  Therefore, the pigment ink used for the production of the color filter usually has a pigment concentration in the high concentration range of 5 to 20% by mass, but the dispersion state is such that the pigment particles do not agglomerate with each other. The viscosity must be low (for example, about 5 to 20 mPa · s) and excellent in storage stability as compared with dry paint or baking paint.

In order to satisfy the above requirements, conventionally, a method of adding a sulfonated pigment having a sulfonation degree of 1 or more per molecule to the pigment, or treating the pigment with the above-described derivative has been proposed.
JP 2000-160084 A

  On the other hand, liquid crystal display devices have been expanded from monitors for personal computers to color displays for color televisions, and there has been an increasing demand for further performance improvements for color filters, improving pixel pattern transparency and transmitting pixel patterns. It has become necessary to increase the contrast of light and increase the pigment content of the pixel pattern.

  However, in the method using the above-described pigment derivative, it is possible to improve the transparency of the pixel pattern by improving the dispersibility of the pigment, and to prevent an increase in the viscosity of the pigment ink and a decrease in storage stability due to an increase in the pigment concentration. It is difficult to control the sulfonation reaction of the pigment, and when the above pigment derivative into which many sulfone groups are introduced is used, a compound that forms a salt with the cationic polymer dispersant in the pigment ink is used as the dispersion medium. In some cases, it becomes a semi-dissolved sol or a gel that swells by absorbing the dispersion medium, which may cause the generation of foreign matter in the pigment ink, and these improvements are desired. .

  The present inventors have solved the above-mentioned problems when using the sulfonated product of the pigment in the pigment ink, and can improve the color quality of the pigment ink for color filters, reduce the viscosity, and prevent the occurrence of foreign matter. As a result of intensive research, as a result of using a complex of pigment molecule sulfonated and non-sulfonated pigment molecule, a pigment complex having an average number of introduced sulfone groups per molecule of 0.05 to 0.5 is used. As a result, the viscosity of the pigment ink can be reduced, the gel ink can be prevented from thickening during storage, and foreign matter can be prevented, and the transparency of the most important pixel pattern as a color filter is improved. As a result, the present invention has been completed.

  That is, the present invention includes a pigment, a pigment modifier, and a resin varnish, wherein the pigment modifier is a pigment complex of a pigment molecule component containing a sulfone group and a pigment molecule component not containing a sulfone group, A pigment ink is provided wherein the number of introduced sulfone groups (sulfonic acid groups) per molecule in terms of all pigment molecules in the pigment composite is 0.05 to 0.5.

  In the pigment ink, the pigment, the pigment molecule containing a sulfone group and the pigment molecule not containing a sulfone group are respectively soluble / insoluble azo pigment, high molecular weight azo pigment, methine / azomethine pigment, azomethine azo pigment, diketopyrrolopyrrole pigment, At least one pigment or pigment molecule selected from the group consisting of phthalocyanine pigments, isoindolinone pigments, anthraquinone pigments, ansanthrone pigments, quinophthalone pigments, indigo thioindigo pigments, dioxazine pigments, quinacridone pigments, and metal complex pigments It is preferable that the sulfone group is a free sulfone group, a metal salt, an ammonium salt and / or an amine salt thereof; and further, a cationic polymer dispersant is contained. The pigment ink is useful as a pixel forming ink for a color filter.

  Further, the present invention provides a method for producing a color filter, wherein the pixel pattern is formed using the pigment ink in a method for producing a color filter including a step of forming a pixel pattern on a color filter substrate. , A color filter formed by the method, an image display device equipped with the color filter, and an information transmission device equipped with the image display device I will provide a.

  According to the present invention described above, in the composite of a sulfonated product of pigment molecules and a non-sulfonated pigment molecule, a composite in which the average number of introduced sulfone groups per molecule is 0.05 to 0.5, By adding and using as a pigment dispersibility improving agent for a pigment ink for forming a pixel pattern of a color filter, the pigment ink can be stably produced and the generation of foreign matters can be prevented. In addition, by using the pigment ink, it has excellent spectral curve characteristics, sharpness, high transparency, and various properties such as light resistance, heat resistance, solvent resistance, chemical resistance and water resistance. A color filter having a pixel pattern with excellent robustness can be obtained.

Next, the present invention will be described in more detail with reference to the best mode for carrying out the invention.
The pigment modifier used in the present invention and mainly characterizing the present invention is a complex of a pigment molecule component containing a sulfone group and a pigment molecule component not containing a sulfone group, and the total amount in the sulfonated pigment complex. The average number of introduced sulfone groups per molecule in terms of pigment molecules is 0.05 to 0.5.

  The pigments constituting the pigment modifier are all known organic pigments, specifically soluble / insoluble azo pigments, high molecular weight azo pigments, methine / azomethine pigments, azomethine azo pigments, diketopyrrolopyrrole pigments, Examples include phthalocyanine pigments, isoindolinone pigments, anthraquinone pigments, indanthrene pigments, ansanthrone pigments, quinophthalone pigments, indigo thioindigo pigments, dioxazine pigments, quinacridone pigments, and metal complex pigments.

  An example of a method for preparing the pigment modifier is as follows. The pigment is sulfonated with a sulfonating agent such as fuming sulfuric acid, and elemental analysis of sulfur in the obtained sulfonated product is performed to determine the average number of sulfone groups per molecule. When the number of sulfone groups is larger than the target number, an unsulfonated pigment is added so that the average number of sulfone groups is 0.05 to 0.5, dissolved in concentrated sulfuric acid, ice water precipitation, The pigment modifier used in the present invention can be obtained by washing with water and drying.

  The pigment modifier whose average number of introduced sulfone groups is adjusted to 0.05 to 0.5 can be used as it is in the pigment ink or in the form of a salt with the cationic polymer dispersant. The affinity and solubility were remarkably lowered, and the pigment behavior was substantially insoluble or hardly soluble. This is considered to be because the non-sulfonated pigment molecules are stacked on the sulfonated pigment molecules, and the affinity and solubility in water are lowered.

  When the average number of introduced sulfone groups in the pigment modifier is less than 0.05, the anionic property as the pigment modifier is insufficient, and the function as the pigment modifier is insufficient. When the average number of introduced sulfone groups exceeds 0.5, the pigment modifier itself in the pigment ink or the salt of the pigment modifier and the cationic polymer dispersant is semi-dissolved in the dispersion medium. It is insufficient in that it becomes a sol form (foreign matter) or a swollen gel form (foreign matter) by absorbing the dispersion medium and impairs the quality of the pigment ink.

  The sulfone group of the pigment modifier may be a free sulfone group or a salt with a base. Examples of the base include alkali metals such as Li, Na and K, and polyvalent metals such as Ca, Ba, Al, Mn, Sr, Mg and Ni. Examples of amines that form amine salts include (mono, di, or tri) alkylamines, substituted or unsubstituted alkylenediamines, alkanolamines, and alkylammonium chlorides.

  The pigment ink for a color filter of the present invention is composed of a pigment, the pigment modifier, and a resin varnish. The pigments used in the present invention are all known organic pigments, specifically soluble / insoluble azo pigments, high molecular weight azo pigments, methine / azomethine pigments, azomethine azo pigments, diketopyrrolopyrrole pigments, phthalocyanine pigments. , Isoindolinone pigments, anthraquinone pigments, ansanthrone pigments, quinophthalone pigments, indigo thioindigo pigments, dioxazine pigments, quinacridone pigments, and metal complex pigments.

  As a particularly preferable pigment, when a red pixel pattern is formed, examples of the red pigment include a color index (CI) pigment red (PR) 56, 58, 122, 166, 168, 176, 177, 178, 224, 242, and 254, green pigments include Pigment Green (PG) 7 and 36, and blue pigments include Pigment Blue 15: 1, 15: 3, 15: 6, 60, and 80. Etc.

  For example, Pigment Yellow (PY) 12, 13, 14, 17, 24, 55, 60, 74, 83, 90, 93, 126, 128, 138, 139 may be used as complementary pigments to the above pigments. 150, 154, 155, 180, 185, 216, 219, pigment violet (PV) 19, 23 can be used.

  Although the usage-amount of a pigment is not specifically limited, Usually, it is used in the ratio of 5-500 mass parts per 100 mass parts of resin in the below-mentioned resin varnish. The blending ratio of the pigment modifier used in the present invention to the pigment is preferably 0.5 to 50 parts by mass, more preferably 1 to 10 parts by mass per 100 parts by mass of the pigment. If the blending ratio of the pigment modifier is too small, it is difficult to sufficiently obtain the effect of the target pigment modifier. In addition, if the blending ratio of the pigment modifier is too large, the effect of using only a large amount will not be obtained, and conversely, the physical properties of the resin varnish of the pigment ink obtained will be reduced. The hue of the pigment to be dispersed greatly changes depending on the color of the agent itself.

  In the present invention, when an organic solvent-based dispersion medium is used as a pigment ink dispersion medium, a cationic polymer dispersant is used together with the pigment modifier in order to further improve pigment dispersion. It is preferable to do. It is preferable to use the cationic polymer dispersant in an amount equivalent to the sulfone group of the pigment modifier. Further, since the pigment modifier also has a function as a pigment dispersant, it can be used in an amount more than the equivalent amount with respect to the cationic polymer dispersant.

  As the resin varnish for dispersing the pigment in the present invention, any known resin varnish conventionally used in pigment inks for color filters can be used, and is not particularly limited. In addition, a solvent or an aqueous medium suitable for the resin varnish as a dispersion medium is used. Moreover, conventionally well-known additives, for example, a dispersion aid, a smoothing agent, an adhesive agent, and the like are appropriately added and used as necessary.

  As the resin varnish, a photosensitive resin varnish and a non-photosensitive resin varnish are used. Examples of the photosensitive resin varnish include photosensitive resin varnishes used in ultraviolet curable inks and electron beam curable inks. Non-photosensitive resin varnishes include, for example, letterpress ink, planographic ink, and intaglio gravure ink. Resin varnishes used for printing inks such as stencil screen ink, resin varnishes used for inkjet printing, resin varnishes used for electrodeposition coating, resin varnishes used for developers of electronic printing and electrostatic printing, thermal transfer films or ribbons Resin varnish used for the above.

  Specific examples of the photosensitive resin varnish include, for example, photosensitive cyclized rubber resins, photosensitive phenol resins, photosensitive polyacrylate resins, photosensitive polyamide resins, photosensitive polyimide resins, and unsaturated polyesters. Varnishes such as polyester resins, polyester acrylate resins, polyepoxy acrylate resins, polyurethane acrylate resins, polyether acrylate resins, polyol acrylate resins, or varnishes to which monomers are further added as reactive diluents. It is done. As a suitable resin among the photosensitive resin varnish, an alkali-developable acrylate resin having a free carboxylic acid group in the molecule is desirable.

  Specific examples of the non-photosensitive resin varnish include, for example, a cellulose acetate resin, a nitrocellulose resin, a styrene (co) polymer, a polyvinyl butyral resin, an aminoalkyd resin, a polyester resin, and an amino resin modified polyester. Water-soluble resin, polyurethane resin, acrylic polyol urethane resin, soluble polyamide resin, soluble polyimide resin, soluble polyamideimide resin, soluble polyesterimide resin, hydroxyethyl cellulose, styrene-maleic acid ester copolymer Salts, water-soluble salts of (meth) acrylic acid ester-based (co) polymers, water-soluble amino alkyd resins, water-soluble amino polyester resins, water-soluble polyamide resins, and the like. These may be used alone or in combination of two or more. Used in combination It is.

Although the manufacturing method of the pigment ink comprised from said each component of this invention is not restrict | limited in particular, For example, the following method etc. are mentioned.
(A) A method in which a pigment and a pigment modifier are dissolved in sulfuric acid and the like, and then precipitated in water, both are made into a solid solution, and added to a resin varnish together with a cationic polymer dispersant as necessary, and then kneaded.
(B) It is necessary to suspend the pigment uniformly in water or an organic solvent, add a solution containing the pigment modifier to the suspension, and deposit the pigment modifier on the surface of the pigment particles. Depending on the method, it is added to the resin varnish together with the cationic polymer dispersant and kneaded.
(C) A method in which a pigment, a pigment modifier and, if necessary, a cationic polymer dispersant are finely dispersed with a wet medium disperser such as an attritor or a ball mill, and added to a resin varnish for kneading.
(D) A method in which a pigment, a pigment modifier and, if necessary, a cationic polymer dispersant are added to a resin varnish at the time of premixing, and the mixture is dispersed by a wet medium disperser.

  When producing a color filter using the pigment ink for color filter of the present invention, when a photosensitive resin varnish is used as the resin varnish, conventionally known photopolymerization initiators such as benzoin ether and benzophenone are used as the pigment ink. And is used as a photosensitive pigment ink prepared by kneading by a conventionally known method. Moreover, it can replace with said photoinitiator and can also be used as a thermopolymerizable pigment ink using a thermal polymerization initiator.

  When forming a color filter pattern on a substrate using the above-described photosensitive pigment ink, the photosensitive pigment ink is formed on a transparent substrate, for example, a spin coater, a low-speed rotation coater, a roll coater, a knife coater, etc. Use this method to coat the entire surface, or perform full surface printing by various printing methods or partial printing that is slightly larger than the pattern, and after pre-drying, attach the photomask and expose using an ultra-high pressure mercury lamp to print the pattern. .

  Subsequently, development and washing are performed, and post-baking is performed as necessary to form a color filter pattern. These color filter pattern formation methods are known per se, and the color filter pattern formation method is not particularly limited in the present invention.

  When forming a color filter pattern using the color filter pigment ink of the present invention (non-photosensitive pigment ink) using a non-photosensitive resin varnish, the non-photosensitive pigment ink is used on a transparent substrate, for example, , A method of printing a pixel pattern directly on a substrate by the above-described various printing methods as a color filter printing ink, a method of forming a pixel pattern on a substrate by electrodeposition coating as an aqueous electrodeposition coating composition for a color filter, and ink jet Use a method of forming a colored pattern on a substrate by ink jet printing as an ink, an electronic printing method or an electrostatic printing method, or once forming a colored pattern on a transferable substrate by the above method, etc. Examples include a method of transferring.

  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. Further, an RGB color filter can be obtained by forming a black matrix according to a conventional method. The manufacturing methods of these color filters are known per se, and the manufacturing method of the color filters is not particularly limited in the present invention.

Next, the present invention will be described more specifically with reference to synthesis examples, examples and comparative examples. In the text, “part” or “%” is based on mass.
Synthesis example 1
30 parts of diketopyrrolopyrrole pigment (CI Pigment Red 254) is added to 300 parts of 20% fuming sulfuric acid, and then reacted at 60 to 65 ° C. for 6 hours. After cooling, the reaction mixture was precipitated in 3,000 parts of ice water, filtered and washed with water to obtain 110 parts of water paste (pure 28 parts). This water paste was dried, and 28 parts of diketopyrrolopyrrole (pigment modifier 1) having an average of 0.8 sulfone groups introduced per molecule was obtained from the result of elemental analysis of sulfur.

  5 parts of the above pigment modifier 1 and 5 parts of C.I. I. Pigment Red 254 is added to 100 parts of 95% concentrated sulfuric acid and stirred at 60 to 65 ° C. for 1 hour. After cooling, it was precipitated in 1,000 parts of ice water, filtered and washed with water to obtain 39 parts of water paste (pure amount of 10 parts). This water paste was dried, and 10 parts of diketopyrrolopyrrole (pigment modifier 2) having an average of 0.4 sulfone groups introduced per molecule was obtained from the result of elemental analysis of sulfur.

Synthesis example 2
30 parts of isoindolinone pigment (CI Pigment Yellow 139) is added to 300 parts of 100% sulfuric acid and then reacted at 20-25 ° C. for 6 hours. After cooling, the reaction mixture was precipitated in 3,000 parts of ice water, filtered and washed with water to obtain 108 parts of water paste (pure amount 26 parts). This water paste was dried, and 26 parts of isoindolinone (pigment modifier 3) having an average of 0.8 sulfone groups introduced per molecule was obtained from the results of elemental analysis of sulfur.

  5 parts of the above pigment modifier 3 and 5 parts of C.I. I. Pigment Yellow 139 is added to 100 parts of 95% concentrated sulfuric acid and stirred at 60 to 65 ° C. for 1 hour. After cooling, it was precipitated in 1,000 parts of ice water, filtered and washed with water to obtain 40 parts of water paste (pure amount 10 parts). This water paste was dried, and 10 parts of isoindolinone (pigment modifier 4) into which an average of 0.4 sulfone groups were introduced per molecule was obtained from the result of elemental analysis of sulfur.

Synthesis example 3
30 parts of a polyhalogenated phthalocyanine pigment (CI Pigment Green 36) are added to 300 parts of 20% fuming sulfuric acid and then reacted at 80 to 85 ° C. for 6 hours. After cooling, the reaction mixture was precipitated in 3,000 parts of ice water, filtered and washed with water to obtain 115 parts of water paste (pure 29 parts). This water paste was dried, and 29 parts of polyhalogenated phthalocyanine (pigment modifier 5) into which 0.9 sulfone groups on average were introduced per molecule was obtained from the result of elemental analysis of sulfur.

  4.4 parts of the above pigment modifier 5 and 5.6 parts of C.I. I. Pigment Green 36 is added to 100 parts of 95% concentrated sulfuric acid and stirred at 60 to 65 ° C. for 1 hour. After cooling, it was precipitated in 1,000 parts of ice water, filtered and washed with water to obtain 37 parts of water paste (pure amount 10 parts). This water paste was dried, and 10 parts of polyhalogenated phthalocyanine (pigment modifier 6) into which 0.4 sulfone groups per molecule were introduced on average was obtained from the result of elemental analysis of sulfur.

Synthesis example 4
30 parts of quinophthalone pigment (CI Pigment Yellow 138) are added to 300 parts of 20% fuming sulfuric acid and then reacted at 60 to 65 ° C. for 3 hours. After cooling, the reaction mixture was precipitated in 3,000 parts of ice water, filtered and washed with water to obtain 110 parts of water paste (pure 28 parts). This water paste was dried, and 28 parts of quinophthalone (pigment modifier 7) having an average of 0.9 sulfone groups introduced per molecule was obtained from the result of elemental analysis of sulfur.

  4.4 parts of the pigment modifier 7 and 5.6 parts of C.I. I. Pigment Yellow 138 is added to 100 parts of 95% concentrated sulfuric acid and stirred at 60 to 65 ° C. for 1 hour. After cooling, it was precipitated in 1,000 parts of ice water, filtered and washed with water to obtain 41 parts of water paste (pure amount 10 parts). This water paste was dried, and 10 parts of quinophthalone (pigment modifier 8) having an average of 0.4 sulfone groups introduced per molecule was obtained from the result of elemental analysis of sulfur.

Synthesis example 5
30 parts of a phthalocyanine pigment (CI Pigment Blue 15: 6) is added to 300 parts of 100% sulfuric acid, and then reacted at 60 to 65 ° C. for 6 hours. After cooling, the reaction mixture was precipitated in 3,000 parts of ice water, filtered and washed with water to obtain 110 parts of water paste (pure 28 parts). This water paste was dried, and 28 parts of phthalocyanine (pigment modifier 9) having an average of 0.8 sulfone groups introduced per molecule was obtained from the result of elemental analysis of sulfur.

  5 parts of the pigment modifier 9 and 5 parts of C.I. I. Pigment Blue 15: 6 is added to 100 parts of 95% concentrated sulfuric acid and stirred at 60 to 65 ° C. for 1 hour. After cooling, it was precipitated in 1,000 parts of ice water, filtered and washed with water to obtain 38 parts of water paste (pure amount 10 parts). This water paste was dried, and 10 parts of phthalocyanine (pigment modifier 10) having an average of 0.4 sulfone groups introduced per molecule was obtained from the result of elemental analysis of sulfur.

Synthesis Example 6
30 parts of dioxazine violet pigment (CI Pigment Violet 23) are added to 300 parts of 95% sulfuric acid and then reacted at 5-10 ° C. for 6 hours. After cooling, the reaction mixture was precipitated in 3,000 parts of ice water, filtered and washed with water to obtain 110 parts of water paste (pure amount 27 parts). This water paste was dried, and 27 parts of dioxazine violet (pigment modifier 11) having an average of 0.9 sulfone groups introduced per molecule was obtained from the result of elemental analysis of sulfur.

  4.4 parts of the pigment modifier 11 and 5.6 parts of C.I. I. Pigment Violet 23 is added to 100 parts of 95% concentrated sulfuric acid and stirred at 5 to 10 ° C. for 30 minutes. After cooling, it was precipitated in 1,000 parts of ice water, filtered and washed with water to obtain 39 parts of water paste (pure amount of 10 parts). This water paste was dried, and 10 parts of dioxazine violet (pigment modifier 12) having an average of 0.4 sulfone groups introduced per molecule was obtained from the result of elemental analysis of sulfur.

Synthesis example 7
30 parts of indanthrene blue pigment (CI Pigment Blue 60) are added to 300 parts of 20% fuming sulfuric acid and then reacted at 80 to 85 ° C. for 6 hours. After cooling, the reaction mixture was precipitated in 3,000 parts of ice water, filtered and washed with water to obtain 120 parts of a water paste (pure amount of 30 parts). This water paste was dried, and 30 parts of Indanthrene Blue (pigment modifier 13) having an average of 0.8 sulfone groups introduced per molecule were obtained from the results of elemental analysis of sulfur.

  5 parts of the pigment modifier 13 and 5 parts of C.I. I. Pigment Blue 60 is added to 100 parts of 95% concentrated sulfuric acid and stirred at 60 to 65 ° C. for 1 hour. After cooling, it was precipitated in 1,000 parts of ice water, filtered and washed with water to obtain 40 parts of water paste (pure amount 10 parts). This water paste was dried, and 10 parts of indanthrene blue (pigment modifier 14) having an average of 0.4 sulfone groups introduced per molecule was obtained from the result of elemental analysis of sulfur.

Example 1
50 parts of acrylic resin varnish (methacrylic acid / butyl acrylate / styrene / hydroxyethyl acrylate copolymerized at a molar ratio of 25/50/15/10, molecular weight 12,000, solid content 30%) I. 20 parts of Pigment Red 254, 1 part of pigment modifier 2 obtained in Synthesis Example 1, 4 parts of cationic polymer dispersant and 20 parts of solvent (propylene glycol monomethyl ether acetate) (hereinafter abbreviated as PGMAc) After premixing, the mixture was dispersed by a horizontal bead mill to obtain a red base color (high concentration pigment ink) for a color filter.

Example 2
C. of Example 1 I. Pigment Red 254 instead of C.I. I. A yellow base color was obtained in the same manner as in Example 1 except that Pigment Yellow 139 was used instead of Pigment Modifying Agent 2 and Pigment Modifying Agent 4 obtained in Synthesis Example 2.

Example 3
C. of Example 1 I. Pigment Red 254 instead of C.I. I. A green base color was obtained in the same manner as in Example 1 except that Pigment Green 36 was replaced with Pigment Modification Agent 2 and Pigment Modification Agent 6 obtained in Synthesis Example 3.

Example 4
C. of Example 1 I. Pigment Red 254 instead of C.I. I. A yellow base color was obtained in the same manner as in Example 1 except that Pigment Yellow 138 was used instead of Pigment Modifier 2 and Pigment Modifier 8 obtained in Synthesis Example 4.

Example 5
C. of Example 1 I. Pigment Red 254 instead of C.I. I. A blue base color was obtained in the same manner as in Example 1 except that Pigment Blue 15: 6 was used instead of Pigment Modifier 2 and Pigment Modifier 10 obtained in Synthesis Example 5 was used.

Example 6
C. of Example 1 I. Pigment Red 254 instead of C.I. I. The pigment violet 23 was replaced with the pigment modifier 2, and the pigment modifier 12 obtained in Synthesis Example 6 was used to obtain a purple base color in the same manner as in Example 1.

Example 7
C. of Example 1 I. Pigment Red 254 instead of C.I. I. The pigment violet 23 was replaced by the pigment modifier 14 obtained in Synthesis Example 7 instead of the pigment modifier 2, and a purple base color was obtained in the same manner as in Example 1.

Comparative Example 1
Instead of the pigment modifier 2 of Example 1, 0.5 part of the pigment modifier 1 obtained in Synthesis Example 1 was used, and a red base color was obtained in the same manner as in Example 1.

Comparative Example 2
Instead of the pigment modifier 4 of Example 2, 0.5 part of the pigment modifier 3 obtained in Synthesis Example 2 was used to obtain a yellow base color in the same manner as in Example 2.

Comparative Example 3
Instead of the pigment modifier 6 of Example 3, 0.5 part of the pigment modifier 5 obtained in Synthesis Example 3 was used, and a green base color was obtained in the same manner as in Example 3.

Comparative Example 4
Instead of the pigment modifier 8 of Example 4, 0.5 part of the pigment modifier 7 obtained in Synthesis Example 4 was used, and a yellow base color was obtained in the same manner as in Example 4.

Comparative Example 5
Instead of the pigment modifier 10 of Example 5, 0.5 part of the pigment modifier 9 obtained in Synthesis Example 5 was used, and a blue base color was obtained in the same manner as in Example 5.

Comparative Example 6
Instead of the pigment modifier 12 of Example 6, 0.5 part of the pigment modifier 11 obtained in Synthesis Example 6 was used to obtain a purple base color in the same manner as in Example 6.

Comparative Example 7
Instead of the pigment modifier 14 of Example 7, 0.5 part of the pigment modifier 13 obtained in Synthesis Example 7 was used to obtain a purple base color in the same manner as in Example 7.

  The fluidity of the base color of Examples 1 to 7, the gloss of the color development surface, and the presence or absence of foreign matter generation were compared with those of Comparative Examples 1 to 7. Observation of base color fluidity, color development surface gloss, and the presence or absence of foreign matter was measured according to the following method, and relative evaluation was performed for the base color immediately after production and after storage for 1 month at room temperature. It was.

Fluidity: Measured using a B-type viscometer under conditions of room temperature (25 ° C.) and rotor rotation speed of 6 rpm.
Gloss: Using a bar coater (winding thickness: 0.45 mm), the film was developed on a polypropylene film, and the gloss of the developed surface was compared visually and with a gloss meter. In addition, the thing with high gloss was made favorable and displayed with the following parameter | index.
○: Good △: Slightly good ×: Poor

Observation of foreign matter: It was applied to a glass substrate with a spinner, dried at 90 ° C. for 2 minutes, and then observed for the presence or absence of foreign matter at 200 times using a microscope, and indicated by the following index.
○: No foreign matter Δ: Slightly foreign matter ×: Foreign matter present The above results are shown in Table 1.

  As is apparent from Table 1, pigment modifiers (2), (4), (6), (8), (10), which are composites of sulfonated pigment molecules and non-sulfonated pigment molecules. The pigment inks for color filters of Examples 1 to 7 using (12) and (14) are pigment modifiers (1), (3), (5), (7), which are simply sulfonated pigments. Compared to the inks of Comparative Examples 1 to 7 using (9), (11), and (13), the viscosity after storage (after one month) is low, the gloss is good, and foreign matter is initially and after one month. The color filter pigment ink had excellent properties.

Example 8
In order to produce an RGB color filter, R, G and B photosensitive resists were obtained according to the formulation shown in Table 2 below.

The glass substrate treated with the silane coupling agent was set on a spin coater, and the photosensitive resist of Table 2 R was first spin-coated at 300 rpm for 5 seconds and then at 1200 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, 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, a green mosaic pattern and a blue mosaic pattern were formed by coating and baking in accordance with the above-described method using the photosensitive resists G and B shown in Table 2 to obtain RGB color filters.

  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 described above, in the complex of a sulfonated product of pigment molecules and a non-sulfonated pigment molecule, a complex having an average number of introduced sulfone groups per molecule of 0.05 to 0.5 is colored. By adding and using as a dispersibility-improving treatment agent in the filter pattern forming pigment ink, the pigment ink can be stably produced in the production process, preventing the generation of foreign matters, and finally When used as a pigment ink for color filters, it has excellent spectral curve characteristics, sharpness, high transparency, and various fastnesses such as light resistance, heat resistance, solvent resistance, chemical resistance and water resistance. An excellent color filter can be obtained.

Claims (9)

  A pigment complex of a pigment molecule component containing a sulfone group and a pigment molecule component not containing a sulfone group, and the pigment modifier includes a pigment, a pigment modifier, and a resin varnish. A pigment composition, wherein the average number of introduced sulfone groups per molecule in terms of all pigment molecules is 0.05 to 0.5.   Pigment, pigment molecule containing sulfone group and pigment molecule not containing sulfone group are soluble / insoluble azo pigment, high molecular weight azo pigment, methine / azomethine pigment, azomethine azo pigment, diketopyrrolopyrrole pigment, phthalocyanine pigment, isoindolinone, respectively. The at least one pigment or pigment molecule selected from the group consisting of a pigment, anthraquinone pigment, ansanthrone pigment, quinophthalone pigment, indigo / thioindigo pigment, dioxazine pigment, quinacridone pigment, and metal complex pigment. Pigment composition.   The pigment composition according to claim 1, wherein the sulfone group is a free sulfone group, a metal salt, an ammonium salt and / or an amine salt thereof.   The pigment composition according to claim 1, further comprising a cationic polymer dispersant.   The pigment composition according to claim 1, which is a color filter pixel forming ink.   A color filter manufacturing method including a step of forming a pixel pattern on a color filter substrate, wherein the pixel pattern is formed using the color filter pixel forming ink according to claim 5. The manufacturing method of the filter.   A color filter formed by the method according to claim 6.   An image display device comprising the color filter according to claim 7.   An information transmission device equipped with the image display device according to claim 8.