JP2008007775A - Pigment dispersion composition, colored photosensitive composition, photosensitive resin transfer material, inkjet ink using the same and, color filter, liquid crystal display and ccd device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a pigment-dispersion composition comprising organic pigment nanoparticles having high dispersion stability with a nanometer size and a sharp particle diameter distribution and having low ratio of water content; to provide a colored photosensitive composition with excellent stability, inkjet ink, and a photosensitive resin printing material using the above pigment-dispersion composition; and further to provide a color filter having high contrast and showing excellent display characteristics, a liquid crystal display and CCD device using the above. <P>SOLUTION: The pigment-dispersion composition comprises organic pigment nanoparticles and an organic solvent; wherein, of the organic pigment nanoparticles, the ratio of particles having a primary particle size of not more than 15 nm is less than 10% (number%); the ratio of particles of above 60 nm is less than 10%; and the amount of water content is 0.01-5 mass%. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a pigment dispersion composition, a colored photosensitive composition using the same, a photosensitive resin transfer material, and an inkjet ink, and a color filter, a liquid crystal display device, and a CCD device using the same.

In recent years, efforts have been made to reduce the size of particles. In particular, research is being conducted to reduce the size to nanometer size (for example, in the range of 10 to 100 nm), which is difficult to produce by a pulverization method, a precipitation method, or the like. Furthermore, attempts have been made to reduce the size to nanometer size and to obtain particles having high monodispersity (in the present invention, monodispersity means the degree of uniform particle size).
The size of such nanometer-sized fine particles is located in the middle of larger bulk particles, smaller molecules and atoms, and is an unprecedented size region, which can bring out new characteristics that could not be anticipated. It has been pointed out. Moreover, if this monodispersity can be increased, it is possible to stabilize the characteristics, and the potential of such nanoparticles is expected in various fields. Biochemistry, new materials, electronic devices, light-emitting displays Research is becoming active in a wide range of fields such as devices, printing, and medicine.
In particular, organic nanoparticles made of an organic compound have a high potential as a functional material because the organic compound itself has diversity. For example, polyimide is used in many fields because it is a chemically and mechanically stable material such as heat resistance, solvent resistance, and mechanical properties, and has excellent electrical insulation. Then, the polyimide is finely divided and combined with the characteristics and shape of the polyimide, and has been used in a wider range of fields. For example, it has been proposed to use finely divided polyimide as an additive for powder toner for image formation (Patent Document 1).

Further, regarding organic pigments among organic nanoparticles, for example, paints, printing inks, electrophotographic toners, inkjet inks, color filters, and the like can be used. These are now important compounds that are indispensable in daily life. Among them, high performance is required, and pigments for inkjet ink and pigments for color filters are particularly important in practical use.
Conventionally, dyes have been used for coloring materials for ink jet inks, but there are problems in terms of water resistance and light resistance, and pigments have been used to improve them. An image obtained with a pigment ink has the advantage of being excellent in light resistance and water resistance as compared with an image obtained with a dye-based ink. However, it is difficult to increase the monodispersibility at a nanometer size that can penetrate into the voids on the paper surface, and the adhesion to paper is poor.
In addition, with the increase in the number of pixels in a digital camera, it is desired to reduce the thickness of color filters used for optical elements such as CCD sensors and display elements. An organic pigment is used for the color filter. However, since the thickness of the filter greatly depends on the particle diameter of the organic pigment, it is desired to produce fine particles having a nanometer size level and being monodispersed and stable.

  Regarding the method for producing organic particles, a gas phase method (a method in which a sample is sublimated in an inert gas atmosphere and the particles are collected on a substrate), a liquid phase method (for example, a sample dissolved in a good solvent under stirring conditions and temperature). Research into reprecipitation method to obtain fine particles by injecting into a controlled poor solvent), laser ablation method (method of refining particles by ablating by irradiating laser to sample dispersed in solution) Has been. In addition, production examples in which monodispersion with a desired size is attempted by these methods have been reported. Among these, the liquid phase method has attracted attention as a method for producing organic particles having excellent simplicity and productivity (see Patent Documents 2 and 3). The organic particles produced by this liquid phase method can adjust the crystal form and particle surface properties by adjusting the precipitation conditions with the solvent species, injection speed, temperature, etc. Patent Document 3 describes the crystal form of the quinacridone pigment. Examples adjusted by the poor solvent species are described.

  On the other hand, regarding the improvement of the dispersibility of particles, the dispersion of organic pigments is conventionally carried out industrially using various dispersers (roll mill, ball mill, attritor, etc.), but by making the particles finer The viscosity may increase. If the viscosity increases, it becomes difficult to take out from the disperser, it cannot be transported by pipeline, or it becomes gelled during storage and becomes unusable. In order to solve these problems, a dispersing agent that aids dispersion and a polymer that stabilizes dispersion are added, but a sufficient effect is not obtained (see Non-Patent Document 1, etc.). In order to enhance the dispersibility of organic pigment dispersions for color filters, polymers and pigment dispersants that can impart both properties of alkali developability and dispersion stability necessary for the production of color filters are added ( For example, see Patent Document 4). However, these methods do not satisfy the requirements because dispersion takes time and the viscosity increases.

  Although examples of using pigment particles prepared by the liquid phase method to improve dispersibility have been reported, none of them sufficiently satisfy the demand for monodispersed nanoparticles. For example, Patent Document 5 is a method for providing an aqueous dispersion, and no mention is made of a method for providing it as an organic solvent dispersion. The method disclosed in Patent Document 6 has a large primary particle size. Further, in Patent Document 7, although provisions on pigment particle size and distribution are disclosed, the moisture content is not taken into consideration, storage stability is poor, and contrast is not sufficiently obtained. Further, Patent Document 8 discloses the regulation of the water content only for the dispersant, but the particle size is not taken into consideration, the storage stability is inferior, and the contrast is not sufficiently obtained.

JP-A-11-237760 JP-A-6-79168 JP 2004-91560 A JP 2000-239554 A JP 2004-43776 A JP 2004-123853 A JP 2002-328215 A JP 2002-241640 A Pigment Dispersion Technology-Surface Treatment and Use of Dispersing Agents and Dispersibility Evaluation-Technical Information Association 1999

  An object of the present invention is to provide a pigment dispersion composition having a low water content, including organic pigment nanoparticles having a nanometer size with a high dispersion stability and a sharp particle size distribution peak. Furthermore, it aims at provision of the colored photosensitive resin composition excellent in stability using the said pigment dispersion composition, an inkjet ink, and the photosensitive resin transfer material. It is another object of the present invention to provide a color filter, a liquid crystal display device, and a CCD device which have high contrast and exhibit excellent display characteristics.

〔式中、Ｒ^１は、（ｍ＋ｎ）価の連結基を表し、Ｒ^２は単結合あるいは２価の連結基を表す。Ａ^１は、酸性基、塩基性窒素原子を有する基、ウレア基、ウレタン基、配位性酸素原子を有する基、炭素数４以上の炭化水素基、アルコキシシリル基、エポキシ基、イソシアネート基、および水酸基からなる群より選ばれる基を有する１価の有機基、または置換基を有してもよい有機色素構造もしくは複素環を含有する１価の有機基を表す。ただし、ｎ個のＡ^１は互いに同一であっても、異なっていてもよい。ｍは１〜８の数を表し、ｎは２〜９の数を表し、ｍ＋ｎは３〜１０を満たす。Ｐ^１は高分子化合物残基を表す。〕
（６）（１）〜（５）のいずれか１項に記載の顔料分散組成物と、エチレン性不飽和二重結合を２個以上有する多官能モノマーと、光重合開始剤ないしは光重合開始剤系とを含むことを特徴とする着色感光性樹脂組成物。
（７）仮支持体上に、少なくとも、（６）に記載の着色感光性樹脂組成物を含む感光性樹脂層を設けたことを特徴とする感光性樹脂転写材料。
（８）（１）〜（５）のいずれか１項に記載の顔料分散組成物を用いたことを特徴とするインクジェットインク。
（９）さらに、エチレン性不飽和二重結合を２個以上有するモノマーを含み、カラーフィルタ作製用とした（８）に記載のインクジェットインク。
（１０）（６）に記載の着色感光性樹脂組成物、（７）に記載の感光性樹脂転写材料、及び／又は（９）に記載のインクジェットインクを用いて作製したことを特徴とするカラーフィルタ。
（１１）（１０）に記載のカラーフィルタを備えたことを特徴とする液晶表示装置。
（１２）前記液晶表示装置がＶＡ方式であることを特徴とする（１１）に記載の液晶表示装置。
（１３）（１０）に記載のカラーフィルターを備えたことを特徴とするＣＣＤデバイス。 The above problems have been achieved by the following means.
(1) A pigment dispersion composition containing organic pigment nanoparticles and an organic solvent, wherein the ratio of particles having a primary particle size of less than 15 nm in the organic pigment nanoparticles is less than 10% (number%) and 60 nm. The pigment dispersion composition is characterized in that the proportion of particles exceeding 10% is less than 10% (number%) and the water content is 0.01% by mass to 5% by mass.
(2) The organic pigment nanoparticles are nanoparticles formed by mixing a solution in which an organic pigment is dissolved in a good solvent and a poor solvent for the organic pigment that is compatible with the solvent. The pigment dispersion composition according to (1).
(3) The pigment dispersion composition according to (1) or (2), wherein the water content is 3% by mass or less.
(4) The pigment dispersion composition according to (1) or (2), wherein the water content is 1% by mass or less.
(5) The pigment dispersion composition according to any one of (1) to (4), comprising a compound represented by the following general formula (1).

[Wherein, R ¹ represents a (m + n) -valent linking group, and R ² represents a single bond or a divalent linking group. A ¹ is an acidic group, a group having a basic nitrogen atom, a urea group, a urethane group, a group having a coordinating oxygen atom, a hydrocarbon group having 4 or more carbon atoms, an alkoxysilyl group, an epoxy group, an isocyanate group, and A monovalent organic group having a group selected from the group consisting of a hydroxyl group, or a monovalent organic group containing an organic dye structure or a heterocyclic ring which may have a substituent. However, n pieces of A ¹ may be the same as or different from each other. m represents a number of 1 to 8, n represents a number of 2 to 9, and m + n satisfies 3 to 10. P ¹ represents a polymer compound residue. ]
(6) The pigment dispersion composition according to any one of (1) to (5), a polyfunctional monomer having two or more ethylenically unsaturated double bonds, and a photopolymerization initiator or photopolymerization initiator. A colored photosensitive resin composition comprising a system.
(7) A photosensitive resin transfer material, wherein a photosensitive resin layer containing at least the colored photosensitive resin composition according to (6) is provided on a temporary support.
(8) An inkjet ink using the pigment dispersion composition according to any one of (1) to (5).
(9) The inkjet ink according to (8), which further contains a monomer having two or more ethylenically unsaturated double bonds and is for producing a color filter.
(10) A color produced using the colored photosensitive resin composition according to (6), the photosensitive resin transfer material according to (7), and / or the inkjet ink according to (9). filter.
(11) A liquid crystal display device comprising the color filter according to (10).
(12) The liquid crystal display device according to (11), wherein the liquid crystal display device is a VA system.
(13) A CCD device comprising the color filter according to (10).

  The pigment dispersion composition of the present invention contains organic pigment nanoparticles having a nanometer size and high dispersion stability, has a low water content, and can be suitably used for production of a high-contrast color filter. In addition, the colored photosensitive composition, photosensitive resin transfer material, and inkjet ink of the present invention including this can provide a color filter with excellent stability and high display quality with stable quality. In addition, the color filter of the present invention produced using these has the desired color purity and high contrast, and is excellent in weather resistance, and the liquid crystal display device using this color filter is black and has good reproducibility. This produces an excellent effect of improving display unevenness.

The pigment dispersion composition of the present invention comprises organic pigment nanoparticles and an organic solvent, and the proportion of particles having a primary particle size of less than 15 nm in the organic pigment nanoparticles is less than 10% (number%) and more than 60 nm. The ratio is less than 10% (number%), and the water content is 0.01% by mass to 5% by mass (hereinafter, when the percentage of particles is simply expressed as%, unless otherwise specified, It means the number%.)
In the present invention, the ratio of particles having a primary particle size of less than 15 nm is more preferably less than 7%, and particularly preferably less than 5%.
When the ratio of the particles of less than 15 nm is 10% or more, heat resistance and light resistance may be deteriorated, which is not preferable.
In the present invention, the proportion of the particles having a primary particle size exceeding 60 nm is preferably less than 7%, particularly preferably less than 5%.
If the ratio of the particles exceeding 60 nm is 10% or more, it may cause a decrease in contrast, which is not preferable.
In the present invention, the water content is preferably 3% by mass or less, more preferably 0.01% by mass to 3% by mass, still more preferably 1% by mass or less, and particularly preferably 0.01% by mass to 1% by mass.
When the water content is higher than 5% by mass, the stability may be deteriorated, which is not preferable. Further, in order to reduce the water content below 0.01% by mass, it takes an enormous energy cost to dehydrate the solvent used. Therefore, it is industrial to reduce the water content below 0.01% by mass. It is not preferable for production.

The organic pigment used in the present invention is not particularly limited as long as particles can be formed by a reprecipitation method. The organic pigment may be used alone, or may be a plurality or a combination thereof.
The organic pigment is not limited in hue, for example, perylene, perinone, quinacridone, quinacridonequinone, anthraquinone, anthanthrone, benzimidazolone, disazo condensation, disazo, azo, indanthrone, phthalocyanine, triarylcarbonium , Dioxazine, aminoanthraquinone, diketopyrrolopyrrole, thioindigo, isoindoline, isoindolinone, pyranthrone or isoviolanthrone compound pigment, or a mixture thereof.

More specifically, for example, C.I. I. Pigment red 190 (C.I. No. 71140), C.I. I. Pigment red 224 (C.I. No. 71127), C.I. I. Perylene compound pigments such as C.I. Pigment Violet 29 (C.I. No. 71129); I. Pigment orange 43 (C.I. No. 71105), or C.I. I. Perinone compound pigments such as C.I. Pigment Red 194 (C.I. No. 71100); I. Pigment violet 19 (C.I. No. 73900), C.I. I. Pigment violet 42, C.I. I. Pigment red 122 (C.I. No. 73915), C.I. I. Pigment red 192, C.I. I. Pigment red 202 (C.I. No. 73907), C.I. I. Pigment Red 207 (C.I. No. 73900, 73906) or C.I. I. Pigment Red 209 (C.I. No. 73905), a quinacridone compound pigment; I. Pigment red 206 (C.I. No. 73900/73920), C.I. I. Pigment orange 48 (C.I. No. 73900/73920), or C.I. I. Quinacridonequinone compound pigments such as CI Pigment Orange 49 (C.I. No. 73900/73920); I. Anthraquinone compound pigments such as C.I. Pigment Yellow 147 (C.I. No. 60645); I. Anthanthrone compound pigments such as CI Pigment Red 168 (C.I. No. 59300); I. Pigment brown 25 (C.I. No. 12510), C.I. I. Pigment violet 32 (C.I. No. 12517), C.I. I. Pigment yellow 180 (C.I. No. 21290), C.I. I. Pigment yellow 181 (C.I. No. 11777), C.I. I. Pigment orange 62 (C.I. No. 11775), or C.I. I. Benzimidazolone compound pigments such as CI Pigment Red 185 (C.I. No. 12516); I. Pigment yellow 93 (C.I. No. 20710), C.I. I. Pigment yellow 94 (C.I. No. 20038), C.I. I. Pigment yellow 95 (C.I. No. 20034), C.I. I. Pigment yellow 128 (C.I. No. 20037), C.I. I. Pigment yellow 166 (C.I. No. 20035), C.I. I. Pigment orange 34 (C.I. No. 21115), C.I. I. Pigment orange 13 (C.I. No. 21110), C.I. I. Pigment orange 31 (C.I. No. 20050), C.I. I. Pigment red 144 (C.I. No. 20735), C.I. I. Pigment red 166 (C.I. No. 20730), C.I. I. Pigment red 220 (C.I. No. 20055), C.I. I. Pigment red 221 (C.I. No. 20065), C.I. I. Pigment red 242 (C.I. No. 20067), C.I. I. Pigment red 248, C.I. I. Pigment red 262, or C.I. I. Disazo condensed compound pigments such as CI Pigment Brown 23 (C.I. No. 20060); I. Pigment yellow 13 (C.I. No. 21100), C.I. I. Pigment yellow 83 (C.I. No. 21108), or C.I. I. Disazo compound pigments such as CI Pigment Yellow 188 (C.I. No. 21094); I. Pigment red 187 (C.I. No. 12486), C.I. I. Pigment red 170 (C.I. No. 12475), C.I. I. Pigment yellow 74 (C.I. No. 11714), C.I. I. Pigment yellow 150 (C.I. No. 48545), C.I. I. Pigment red 48 (C.I. No. 15865), C.I. I. Pigment red 53 (C.I. No. 15585), C.I. I. Pigment orange 64 (C.I. No. 12760), or C.I. I. Azo compound pigments such as CI Pigment Red 247 (C.I. No. 15915), C.I. I. Indanthrone compound pigments such as C.I. Pigment Blue 60 (C.I. No. 69800); I. Pigment green 7 (C.I. No. 74260), C.I. I. Pigment Green 36 (C.I. No. 74265), Pigment Green 37 (C.I. No. 74255), Pigment Blue 16 (C.I. No. 74100), C.I. I. Phthalocyanine compound pigments such as CI Pigment Blue 75 (C.I. No. 74160: 2) or 15 (C.I. No. 74160); I. Pigment blue 56 (C.I. No. 42800), or C.I. I. Pigment Blue 61 (C.I. No. 42765: 1) and the like triarylcarbonium compound pigments, C.I. I. Pigment violet 23 (C.I. No. 51319) or C.I. I. Pigment Violet 37 (C.I. No. 51345) and other dioxazine compound pigments, C.I. I. Aminoanthraquinone compound pigments such as C.I. Pigment Red 177 (C.I. No. 65300); I. Pigment red 254 (C.I. No. 56110), C.I. I. Pigment Red 255 (C.I. No. 561050), C.I. I. Pigment red 264, C.I. I. Pigment red 272 (C.I. No. 561150), C.I. I. Pigment orange 71, or C.I. I. Diketopyrrolopyrrole compound pigments such as C.I. Pigment Orange 73; I. Thioindigo compound pigments such as C.I. Pigment Red 88 (C.I. No. 7313); I. Pigment yellow 139 (C.I. No. 56298), C.I. I. Pigment Orange 66 (C.I. No. 48210), an isoindoline compound pigment such as C.I. I. Pigment yellow 109 (C.I. No. 56284), or C.I. I. Pigment Orange 61 (C.I. No. 11295) and the like, an inindolinone compound pigment such as C.I. I. Pigment Orange 40 (C.I. No. 59700), or C.I. I. Pigment red 216 (C.I. No. 59710) and the like, or C.I. I. And isoviolanthrone compound pigments such as CI Pigment Violet 31 (60010). Among these, a quinacridone compound pigment, a diketopyrrolopyrrole compound pigment, a dioxazine compound pigment, a phthalocyanine compound pigment, or an azo compound pigment is preferable, and a diketopyrrolopyrrole compound pigment or a dioxazine compound pigment is more preferable.
Hereinafter, the diketopyrrolopyrrole compound pigment or the dioxazine compound pigment will be described in more detail.
C. I. P. R. Since pyrrolopyrrole compound pigments represented by 254, 255, and 264 have an absorption range suitable for increasing the color purity of the red pixel constituting the color filter and the color reproduction range can be expanded, An attempt is being made to use it. However, conventional pigments do not meet demands such as color purity and contrast. For example, an ink-jet ink described in JP-A-2003-336001, an ink obtained by a method using bead dispersion or salt milling, or the like cannot provide a good color filter.
According to the present invention, nano-sized pyrrolopyrrole compound pigment fine particles can be obtained with a sharp particle size distribution. In addition, when the pigment fine particles are used in a color filter, desired color purity and high contrast can be achieved at the same time, and the light resistance is excellent, and the occurrence of protrusions can be suppressed. And the liquid crystal display device provided with the color filter is excellent in blackness and red descriptive power, and display unevenness is suppressed.

  Among the above diketopyrrolopyrrole compound pigments, C.I. I. P. R. 254 (compound represented by the following formula (Z)), 255 (compound represented by the following formula (W)), and 264 (compound represented by the following formula (V)) are preferable. I. P. R. 254 is more preferable from the viewpoint of the absorption spectrum. Note that C.I. I. P. R. As 254, any commercially available product such as Irgaphor Red B-CF, Chromophthal DPP Red BO, Irgadin DPP Red BO, and Microlen DPP RED BP can be used. C. I. P. R. As 255, Croftal Coral Red C, Irgadin DPP Red 5G, or the like can be used. C. I. P. R. As H.264, Hostepperum Rubin D3B LP2615, Irgadin DPP Rubin TR, or the like can be used.

Next, the dioxazine compound pigment will be described. In recent years, C.I. I. P. B. 15: 6 has been frequently used, and the color purity of the color filter has increased. However, a light source such as a cold-cathode tube, which is a light source frequently used in liquid crystal display devices, emits a little light on the long wave side of the blue light emission peak, which makes the chromaticity inferior to NTSC.
The problem is that C.I. I. P. V. It can be improved by adding a dioxazine compound pigment represented by Nos. 23 and 37 (for example, about 5%). Although it is conceivable to improve contrast and further improve display characteristics with this color filter having high color purity, satisfactory results cannot be obtained by the conventional bead dispersion method or salt milling method.
On the other hand, according to the method for producing a pigment dispersion composition of the present invention, the dioxazine compound pigment can be obtained as a nano-sized pigment having a uniform particle size distribution. The dispersion containing the dioxazine compound pigment fine particles can be excellent in stability over time. Therefore, the color filter used therefor can achieve both high color purity and high contrast, and is excellent in light resistance. In addition, the liquid crystal display device provided with the color filter is excellent in depiction and reproducibility of black spots and blue, and display unevenness can be suppressed. Note that C.I. I. P. V. As 23, all commercially available ones such as Cromofine Violet RE, Fastgen Super Violet BBL, Helio Fast Violet EB, Microlith Violet RL-WA, and Sanyo Fast Violet BLD can be used. C. I. P. V. As 37, it is possible to use any commercially available product such as Chromophthal Violet B and Microlith Violet B-A.

  In the pigment dispersion composition of the present invention, two or more kinds of organic pigments or solid solutions of organic pigments can be used in combination.

  Examples of organic dyes include azo dyes, cyanine dyes, merocyanine dyes, and coumarin dyes. Examples of the polymer organic material include polydiacetylene and polyimide.

In the present invention, the organic pigment nanoparticles are an organic pigment solution in which an organic pigment is dissolved in a good solvent, a solvent that is compatible with the good solvent and is a poor solvent for the organic pigment (hereinafter, This solvent is also referred to as [poor solvent for organic pigments] or simply [poor solvent].) (Hereinafter, this method is sometimes referred to as “reprecipitation method”. Sometimes, the resulting dispersion containing organic pigment nanoparticles is also referred to as “organic particle reprecipitation liquid”. Here, “good solvent” refers to a solvent having a high solubility in an organic pigment, and “poor solvent” refers to a solvent having a low solubility in an organic pigment. The good solvent and the poor solvent used in the present invention are required to have a sufficient difference in solubility of the organic pigment to produce organic pigment nanoparticles, and can be used in combination with solvents that satisfy this. .
The poor solvent for the organic pigment is not particularly limited as long as it is compatible with or uniformly mixed with a good solvent for dissolving the organic pigment. As a poor solvent for the organic pigment, the solubility of the organic pigment is preferably 0.02% by mass or less, and more preferably 0.01% by mass or less. Although there is no particular lower limit to the solubility of the organic pigment in the poor solvent, 0.000001% by mass or more is practical in consideration of a commonly used organic pigment. This solubility may be the solubility when dissolved in the presence of an acid or alkali. In addition, the compatibility or uniform mixing property of the good solvent and the poor solvent is preferably 30% by mass or more, more preferably 50% by mass or more, with respect to the poor solvent. There is no particular upper limit to the amount of good solvent dissolved in the poor solvent, but it is practical to mix them in an arbitrary ratio.
Examples of the poor solvent include an aqueous solvent (for example, water or hydrochloric acid, an aqueous sodium hydroxide solution), an alcohol compound solvent, a ketone compound solvent, an ether compound solvent, an aromatic compound solvent, a carbon disulfide solvent, an aliphatic compound solvent, Examples thereof include nitrile compound solvents, halogen compound solvents, ester compound solvents, ionic liquids, mixed solvents thereof, and aqueous solvents, alcohol compound solvents, ketone compound solvents, ether compound solvents, ester compound solvents, or mixtures thereof. Preferably, an aqueous solvent, an alcohol compound solvent or an ester compound solvent is more preferable.
Examples of the alcohol compound solvent include methanol, ethanol, isopropyl alcohol, n-propyl alcohol, 1-methoxy-2-propanol and the like. Examples of the ketone compound solvent include acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone. Examples of the ether compound solvent include dimethyl ether, diethyl ether, tetrahydrofuran, and the like. Examples of the aromatic compound solvent include benzene and toluene. Examples of the aliphatic compound solvent include hexane. Examples of the nitrile compound solvent include acetonitrile. Examples of the halogen compound solvent include dichloromethane and trichloroethylene. Examples of the ester compound solvent include ethyl acetate, ethyl lactate, 2- (1-methoxy) propyl acetate and the like. The ionic liquids, for example, 1-butyl-3-methylimidazolium and PF ₆ ^-, etc. and salts thereof.

Next, a good solvent for dissolving the organic pigment will be described.
The good solvent is not particularly limited as long as it can dissolve the organic pigment to be used and is compatible with or uniformly mixed with the poor solvent. As for the solubility of the organic pigment in a good solvent, the solubility of the organic pigment is preferably 0.2% by mass or more, and more preferably 0.5% by mass or more. Although there is no particular upper limit to the solubility of the organic pigment in the good solvent, it is practical that it is 50% by mass or less in consideration of a commonly used organic pigment. This solubility may be the solubility when dissolved in the presence of an acid or alkali. The preferred range of the compatibility or uniform mixing property between the poor solvent and the good solvent is as described above.
Examples of the good solvent include an aqueous solvent (for example, water or hydrochloric acid, an aqueous sodium hydroxide solution), an alcohol compound solvent, an amide compound solvent, a ketone compound solvent, an ether compound solvent, an aromatic compound solvent, a carbon disulfide solvent, and a fat. Group compound solvents, nitrile compound solvents, sulfoxide compound solvents, halogen compound solvents, ester compound solvents, ionic liquids, mixed solvents thereof, and the like, aqueous solvents, alcohol compound solvents, ketone compound solvents, ether compound solvents, sulfoxide compounds Solvents, ester compound solvents, amide compound solvents, or mixtures thereof are preferred, aqueous solvents, alcohol compound solvents, ester compound solvents, sulfoxide compound solvents or amide compound solvents are preferred, aqueous solvents, sulfoxide compound solvents or amide compounds. More preferably medium, sulfoxide compound solvent or the amide compound solvent is particularly preferred.
Examples of the sulfoxide compound solvent include dimethyl sulfoxide, diethyl sulfoxide, hexamethylene sulfoxide, sulfolane and the like. Examples of the amide compound solvent include N, N-dimethylformamide, 1-methyl-2-pyrrolidone, 2-pyrrolidinone, 1,3-dimethyl-2-imidazolidinone, 2-pyrrolidinone, ε-caprolactam, formamide, N -Methylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, N-methylpropanamide, hexamethylphosphoric triamide and the like.
In addition, the concentration of the organic pigment solution in which the organic pigment is dissolved in the good solvent is preferably a saturated concentration of the organic pigment with respect to the good solvent under the dissolution conditions or a range of about 1/100 of this.
There are no particular limitations on the conditions for preparing the organic pigment solution, and a range from normal pressure to subcritical and supercritical conditions can be selected. The temperature at normal pressure is preferably −10 to 150 ° C., more preferably −5 to 130 ° C., and particularly preferably 0 to 100 ° C.

  In the present invention, the organic pigment must be uniformly dissolved in a good solvent, but it is also preferable to dissolve it in an acidic or alkaline manner. In general, in the case of a pigment having an alkaline and dissociable group in the molecule, alkali is used, and when there is no alkaline and dissociable group and there are many nitrogen atoms in the molecule that are prone to add protons, acidity is used. For example, quinacridone, diketopyrrolopyrrole, disazo condensation compound pigments are alkaline, and phthalocyanine compound pigments are acidic.

  Bases used for alkaline dissolution are inorganic bases such as lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, or barium hydroxide, or trialkylamine, diazabicycloundecene (DBU), An organic base such as a metal alkoxide is preferable, but an inorganic base is preferable.

  The amount of the base used is an amount capable of uniformly dissolving the pigment, and is not particularly limited. However, in the case of an inorganic base, it is preferably 1.0 to 30 molar equivalents, more preferably 1 with respect to the organic pigment. 0.0 to 25 molar equivalents, more preferably 1.0 to 20 molar equivalents. In the case of an organic base, it is preferably 1.0 to 100 molar equivalents relative to the organic pigment, more preferably 5.0 to 100 molar equivalents, and even more preferably 20 to 100 molar equivalents.

The acid used for the acidic dissolution is preferably an inorganic acid such as sulfuric acid, hydrochloric acid, or phosphoric acid, or an organic acid such as acetic acid, trifluoroacetic acid, oxalic acid, methanesulfonic acid, or trifluoromethanesulfonic acid. It is an inorganic acid. Particularly preferred is sulfuric acid.
The amount of the acid used is an amount capable of uniformly dissolving the organic pigment, and is not particularly limited, but is often used in an excessive amount as compared with the base. Regardless of the inorganic acid or organic acid, it is preferably 3 to 500 molar equivalents, more preferably 10 to 500 molar equivalents, and further preferably 30 to 200 molar equivalents with respect to the organic pigment.

  When mixing alkali or acid with an organic solvent and using it as a good solvent for organic pigments, a solvent having high solubility in some alkali or acid such as water or lower alcohol in order to completely dissolve the alkali or acid Can be added to the organic solvent. The amount of water or lower alcohol is preferably 50% by mass or less, more preferably 30% by mass or less, based on the total amount of the organic pigment solution. Specifically, water, methanol, ethanol, n-propanol, isopropanol, butyl alcohol, or the like can be used.

There are no particular limitations on the conditions of the poor solvent when the organic particles are produced, that is, when the organic particles are deposited and formed, and a range from normal pressure to subcritical and supercritical conditions can be selected. The temperature at normal pressure is preferably −30 to 100 ° C., more preferably −10 to 60 ° C., and particularly preferably 0 to 30 ° C.
When mixing the organic pigment solution and the poor solvent, either of them may be added and mixed. However, the organic pigment solution is preferably added to the poor solvent and mixed, and the poor solvent is stirred at that time. It is preferable that the The stirring speed is preferably 100 to 10,000 rpm, more preferably 150 to 8000 rpm, and particularly preferably 200 to 6000 rpm. A pump or the like may be used for the addition, or it may not be used. Moreover, although addition in a liquid or addition outside a liquid may be sufficient, addition in a liquid is more preferable.
The mixing ratio of the organic pigment solution and the poor solvent (ratio of good solvent / poor solvent in the organic particle reprecipitation liquid) is preferably 1/50 to 2/3, more preferably 1/40 to 1/2, in terms of volume ratio. / 20 to 3/8 is particularly preferable.
The concentration of the organic particle reprecipitation liquid is not particularly limited as long as the organic particles can be generated, but the organic pigment nanoparticles are preferably in the range of 10 to 40,000 mg, more preferably 20 to 30000 mg with respect to 1000 ml of the dispersion solvent. It is a range, Most preferably, it is the range of 50-25000 mg.
Moreover, the preparation scale at the time of producing | generating an organic pigment nanoparticle is although it does not specifically limit, It is preferable that the mixing amount of a poor solvent is a preparation scale of 10-2000L, and it is more preferable that it is a preparation scale of 50-1000L. .

Regarding the particle size of organic pigment nanoparticles, there is a method of expressing the average size of the population by quantifying by a measurement method, but as a common method, the mode diameter indicating the maximum value of distribution, the integral distribution curve There are median diameter corresponding to the median, various average diameters (number average, length average, area average, mass average, volume average, etc.). In the present invention, unless otherwise specified, the average particle diameter is Number average diameter. The average particle diameter of the organic pigment nanoparticles (primary particles) is a nanometer size, the average particle diameter is preferably 1 nm to 1 μm, more preferably 1 to 200 nm, and further preferably 2 to 100 nm. Preferably, it is 5-80 nm, and it is especially preferable. The particles formed by the method for producing a pigment dispersion composition of the present invention may be crystalline particles, amorphous particles, or a mixture thereof.
In the present invention, the ratio (Mv / Mn) of the volume average particle diameter (Mv) and the number average particle diameter (Mn) is used as an index representing the monodispersity of the particles unless otherwise specified. The monodispersity of particles (primary particles) contained in the organic particle dispersion used in the method for concentrating organic pigment nanoparticles, that is, Mv / Mn is preferably 1.0 to 2.0, and preferably 1.0 to 2.0. 1.8 is more preferable, and 1.0 to 1.5 is particularly preferable.
Methods for measuring the particle size of organic pigment nanoparticles include microscopy, mass method, light scattering method, light blocking method, electrical resistance method, acoustic method, dynamic light scattering method, microscopy method, dynamic light scattering method. The method is particularly preferred. Examples of the microscope used for the microscopy include a scanning electron microscope and a transmission electron microscope. Examples of the particle measuring apparatus by the dynamic light scattering method include Nanotrack UPA-EX150 manufactured by Nikkiso Co., Ltd. and Dynamic Light Scattering Photometer DLS-7000 series manufactured by Otsuka Electronics Co., Ltd.

  The pigment dispersion composition of the present invention preferably contains a dispersant. The step of adding a dispersant to the pigment dispersion composition is not particularly limited, but it is preferable to add a dispersant to and / or one of the organic pigment solution and the poor solvent. Moreover, it is also preferable to add a dispersing agent solution at the time of formation of organic nanoparticles in a system different from the above two solutions. It is also preferable to use pigment particles that have been surface-treated with a dispersant in advance, and the pigment particles may be subjected to a surface treatment that can promote adsorption of the dispersant. The dispersant (1) has a function of quickly adsorbing on the surface of the deposited pigment to form fine nanoparticles and (2) preventing these particles from aggregating again.

  As a dispersant that can be used, for example, a low molecular or high molecular dispersant of anionic, cationic, amphoteric, nonionic or pigment derivative can be used. The molecular weight of the polymer dispersant can be used without limitation as long as it can be uniformly dissolved in a solution, but preferably has a molecular weight of 1,000 to 2,000,000, and 5,000 to 1,000,000. 000 is more preferable, 10,000 to 500,000 is more preferable, and 10,000 to 100,000 is particularly preferable. Specific examples of the polymer dispersant include polyvinyl pyrrolidone, polyvinyl alcohol, polyvinyl methyl ether, polyethylene glycol, polypropylene glycol, polyacrylamide, vinyl alcohol-vinyl acetate copolymer, polyvinyl alcohol-partial formalized product, polyvinyl alcohol- Partial butyral, vinyl pyrrolidone-vinyl acetate copolymer, polyethylene oxide / propylene oxide block copolymer, polyacrylate, polyvinyl sulfate, poly (4-vinylpyridine) salt, polyamide, polyallylamine salt, condensed naphthalene sulfone Acid salts, cellulose derivatives, starch derivatives and the like can be mentioned. In addition, natural polymers such as alginate, gelatin, albumin, casein, gum arabic, tonganto gum and lignin sulfonate can also be used. Of these, polyvinylpyrrolidone is preferable. These polymers can be used alone or in combination of two or more. These dispersants can be used alone or in combination. The dispersant used for dispersing the pigment is described in detail on pages 29 to 46 of “Pigment dispersion stabilization and surface treatment technology / evaluation” (Chemical Information Association, issued in December 2001).

  Examples of anionic dispersants (anionic surfactants) include N-acyl-N-alkyl taurine salts, fatty acid salts, alkyl sulfate esters, alkyl benzene sulfonates, alkyl naphthalene sulfonates, dialkyl sulfosuccinates, alkyl phosphorus Examples include acid ester salts, naphthalene sulfonic acid formalin condensate, polyoxyethylene alkyl sulfate ester salts, and the like. Of these, N-acyl-N-alkyltaurine salts are preferred. As the N-acyl-N-alkyltaurine salt, those described in JP-A-3-273067 are preferable. These anionic dispersants can be used alone or in combination of two or more.

  Cationic dispersants (cationic surfactants) include quaternary ammonium salts, alkoxylated polyamines, aliphatic amine polyglycol ethers, aliphatic amines, diamines and polyamines derived from aliphatic amines and fatty alcohols, fatty acids And imidazolines derived from these and salts of these cationic substances. These cationic dispersants can be used alone or in combination of two or more.

The amphoteric dispersant is a dispersant having both an anion group part in the molecule of the anionic dispersant and a cationic group part in the molecule of the cationic dispersant.
Nonionic dispersants (nonionic surfactants) include polyoxyethylene alkyl ether, polyoxyethylene alkyl aryl ether, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene alkylamine, Examples thereof include glycerin fatty acid esters. Of these, polyoxyethylene alkylaryl ether is preferable. These nonionic dispersants can be used alone or in combination of two or more.

  A pigment derivative type dispersant is derived from an organic pigment as a parent substance, and is obtained by a pigmentation reaction of a pigment derivative type dispersant produced by chemically modifying the parent structure or a chemically modified pigment precursor. Defined as a pigment derivative type dispersant. For example, a sugar-containing pigment derivative-type dispersant, a piperidyl-containing pigment derivative-type dispersant, a naphthalene or perylene-derived pigment derivative-type dispersant, a pigment derivative-type dispersant having a functional group linked to a pigment parent structure via a methylene group, Pigment parent structure chemically modified with polymer, pigment derivative type dispersant having sulfonic acid group, pigment derivative type dispersant having sulfonamide group, pigment derivative type dispersant having ether group, carboxylic acid group, carboxylic acid ester And pigment derivative type dispersants having a group or a carboxamide group.

  When the pigment dispersion composition of the present invention is produced, it is preferable to coexist a pigment dispersant containing an amino group when preparing an organic pigment solution dissolved in a good solvent. Here, the amino group includes a primary amino group, a secondary amino group, and a tertiary amino group, and the number of amino groups may be one or more. A pigment derivative compound in which a substituent having an amino group is introduced into the pigment skeleton, or a polymer compound having a monomer having an amino group as a polymerization component may be used. Examples thereof include, for example, compounds described in JP-A Nos. 2000-239554, 2003-96329, 2001-31885, JP-A-10-339949, and JP-B-5-72943. However, it is not limited to these.

The dispersant having an amino group used in the method for producing the pigment dispersion composition of the present invention is not limited thereto, but is represented by the following general formulas (D1), (D3), and formula (D4). At least one selected from the compounds described above can be used.
<1. Compound represented by general formula (D1)>

  In general formula (D1), A represents a component capable of forming an azo dye together with XY. A can be arbitrarily selected as long as it is a compound capable of forming an azo dye by coupling with a diazonium compound. Specific examples of A will be shown below, but the present invention is not limited thereto.

  In general formula (D1), X represents a single bond or a group selected from divalent linking groups represented by structural formulas of the following formulas (i) to (v).

  In General Formula (D1), Y represents a group represented by the following General Formula (D2).

In general formula (D2), Z represents a lower alkylene group. Z is represented as — (CH ₂ ) _b —, wherein b represents an integer of 1 to 5, preferably 2 or 3. In General Formula (D2), —NR ₂₁ represents a lower alkylamino group or a 5- to 6-membered saturated heterocyclic group containing a nitrogen atom. When —NR ₂₁ represents a lower alkylamino group, it is represented as —N (C _r H _{2r + 1} ) ₂ , r represents an integer of 1 to 4, preferably 1 or 2. When —NR ₂₁ represents a 5- to 6-membered saturated heterocyclic group containing a nitrogen atom, any heterocyclic group represented by the following structural formula is preferable.

In the general formula (D2), Z and —NR ₂₁ may each have a lower alkyl group or an alkoxy group as a substituent. In the general formula (D2), a represents 1 or 2, preferably 2.

  Specific examples of the compound represented by the general formula (D1) are shown below, but the present invention is not limited to these specific examples.

  The compound represented by the general formula (D1) can be synthesized by, for example, a method described in JP-A No. 2000-239554.

<2. Compound represented by general formula (D3)>

In general formula (D3), Q is an anthraquinone compound dye, azo compound dye, phthalocyanine compound dye, quinacridone compound dye, dioxazine compound dye, anthrapyrimidine compound dye, ansanthrone compound dye, indanthrone compound dye, flavanthrone compound dye Represents an organic dye residue selected from a pyranthrone compound dye, a perinone compound dye, a perylene compound dye, and a thioindigo compound dye, among which an azo compound dye or a dioxazine compound dye is preferable, and an azo compound dye is preferable. More preferred.
X ₁ represents —CO—, —CONH—Y ₂ —, —SO ₂ NH—Y ₂ —, or —CH ₂ NHCOCH ₂ NH—Y ₂ —, and is —CO— or —CONH—Y ₂ —. It is preferable.
Y ₂ represents an alkylene group or an arylene group that may have a substituent, and among them, phenylene, toluylene, or hexylene is preferable, and phenylene is more preferable.
R ₁₁ and R ₁₂ may each independently form a substituted or unsubstituted alkyl group or a heterocyclic group containing at least a nitrogen atom with R ₁₁ and R ₁₂ . Of these, a methyl group, an ethyl group, a propyl group, or a pyrrolidinyl group including a nitrogen atom is preferable, and an ethyl group is more preferable.
Y ₁ represents —NH— or —O—.
Z ₁ represents a hydroxyl group or a group represented by the general formula (D3a), or when n 1 is 1, —NH—X ₁ -Q may be used. m1 represents the integer of 1-6, and 2-3 are preferable. n1 represents the integer of 1-4, and 1-2 are preferable.

In General Formula (D3a), Y ₃ represents —NH— or —O—, and m1, R ₁₁ , and R ₁₂ have the same meaning as those in General Formula (D3).

  More specifically, the compound represented by the general formula (D3) is represented by the following general formula, for example.

In general formulas (D3-1) to (D3-6), Q, m1, n1, R ₁₁ , and R ₁₂ have the same meanings as those in general formula (D3). Specific examples of the compound represented by formula (D3) are shown below, but the present invention is not limited thereto.
In the formula, Cu-Pc represents copper phthalocyanine.

Compound represented by the general formula (D3), for example R ₁₁ and alcohol compounds having amine compound with R ₁₁ and R ₁₂ having the R ₁₂ and reacted with a halogenated triazine compound, a dye compound resulting intermediate Can be obtained by reacting. The description in Japanese Patent Publication No. 5-72943 can also be referred to.

<3. Pigment Dispersant Containing Graft Copolymer>
In the method for producing a pigment dispersion composition of the present invention, it is also preferable to use a dispersant containing a graft copolymer having an amino group and an ether group and containing other components appropriately selected as necessary.
The graft copolymer has at least an amino group and an ether group, and may contain other monomers as copolymer units.
The mass average molecular weight (Mw) of the graft copolymer is preferably 3000 to 100,000, more preferably 5000 to 50000. When the mass average molecular weight (Mw) is less than 3000, aggregation of the organic nanoparticles cannot be prevented and the viscosity may increase, and when it exceeds 100,000, the solubility in an organic solvent is insufficient. , The viscosity may increase. In addition, this mass average molecular weight is a polystyrene conversion mass average molecular weight measured by gel permeation chromatography (carrier: tetrahydrofuran).

  The graft copolymer includes (i) a polymerizable oligomer having an ethylenically unsaturated double bond at the terminal, (ii) a monomer having an amino group and an ethylenically unsaturated double bond, and (iii) an ether group. It is preferable that it contains at least a polymerizable monomer having a copolymer unit and, if necessary, (iv) another monomer as a copolymer unit.

  The content of these copolymer units in the graft copolymer is preferably (i) 15 to 98% by mass of the polymerizable oligomer, more preferably 25 to 90% by mass, (Ii) The amino group-containing monomer is preferably 1 to 40% by mass, more preferably 5 to 30% by mass, and (iii) the polymerizable monomer having an ether group is 1 to 70% by mass. It is preferably 5 to 60% by mass.

  If the content of the polymerizable oligomer is less than 15% by mass, a steric repulsion effect as a dispersant may not be obtained, and aggregation of organic nanoparticles may not be prevented. In some cases, the proportion of the monomer is reduced, the adsorption ability to organic particles is lowered, and the dispersibility is not sufficient. When the content of the nitrogen-containing monomer is less than 1% by mass, the adsorption ability with respect to the organic particles is lowered and the dispersibility may not be sufficient. When the content exceeds 40% by mass, the ratio of the polymerizable oligomer is decreased. For this reason, the steric repulsion effect as a dispersant cannot be obtained, and aggregation of organic particles may not be sufficiently prevented. When the content of the polymerizable monomer having an ether group is less than 1% by mass, the development suitability in the production of a color filter or the like may not be sufficient, and when it exceeds 70% by mass, the ability as a dispersant. May decrease.

(I) Polymerizable oligomer The polymerizable oligomer (hereinafter sometimes referred to as “macromonomer”) is an oligomer having a terminal group having an ethylenically unsaturated double bond at the terminal. In the present invention, among the polymerizable oligomers, it is preferable to have a group having the ethylenically unsaturated double bond only at one of both ends of the oligomer.

  The oligomer is generally a homopolymer formed from at least one monomer selected from, for example, alkyl (meth) acrylate, hydroxyalkyl (meth) acrylate, styrene, acrylonitrile, vinyl acetate, and butadiene. Examples of the copolymer include alkyl (meth) acrylate homopolymers or copolymers, polystyrene, and the like. In the present invention, these oligomers may be substituted with a substituent, and the substituent is not particularly limited, and examples thereof include a halogen atom.

  Preferred examples of the group having an ethylenically unsaturated double bond include a (meth) acryloyl group and a vinyl group. Among these, a (meth) acryloyl group is particularly preferred.

  In the present invention, among the polymerizable oligomers, oligomers represented by the following general formula (E6) are preferable.

In the general formula (E6), R ⁶¹ and R ⁶³ represent a hydrogen atom or a methyl group. R ⁶² represents an alkylene group which may be substituted by an alcoholic hydroxyl group having 1 to 8 carbon atoms, preferably an alkylene group having 2 to 4 carbon atoms. Y ⁶ represents a phenyl group, a phenyl group having an alkyl group having 1 to 4 carbon atoms, or —COOR ⁶⁴ (where R ⁶⁴ is an alcoholic hydroxyl group having 1 to 6 carbon atoms, or an alkyl which may be substituted with a halogen atom). A phenyl group or —COOR ⁶⁴ (wherein R ⁶⁴ may be substituted with an alcoholic hydroxyl group having 1 to 4 carbon atoms). Represents a good alkyl group). q represents 20-200.

  Specific examples of the polymerizable oligomer include poly-2hydroxyethyl (meth) acrylate, polystyrene, polymethyl (meth) acrylate, poly-n-butyl (meth) acrylate, poly-i-butyl (meth) acrylate, and those A copolymer which is a copolymer and has a (meth) acryloyl group bonded to one molecular end is preferable.

  The polymerizable oligomer may be a commercially available product or an appropriately synthesized product. Examples of the commercially available product include a one-end methacryloylated polystyrene oligomer (Mn = 6000, trade name: AS-6). , Manufactured by Toa Gosei Chemical Co., Ltd.), one-end methacryloylated polymethyl methacrylate oligomer (Mn = 6000, trade name: AA-6, manufactured by Toa Gosei Chemical Co., Ltd.), one-end methacryloylated poly-n -Butyl acrylate oligomer (Mn = 6000, trade name: AB-6, manufactured by Toa Gosei Chemical Co., Ltd.), one-end methacryloylated polymethyl methacrylate / 2-hydroxyethyl methacrylate oligomer (Mn = 7000, trade name: AA) -714, manufactured by Toa Gosei Chemical Co., Ltd.), one-end methacryloylated polybutylmethacrylate / 2-hydroxyethyl methacrylate oligomer (Mn = 7000, trade name: 707S, manufactured by Toa Gosei Chemical Co., Ltd.), one-end methacryloylated poly-2-ethylhexyl methacrylate / 2-hydroxyethyl methacrylate oligomer (Mn = 7000) And trade names: AY-707S, AY-714S, manufactured by Toagosei Chemical Co., Ltd.), and the like.

  Preferred specific examples of the polymerizable oligomer in the present invention include at least one oligomer selected from a polymer of alkyl (meth) acrylate and a copolymer of alkyl (meth) acrylate and polystyrene, A number average molecular weight is 1000-20000, and what has a (meth) acryloyl group at the terminal is mentioned.

(Ii) Amino group-containing monomer As the amino group-containing monomer, for example, at least one selected from compounds represented by the following general formula (E2) is preferably exemplified.

In the general formula (E2), R ²¹ represents a hydrogen atom or a methyl group. R ²² represents an alkylene group having 1 to 8 carbon atoms, and among these, an alkylene group having 1 to 6 carbon atoms is preferable, and an alkylene group having 2 to 3 carbon atoms is particularly preferable.

X ² represents —N (R ²³ ) (R ²⁴ ), —R ²⁵ N (R ²⁶ ) (R ²⁷ ). ^{Wherein, R 23} and ^{R 24} represents a hydrogen atom, an alkyl group or a phenyl group having 1 to 6 carbon atoms. R ²⁵ represents an alkylene group having 1 to 6 carbon atoms, and R ²⁶ and R ²⁷ represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group.

Among the above, R ²³ and R ²⁴ in —N (R ²³ ) (R ²⁴ ) are preferably a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group, and —R ²⁵ —N (R ²⁶ ) (R ^{R 25} of ²⁷⁾ is preferably an alkylene group having 2 to 6 carbon ^{atoms, R 26} and ^{R 27,} preferably an alkyl group having 1 to 4 carbon atoms. m2 and n2 represent 1 or 0, and m2 = 1 and n2 = 1 or m2 = 1 and n2 = 0 are preferable (that is, corresponding to monomers represented by the following general formulas (E3) and (E4)) To do).

  In the present invention, among the monomers represented by the general formula (E2), at least one selected from monomers represented by any of the following general formulas (E3) and (E4) is preferable.

In the general formula (E3), R ³¹ has the same meaning as R ²¹ . R ³² has the same meaning as R ²² . X ³ has the same meaning as X ² .

In the general formula (E4), R ⁴¹ has the same meaning as R ²¹ . X ⁴ is synonymous with X ² , and —N (R ⁴³ ) (R ⁴⁴ ) (where R ⁴³ and R ⁴⁴ are synonymous with R ²³ and R ²⁴ ), or —R ⁴⁵ —. N (R ⁴⁶ ) (R ⁴⁷ ) (where R ⁴⁵ , R ⁴⁶ and R ⁴⁷ have the same meanings as R ²⁵ , R ²⁶ and R ²⁷ , respectively) is preferable.

  Specific examples of the monomer represented by the general formula (E2) include dimethyl (meth) acrylamide, diethyl (meth) acrylamide, diisopropyl (meth) acrylamide, di-n-butyl (meth) acrylamide, and di-i-butyl. (Meth) acrylamide, morpholino (meth) acrylamide, piperidino (meth) acrylamide, N-methyl-2-pyrrolidyl (meth) acrylamide and N, N-methylphenyl (meth) acrylamide (above (meth) acrylamides); (N, N-dimethylamino) ethyl (meth) acrylamide, 2- (N, N-diethylamino) ethyl (meth) acrylamide, 3- (N, N-diethylamino) propyl (meth) acrylamide, 3- (N, N -Dimethylamino) propyl (meth) acrylic 1- (N, N-dimethylamino) -1,1-dimethylmethyl (meth) acrylamide, 6- (N, N-diethylamino) hexyl (meth) acrylamide (aminoalkyl (meth) acrylamides) and the like. It is mentioned as preferable.

(Iii) Polymerizable monomer having an ether group Preferred examples of the polymerizable monomer having an ether group include at least one selected from monomers represented by the following general formula (E1).

In the general formula (E1), R ¹¹ represents a hydrogen atom or a methyl group. R ¹² represents an alkylene group having 1 to 8 carbon atoms. Among them, an alkylene group having 1 to 6 carbon atoms is preferable, and an alkylene group having 2 to 3 carbon atoms is more preferable. X ¹ represents —OR ¹³ or —OCOR ¹⁴ . Here, R ¹³ represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, a phenyl group, or a phenyl group substituted with an alkyl group having 1 to 18 carbon atoms. R ¹⁴ represents an alkyl group having 1 to 18 carbon atoms. Moreover, m3 represents 2-200, 5-100 are preferable and 10-100 are especially preferable.

  The polymerizable monomer having an ether group is not particularly limited as long as it has an ether group and is polymerizable, and can be appropriately selected from ordinary ones. For example, polyethylene glycol mono (meth) Examples include acrylate, polypropylene glycol mono (meth) acrylate, polyethylene glycol polypropylene glycol mono (meth) acrylate, polytetramethylene glycol monomethacrylate, etc., and these may be commercially available products or may be appropriately synthesized. Good. Examples of the commercially available products include methoxypolyethylene glycol methacrylate (trade names: NK esters M-40G, M-90G, M-230G (manufactured by Toa Gosei Chemical Co., Ltd.); trade names: BLEMMER PME-100, PME. -200, PME-400, PME-1000, PME-2000, PME-4000 (manufactured by Nippon Oil & Fats Co., Ltd.)), polyethylene glycol monomethacrylate (trade names: BLEMMER PE-90, PE-200, PE- 350, manufactured by NOF Corporation), polypropylene glycol monomethacrylate (trade names: BLEMMER PP-500, PP-800, PP-1000, manufactured by NOF Corporation), polyethylene glycol polypropylene glycol monomethacrylate (trade name) : Bremmer 70PEP-370B, Japan Manufactured by Yushi Co., Ltd.), polyethylene glycol polytetramethylene glycol monomethacrylate (trade name: Blemmer 55PET-800, manufactured by Nippon Oil & Fats Co., Ltd.), polypropylene glycol polytetramethylene glycol monomethacrylate (trade name: Blemmer NHK-5050) , Manufactured by Nippon Oil & Fats Co., Ltd.).

(Iv) Other monomer The graft copolymer may further contain the other monomer as a copolymer unit, and the other monomer is not particularly limited and is appropriately selected depending on the purpose. For example, aromatic vinyl compounds (eg, styrene, α-methylstyrene and vinyltoluene), (meth) acrylic acid alkyl esters (eg, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl) (Meth) acrylate and i-butyl (meth) acrylate), (meth) acrylic acid alkylaryl ester (eg, benzyl (meth) acrylate), glycidyl (meth) acrylate, carboxylic acid vinyl ester (eg, vinyl acetate and propionic acid) Vinyl), vinyl cyanide (eg, (meth) acrylonitrile and And α-chloroacrylonitrile), aliphatic conjugated dienes (eg, 1,3-butadiene and isoprene), (meth) acrylic acid, and the like. Among these, unsaturated carboxylic acid, (meth) acrylic acid alkyl ester, (meth) acrylic acid alkyl aryl ester, and carboxylic acid vinyl ester are preferable.

  As content of this other monomer in the said graft copolymer, 5-70 mass% is preferable, for example. When the content is less than 5% by mass, the physical properties of the coating film may not be controlled. When the content exceeds 70% by mass, the ability as a dispersant may not be sufficiently exhibited.

As a preferred specific example of the graft copolymer,
(11) 3- (N, N-dimethylamino) propylacrylamide / polyethylene glycol mono (meth) acrylate / terminal methacryloylated polymethyl (meth) acrylate copolymer,
(12) 3- (N, N-dimethylamino) propylacrylamide / polyethylene glycol mono (meth) acrylate / terminal methacryloylated polystyrene copolymer,

(13) 3- (N, N-dimethylamino) propylacrylamide / polyethylene glycol mono (meth) acrylate / methyl (meth) acrylate-terminated methacryloylated polystyrene copolymer,
(14) a copolymer of a copolymer of 3- (N, N-dimethylamino) propylacrylamide / polyethylene glycol mono (meth) acrylate / terminal methacryloylated methyl (meth) acrylate and 2-hydroxyethyl methacrylate,
(15) 3- (N, N-dimethylamino) propylacrylamide / polyethylene glycol mono (meth) acrylate / terminated methacryloylated methyl methacrylate and 2-hydroxyethyl methacrylate copolymer,
(16) a copolymer of a copolymer of 3- (N, N-dimethylamino) propylacrylamide / polyethylene glycol mono (meth) acrylate / terminal methacryloylated methyl methacrylate and 2-hydroxyethyl methacrylate,

(17) 3- (N, N-dimethylamino) propylacrylamide / polypropylene glycol mono (meth) acrylate / terminal methacryloylated polymethyl (meth) acrylate copolymer,
(18) 3- (N, N-dimethylamino) propylacrylamide / polyethylene glycol polypropylene glycol mono (meth) acrylate / terminal methacryloylated polymethyl (meth) acrylate copolymer,
(19) 3- (N, N-dimethylamino) propylacrylamide / polyethylene glycol polytetramethylene glycol mono (meth) acrylate / terminal methacryloylated polymethyl (meth) acrylate copolymer,
(20) 3- (N, N-dimethylamino) propylacrylamide / polypropylene glycol polytetramethylene glycol mono (meth) acrylate / terminal methacryloylated polymethyl (meth) acrylate copolymer, and the like.
Among these, (11), (14), and (18) are preferable, and a compound represented by the following formula (D4) is more preferable. In formula (D4), Me represents a methyl group.

  The graft copolymer can be obtained, for example, by radical polymerization of the components to be the copolymer units in a solvent. In the radical polymerization, a radical polymerization initiator can be used, and a chain transfer agent (eg, 2-mercaptoethanol and dodecyl mercaptan) can be further used. JP-A-2001-31885 can be referred to for the pigment dispersant containing the graft copolymer.

  In order to further improve the uniform dispersibility and storage stability of the organic particles, the content of the dispersant is preferably in the range of 0.1 to 1000 parts by weight, more preferably 100 parts by weight of the pigment. It is the range of 1-500 mass parts, More preferably, it is the range of 5-20 mass parts. If the amount is less than 0.1 parts by mass, the dispersion stability of the organic nanoparticles may not be improved. Moreover, a dispersing agent may be used independently or may be used in combination of multiple things.

[Manufacturing equipment]
Although the preferable embodiment of the manufacturing apparatus used for manufacture of the pigment dispersion composition of this invention is described, this invention is not interpreted limitedly by this.

(Manufacturing device example 1)
FIG. 1 is a preferred embodiment of a production apparatus used for producing the pigment dispersion composition of the present invention. In FIG. 1, the organic material solution is continuously supplied into the container 11 through the supply pipe 14. Here, a poor solvent 11a is contained in the container 11, and the bulk poor solvent is always convected by the action of stirring.
FIG. 2 is a schematic view of another preferred embodiment of the production apparatus used for producing the pigment dispersion composition of the present invention. In the production apparatus of FIG. 1, a mixing chamber (stirring region) 13 is provided in the container 11. Is. The mixing chamber 13 is provided below the surface of the poor solvent, and the inside thereof is filled with the poor solvent. The bulk poor solvent in the reaction vessel 11 is always convected by the agitation action in the mixing chamber 13 so as to cross the mixing chamber 13 from below to above (in the direction of the arrow in the figure).

  FIG. 3 is an enlarged partial sectional view schematically showing the mixing chamber 13 in an enlarged manner as one embodiment of the manufacturing apparatus of FIG. The organic material solution is supplied from the supply pipe 14 into the mixing chamber 13. The mixing chamber 13 is formed by a casing 17 composed of a rectangular cylinder having a constant cross-sectional area, the upper end of the casing 17 is an open end (open portion), and a circular hole 18 is provided at the lower end. The poor solvent is connected to the bulk poor solvent outside the stirring region (in the configuration shown in the drawing, the region other than the mixing chamber 13 in the poor solvent 11a is outside the stirring region and is also referred to as the non-stirring region). It has become. Here, the organic material solution supply pipe 14 is provided in a wall constituting the lower end of the casing 17 and opens toward the circular hole. A stirring blade 12 is provided in the mixer 13. The stirring blade is attached to a shaft 15 and is rotated by a motor 16. The rotation of the stirring blade 12 causes the poor solvent to constantly circulate through the circular hole 18 in the mixer 13 from below to above.

The stirring blade 12 provided in the mixing chamber 13 must produce a desired mixing strength in the mixing chamber. This mixing strength is presumed to be an important operating factor for the size of the droplet when the organic pigment solution is mixed.
In addition, the stirring blade 12 is formed by organic nanoparticles generated in the mixing space remaining in the mixing chamber 13, so that the stirring blade 12 is combined with other organic nanoparticles to become larger particles, or an organic material supplied to the mixing chamber 13. In order to prevent large particles from being generated by exposure to a solution, the organic nanoparticles that have been generated can be quickly extracted and quickly discharged out of the mixing chamber 13. preferable.
As long as the said objective is achieved as the stirring blade 12, what kind of thing may be sufficient, for example, a turbine type, a fan turbine type, etc. may be used.
Moreover, it is preferable that the casing 17 is comprised by the square cylinder as mentioned above. By doing in this way, the angle of the casing 17 disturbs the flow created by the stirring blade 12, and the mixing effect can be further enhanced without requiring an additional material such as a baffle plate.

  FIG. 4 is an enlarged partial sectional view of a mixer having two stirring blades (mixing blade 19a for mixing and stirring blade 19b for discharging) as another embodiment of the manufacturing apparatus of FIG. By providing two stirring blades in this way, the ability to control the mixing strength and the ability to discharge the generated organic pigment particles to the outside of the mixer can be selected independently. It is possible to operate by setting the circulation amount to a desired value independently.

(Manufacturing device example 2)
FIG. 5 is a cross-sectional view schematically showing another embodiment of the production apparatus used for producing the pigment dispersion composition of the present invention. In FIG. 5, the organic material solution and the poor solvent are continuously supplied into the stirring tank 21a through the supply pipes 24a and 24b, respectively. The organic material particles generated in the agitation tank 21a stay in the agitation tank 21a, so that the organic material particles are combined with other organic pigment particles to become larger particles or exposed to the organic material solution supplied from the supply pipes 24a and 24b. The generated organic material particle dispersion is quickly drawn out from the discharge pipe 23 so that the large particles are not generated due to the large particles.

FIG. 6 is a cross-sectional view schematically showing still another embodiment of the apparatus used for producing the pigment dispersion composition of the present invention. In the manufacturing apparatus of FIG. 6, the stirrer 50 includes two liquid supply ports 32 and 33 through which an organic material solution and a poor solvent respectively flow in, and a liquid discharge port 36 through which the mixed liquid after the stirring process is discharged. A cylindrical agitation tank 38 and a pair of agitation blades 41 and 42 which are agitation means for controlling the agitation state of the liquid in the agitation tank 38 by being driven to rotate in the agitation tank 38 are provided.
The agitation tank 38 includes a cylindrical tank body 39 whose central axis is directed in the vertical direction, and a seal plate 40 serving as a tank wall that closes the upper and lower opening ends of the tank body 39. The agitation tank 38 and the tank body 39 are made of a nonmagnetic material having excellent magnetic permeability. The two liquid supply ports 32 and 33 are provided at positions near the lower end of the tank body 39, and the liquid discharge port 36 is provided at a position near the upper end of the tank body 39.

  Then, the pair of stirring blades 41 and 42 are disposed apart from the upper and lower ends facing each other in the stirring tank 38 and are driven to rotate in opposite directions. Each of the stirring blades 41 and 42 constitutes a magnetic coupling C with an external magnet 46 disposed outside the tank wall (seal plate 40) in which the respective stirring blades 41 and 42 are close to each other. That is, the blades 41 and 42 are coupled to the external magnets 46 by magnetic force, and are rotated in opposite directions by driving the external magnets 46 with independent motors 48 and 49.

The pair of stirring blades 41 and 42 disposed opposite to each other in the tank 38 allows the stirring flows having different directions to enter the tank 38 as indicated by the wavy arrow (X) and the solid line arrow (Y) in FIG. Form. And since the stirring flow which each stirring blade 41 and 42 forms differs in the flow direction, it collides with each other, the high speed turbulent flow which accelerates | stimulates stirring in the tank 38 is produced | generated in the tank 38, Is prevented from becoming steady, and even when the rotation speed of the stirring blades 41 and 42 is increased, the formation of a cavity around the rotation axis of the stirring blades 41 and 42 is prevented, and at the same time, the stirring action is sufficiently achieved. Therefore, it is possible to prevent a disadvantage that a steady flow that flows in the tank 38 along the inner peripheral surface of the stirring tank 38 is formed. Therefore, the processing speed can be easily improved by increasing the speed of rotation of the stirring blades 41 and 42. Further, at this time, the liquid flow in the tank 38 becomes steady, and liquid with insufficient stirring and mixing is obtained. It is possible to prevent discharge and prevent deterioration in processing quality.
In addition, since the stirring blades 41 and 42 in the stirring tank 38 are connected to the motors 48 and 49 disposed outside the stirring tank 38 by the magnetic coupling C, the rotating shaft is attached to the tank wall of the stirring tank 38. Since there is no need for insertion, the stirring tank 38 can be made into a closed container structure without the insertion part of the rotating shaft, so that leakage of the stirred and mixed liquid to the outside of the tank can be prevented and at the same time the lubricating liquid (seal for the rotating shaft) It is possible to prevent deterioration in processing quality due to mixing of the liquid) into the liquid in the tank 38 as an impurity.

In the production of the pigment dispersion composition of the present invention, it is possible to produce organic nanoparticles not only in a batch method but also in a continuous flow method using a production apparatus having these configurations, and can be used for mass production. In addition, since the generated organic nanoparticle dispersion liquid is quickly discharged, the ratio of the organic material solution and the poor solvent liquid supplied into the stirring tank can be always kept constant. For this reason, it becomes possible to make the solubility of the organic material of a dispersion liquid constant from the time of manufacture start to the end of manufacture, and it is possible to stably manufacture monodisperse organic nanoparticles.
Furthermore, the liquid flow in the tank becomes steady and the organic nanoparticle dispersion liquid with insufficient stirring and mixing is prevented from being discharged, and the lubricating liquid (seal liquid) for the rotating shaft is an impurity in the tank. By preventing mixing in the liquid, monodispersed organic nanoparticles can be produced more stably.

(Manufacturing device example 3)
As an apparatus used for producing the pigment dispersion composition of the present invention, a production method in which stirring is performed using blades having shearing force, which is still another embodiment, will be described.
The shearing force referred to in the present invention is a shearing force exerted on the droplets (droplets) generated by the stirring blade after the organic material solution is mixed in the poor solvent.
The shape of the stirring unit that can be used in the present invention is not particularly limited as long as it can be subjected to a high shear force, but generally includes paddle blades, turbine blades, screw blades, fowler blades, etc., preferably dissolver blades, An agitating, emulsifying, and dispersing machine of an agitating part composed of a turbine part that can rotate and a fixed stator part that is positioned with a slight gap around it is preferable.
The dissolver blade is a special stirring blade having a function capable of forming a high shearing force. One example of the dissolver blade is schematically shown in a front view in FIG. 7, and a drawing substitute photograph is shown in FIG.
Further, an apparatus having a stirring portion composed of a turbine portion that can rotate as shown in FIG. 9 and a fixed stator portion positioned with a slight gap around the turbine portion is also preferably used. Examples of the disperser include Hiscotron manufactured by Microtech / Nichion Co., Ltd. and T.K. Examples include K homomixer and ULTRA-TURRAX manufactured by IKA.

  The stirring speed varies depending on the viscosity of the poor solvent, the temperature, the type of surfactant and the amount added, but is preferably 100 to 10000 rpm, more preferably 150 to 8000 rpm, and particularly preferably 200 to 6000 rpm. If the rotational speed is too low, the stirring effect is not sufficiently exhibited. Conversely, if the rotational speed is too high, bubbles are involved in the poor solvent, which is not preferable.

[concentrated]
In the method for producing the pigment dispersion composition of the present invention, the organic nanoparticle dispersion can be desalted and concentrated to produce a concentrate suitable for a color filter coating liquid and an inkjet ink on an industrial scale. Is possible.
Below, the concentration method is demonstrated.
The concentration method is not particularly limited as long as the organic nanoparticle liquid can be concentrated. For example, an extraction solvent is added to and mixed with the organic nanoparticle dispersion, and the organic nanoparticles are concentrated and extracted into the extraction solvent phase. The solution is filtered through a filter or the like to obtain a concentrated nanoparticle solution, the method is to concentrate and concentrate organic nanoparticles by centrifugation, the method is to desalinate and concentrate by ultrafiltration, and the solvent is sublimated by vacuum lyophilization. The method of concentrating, the method of drying and concentrating the solvent by heating or pressure reduction, etc. are preferable. Or a combination thereof is very preferably used.
In the process of passing through the low water content pigment dispersion composition of the present invention, when the water dispersion is subjected to the concentration process, the water content of the concentrated wet cake is usually 15% by mass to 95% by mass, but 30% by mass to 90 mass% is preferable and 50 mass%-85 mass% are more preferable.
When the moisture content of the wet cake is less than 15% by mass, the pigment particles may form an irreversible aggregate and become undispersible. Moreover, if the moisture content of the wet cake exceeds 95% by mass, a large amount of organic solvent may be required in the subsequent step.
In the process of obtaining the low water content pigment dispersion composition of the present invention, a pigment solvent concentrate may be passed. The pigment concentration in the solvent concentrate is usually 10% by mass to 70% by mass, preferably 15% by mass to 60% by mass, and more preferably 20% by mass to 50% by mass. Further, the water content in the concentrate is preferably 50% by mass or less, more preferably 30% by mass or less, and particularly preferably 10% by mass or less, based on the pigment.
The moisture content can be measured by any known method, but in the present invention, the moisture content was measured by the Karl Fischer method (Experimental Chemistry Course 15 (below) Analytical Chemistry P241-).
The concentration of the organic nanoparticles after concentration is preferably 1 to 100% by mass, more preferably 5 to 100% by mass, and particularly preferably 10 to 100% by mass.

A method for concentration extraction will be described below.
The extraction solvent used for the concentration extraction is not particularly limited, but does not substantially mix with the dispersion solvent (for example, an aqueous solvent) of the organic nanoparticle dispersion (in the present invention, substantially does not mix) This means that the solubility is low, preferably 50% by mass or less, and more preferably 30% by mass or less, although there is no particular lower limit to this amount, it is 1% by mass or more considering the solubility of ordinary solvents. It is preferable to use a solvent that forms an interface when allowed to stand after mixing, and this extraction solvent also has weak aggregation (such as milling or high-speed stirring) in which organic nanoparticles can be redispersed in the extraction solvent. It is preferable that the solvent be a floc that can be re-dispersed without applying a high shearing force. The organic nanoparticles are preferably wetted with an extraction solvent, while a dispersion solvent such as water can be easily removed by filter filtration, etc. As the extraction solvent, an ester compound solvent, an alcohol compound solvent, an aromatic compound solvent, Aliphatic compound solvents are preferred, ester compound solvents, aromatic compound solvents or aliphatic compound solvents are more preferred, and ester compound solvents are particularly preferred.

  Examples of the ester compound solvent include 2- (1-methoxy) propyl acetate, ethyl acetate, and ethyl lactate. Examples of the alcohol compound solvent include n-butanol and isobutanol. Examples of the aromatic compound solvent include benzene, toluene, xylene and the like. Examples of the aliphatic compound solvent include n-hexane and cyclohexane. Further, the extraction solvent may be a pure solvent based on the above preferred solvent or a mixed solvent composed of a plurality of solvents.

The amount of the extraction solvent is not particularly limited as long as the organic nanoparticles can be extracted, but is preferably smaller than the organic nanoparticle dispersion in consideration of concentration and extraction. When this is shown by volume ratio, when the organic nanoparticle dispersion liquid is 100, the extraction solvent to be added is preferably in the range of 1 to 100, more preferably in the range of 10 to 90, and 20 to 80. The range of is particularly preferable. If it is too much, it will take a lot of time for concentration, and if it is too little, extraction will be insufficient and nanoparticles will remain in the dispersion solvent.
After adding the extraction solvent, it is preferable to stir and mix so as to be in sufficient contact with the dispersion. A normal method can be used for stirring and mixing. Although there is no restriction | limiting in particular in the temperature when adding and mixing an extraction solvent, It is preferable that it is 1-100 degreeC, and it is more preferable that it is 5-60 degreeC. Any device may be used for adding and mixing the extraction solvent as long as each step can be preferably performed. For example, a separation funnel type device can be used.

  In the case of ultrafiltration, for example, a method used for desalting / concentration of a silver halide emulsion can be applied. Research Disclosure No. 10208 (1972), no. 13 122 (1975) and no. 16 351 (1977) is known. The pressure difference and flow rate that are important as operating conditions can be selected by referring to the characteristic curve described in Haruhiko Oya's “Membrane Utilization Technology Handbook”, Koshobo Publishing (1978), p275. In order to process the particles, it is necessary to find an optimum condition in order to suppress the aggregation of particles. There are two methods for replenishing the solvent that is lost due to membrane permeation: a constant volume method in which the solvent is continuously added and a batch method in which the solvent is intermittently added, but the desalting time is relatively short. The formula is preferred. As the solvent to be replenished, pure water obtained by ion exchange or distillation is used. However, a dispersant, a poor solvent for the dispersant may be mixed in pure water, or directly into the organic nanoparticle dispersion. It may be added.

  FIG. 10 shows an example of the configuration of an apparatus for performing ultrafiltration. As shown in FIG. 10, this apparatus comprises a tank 81 containing a fatty acid silver dispersion, a circulation pump 82 for circulating the dispersion in the tank 81, and a dispersion introduced by the circulation pump 82. It has an ultrafiltration module 83 that removes by-product inorganic salts as permeate. The dispersion from which the permeated water has been separated is returned to the tank 81 again, and the same operation is repeated until the predetermined purpose of removing the by-product inorganic salt is achieved. Further, this apparatus is provided with a replenishment pure water measurement flow meter 84 used to replenish a certain amount of solvent lost by permeate as pure water, and is used to determine the replenishment amount of pure water. A permeated water flow meter 85 is installed. Further, a reverse cleaning pump 86 for introducing water for diluting the permeated water is installed.

  Ultrafiltration membranes, such as flat plate type, spiral type, cylindrical type, hollow fiber type and hollow fiber type, which are already incorporated as modules, are available from Asahi Kasei Corporation, Daicel Chemical Co., Ltd., Toray Industries, Inc. ( Although it is commercially available from Nitto Denko Corporation, a spiral type or a hollow fiber type is preferred from the viewpoint of the total membrane area and detergency. In addition, the molecular weight cut off as an index of the threshold value of the component that can permeate the membrane needs to be determined from the molecular weight of the dispersant used, but preferably 5,000 or more and 50,000 or less, More preferred is 5,000 or more and 15,000 or less.

  In order to separate the dispersion solvent from the organic nanoparticle dispersion and the concentrated extract, it is preferable to filter. As the filter filtration device, for example, a device such as pressure filtration can be used. Preferred filters include nanofilters and ultrafilters. It is preferable to remove the remaining dispersion solvent by filter filtration and further concentrate the organic nanoparticles in the concentrated extract to obtain a concentrated nanoparticle solution.

  The method of lyophilization is not particularly limited, and any method that can be used by those skilled in the art may be adopted. For example, a refrigerant direct expansion method, an overlap refrigeration method, a heat medium circulation method, a triple heat exchange method, and an indirect heating freezing method can be mentioned, preferably a refrigerant direct expansion method, an indirect heating freezing method, more preferably an indirect heating freezing method. It is good to use. In any method, it is preferable to perform freeze-drying after preliminary freezing. The pre-freezing conditions are not particularly limited, but it is necessary that the sample to be freeze-dried is completely frozen.

  Indirect heating freezing equipment includes small freeze dryer, FTS freeze dryer, LYOVAC freeze dryer, experimental freeze dryer, research freeze dryer, triple heat exchange vacuum freeze dryer, mono-cooling freeze dryer , HULL freeze dryers, preferably small freeze dryers, laboratory freeze dryers, research freeze dryers, monocooling freeze dryers, more preferably small freeze dryers, monocooling freeze dryers Should be used.

  Although the temperature of freeze-drying is not specifically limited, For example, it is -190--4 degreeC, Preferably it is -120--20 degreeC, More preferably, it is about -80--60 degreeC. The pressure of lyophilization is not particularly limited, and can be appropriately selected by those skilled in the art. For example, the pressure may be 0.1 to 35 Pa, preferably 1 to 15 Pa, and more preferably about 5 to 10 Pa. The freeze-drying time is, for example, 2 to 48 hours, preferably 6 to 36 hours, and more preferably about 16 to 26 hours. However, these conditions can be appropriately selected by those skilled in the art. Regarding the freeze-drying method, for example, Formulation Machine Technology Handbook: Formulation Machine Technology Study Group, Jinshokan, p. 120-129 (September 2000); Vacuum Handbook: Japan Vacuum Technology Co., Ltd., Ohm, p. 328-331 (1992); Journal of the Research Group on Freezing and Drying: Koji Ito et al. 15, p. 82 (1965) or the like.

The centrifugation will be described below.
The centrifuge used for concentration of the organic nanoparticles by centrifugation may be any device as long as it can precipitate the organic nanoparticles in the organic nanoparticle dispersion (or the organic nanoparticle concentrated extract). As a centrifuge, for example, in addition to a general-purpose device, a device with a skimming function (a function of sucking the supernatant layer during rotation and discharging it out of the system) or continuous centrifugation for continuously discharging solid matter Machine.
Centrifugation conditions are preferably 50 to 10000, more preferably 100 to 8000, and particularly preferably 150 to 6000 in terms of centrifugal force (a value representing how many times the gravitational acceleration is applied). Although the temperature at the time of centrifugation is based on the solvent seed | species of a dispersion liquid, -10-80 degreeC is preferable, -5-70 degreeC is more preferable, 0-60 degreeC is especially preferable.

The drying will be described below.
The apparatus used for concentration of the organic nanoparticles by drying under reduced pressure is not particularly limited as long as the solvent of the organic nanoparticle dispersion (or organic nanoparticle concentrated extract) can be evaporated. For example, a general-purpose vacuum dryer and a rotary pump, an apparatus that can be heated and reduced in pressure while stirring the liquid, and an apparatus that can be continuously dried by passing the liquid through a heated and reduced pressure tube.
The heating and drying temperature is preferably 30 to 230 ° C, more preferably 35 to 200 ° C, and particularly preferably 40 to 180 ° C. The pressure during decompression is preferably 100 to 100,000 Pa, more preferably 300 to 90,000 Pa, and particularly preferably 500 to 80,000 Pa.

According to the concentration method as described above, the organic nanoparticles can be efficiently concentrated from the organic nanoparticle dispersion. Regarding the concentration ratio, for example, when the concentration of the nanoparticles in the organic nanoparticle dispersion as a raw material is 1, the concentration in the concentrated organic nanoparticle paste is preferably about 100 to 3000 times, more preferably about 500 to 2000 times. Can be concentrated.
In the method for producing a pigment dispersion composition of the present invention, the organic particles that are in an aggregated state are redispersed by the above concentration (in the present invention, redispersion is to increase the degree of dispersion by deaggregating particles in a dispersion liquid). It is sometimes referred to as fine dispersion).
The organic particles contained in the organic particle liquid concentrated by the extraction solvent, centrifugation, and drying described above are usually aggregated by the concentration. At this time, in order to enable rapid filter filtration and obtain a good dispersion state again, it is preferable to obtain flocs aggregated to such an extent that they can be redispersed.
For this reason, the degree of dispersion using an ordinary dispersion method is insufficient for the formation of fine particles, and a method with higher micronization efficiency is required. Even in such an aggregated organic particle (in the present invention, an aggregated organic particle is a particle in which organic particles such as an aggregate are gathered by a secondary force. When the primary particle is nanometer size, the aggregated nanoparticle According to the method for producing an organic nanoparticle dispersion of the present invention, the organic particles are suitably finely dispersed by containing a polymer compound having a mass average molecular weight of 1000 or more in the aggregated organic particle liquid. (In the present invention, the agglomerated organic particle liquid refers to a liquid containing the agglomerated organic particles in the liquid, and even if the agglomerated organic particles are contained even in a dispersion, a concentrated liquid, a paste, a slurry, etc.) Good.)

Next, a polymer compound that can be preferably used in the method for producing the pigment dispersion composition of the present invention (in the present invention, the “polymer compound” refers to an organic compound having a mass average molecular weight of 1000 or more, although there is no particular upper limit, The mass average molecular weight is practically 500,000 or less, preferably 100,000 or less, and more preferably 50,000 or less.).
The polymer compound that can be preferably used in the pigment dispersion composition of the present invention has a mass average molecular weight of 1000 or more, and is preferably a polymer compound represented by the following general formula (1).

In the general formula (1), A ¹ is an acidic group, a group having a basic nitrogen atom, a urea group, a urethane group, a group having a coordinating oxygen atom, a hydrocarbon group having 4 or more carbon atoms, or an alkoxysilyl group. , A monovalent organic group having a group selected from an epoxy group, an isocyanate group and a hydroxyl group, or a monovalent organic group containing an organic dye structure or a heterocyclic ring which may have a substituent. The n A ¹ may be the same or different.
Specifically, A ¹ is not particularly limited, and examples of the “monovalent organic group having an acidic group” include a carboxylic acid group, a sulfonic acid group, a monosulfate group, a phosphoric acid group, Examples thereof include monovalent organic groups having a monophosphate ester group, a boric acid group, and the like. Examples of the “monovalent organic group having a group having a basic nitrogen atom” include, for example, a monovalent organic group having an amino group (—NH ₂ ), a substituted imino group (—NHR ⁸ , —NR ⁹ R). ¹⁰ ) (wherein R ⁸ , R ⁹ , and R ¹⁰ are each independently an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or 7 carbon atoms). Represents an aralkyl group of 30 or less.), A monovalent organic group having a guanidyl group represented by the following general formula (a1) [in the general formula (a1), R ^a1 and R ^a2 are each independently a carbon number. An alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and an aralkyl group having 7 to 30 carbon atoms. A monovalent organic group having an amidinyl group represented by the following general formula (a2) [in the general formula (a2), R ^a3 and R ^a4 are each independently an alkyl group having 1 to 20 carbon atoms, carbon An aryl group having 6 to 20 carbon atoms and an aralkyl group having 7 to 30 carbon atoms are represented. And the like.

As the “monovalent organic group having a urea group”, for example, —NHCONHR ¹⁵ (where R ¹⁵ is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms). And represents an aralkyl group having 7 to 30 carbon atoms.
Examples of the “monovalent organic group having a urethane group” include —NHCOOR ¹⁶ , —OCONHR ¹⁷ (wherein R ¹⁶ and R ¹⁷ are each independently an alkyl group having 1 to 20 carbon atoms, 6 carbon atoms). And an aryl group having 20 or less and an aralkyl group having 7 to 30 carbon atoms).
Examples of the “group having a group having a coordinating oxygen atom” include a group having an acetylacetonato group and a group having a crown ether.
Examples of the “group having a hydrocarbon group having 4 or more carbon atoms” include an alkyl group having 4 or more carbon atoms (for example, octyl group, dodecyl group, etc.) and an aryl group having 6 or more carbon atoms (for example, phenyl group, naphthyl group). And an aralkyl group having 7 or more carbon atoms (for example, a benzyl group). At this time, there is no upper limit to the number of carbon atoms, but it is preferably 30 or less.
Examples of the “group having an alkoxysilyl group” include groups having a trimethoxysilyl group, a triethoxysilyl group, and the like.
Examples of the “group having an epoxy group” include a group having a glycidyl group.
Examples of the “group having an isocyanate group” include a 3-isocyanatopropyl group.
Examples of the “group having a hydroxyl group” include a 3-hydroxypropyl group.

Among the above, A ¹ is preferably a monovalent organic group having a group selected from an acidic group, a group having a basic nitrogen atom, a urea group, and a hydrocarbon group having 4 or more carbon atoms. .

  The organic dye structure or heterocyclic ring is not particularly limited. More specifically, examples of the organic dye structure include phthalocyanine compounds, insoluble azo compounds, azo lake compounds, anthraquinone compounds, quinacridone compounds, dioxazine compounds, Examples include diketopyrrolopyrrole compounds, anthrapyridine compounds, ansanthrone compounds, indanthrone compounds, flavanthrone compounds, perinone compounds, perylene compounds, and thioindigo compounds. Examples of the heterocyclic ring include thiophene, furan, xanthene, pyrrole, pyrroline, pyrrolidine, dioxolane, pyrazole, pyrazoline, pyrazolidine, imidazole, oxazole, thiazole, oxadiazole, triazole, thiadiazole, pyran, pyridine, piperidine, dioxane, Examples include morpholine, pyridazine, pyrimidine, piperazine, triazine, trithiane, isoindoline, isoindolinone, benzimidazolone, succinimide, phthalimide, naphthalimide, hydantoin, indole, quinoline, carbazole, acridine, acridone, and anthraquinone.

  In addition, the organic dye structure or the heterocyclic ring may have a substituent. Examples of the substituent include an alkyl group having 1 to 20 carbon atoms such as a methyl group and an ethyl group, a phenyl group, and a naphthyl group. C1-C16 acyloxy groups such as aryl groups, hydroxyl groups, amino groups, carboxyl groups, sulfonamido groups, N-sulfonylamido groups, acetoxy groups, etc., methoxy groups, ethoxy groups, etc. Alkoxy groups having 1 to 6 carbon atoms such as halogen atoms such as chlorine and bromine, alkoxycarbonyl groups having 2 to 7 carbon atoms such as methoxycarbonyl group, ethoxycarbonyl group and cyclohexyloxycarbonyl group, cyano group, t- And carbonic acid ester groups such as butyl carbonate.

Further, as the A ^1, it is preferably a monovalent organic group represented by the following general formula (4).

In the general formula (4), B ¹ is an acidic group, a group having a basic nitrogen atom, a urea group, a urethane group, a group having a coordinating oxygen atom, a hydrocarbon group having 4 or more carbon atoms, or an alkoxysilyl group. Represents an organic dye structure or a heterocyclic ring optionally having a substituent selected from an epoxy group, an isocyanate group, and a hydroxyl group, and R ¹⁸ represents a single bond or an a1-valent organic or inorganic linking group. . a1 represents 1 to 5, a1 amino ^{B 1} represents may be the same or different.

B ¹ has the same meaning as A ¹ in formula (4), and the preferred embodiment is the same. Examples of the organic dye structure or heterocyclic ring include phthalocyanine compounds, insoluble azo compounds, azo lake compounds, anthraquinone compounds, Organic pigment structures such as quinacridone compounds, dioxazine compounds, diketopyrrolopyrrole compounds, anthrapyridine compounds, ansanthrone compounds, indanthrone compounds, flavanthrone compounds, perinone compounds, perylene compounds, thioindigo compounds, such as thiophene, furan, xanthene, Pyrrole, pyrroline, pyrrolidine, dioxolane, pyrazole, pyrazoline, pyrazolidine, imidazole, oxazole, thiazole, oxadiazole, triazole, thiadiazole, pyran, pyridine, piperidi , Dioxane, morpholine, pyridazine, pyrimidine, piperazine, triazine, trithiane, isoindoline, isoindolinone, benzimidazolone, succinimide, phthalimide, naphthalimide, hydantoin, indole, quinoline, carbazole, acridine, acridone, anthraquinone Is mentioned.

  In addition, the organic dye structure or the heterocyclic ring may have a substituent. Examples of the substituent include an alkyl group having 1 to 20 carbon atoms such as a methyl group and an ethyl group, a phenyl group, and a naphthyl group. C1-C16 acyloxy groups such as aryl groups, hydroxyl groups, amino groups, carboxyl groups, sulfonamido groups, N-sulfonylamido groups, acetoxy groups, etc., methoxy groups, ethoxy groups, etc. Alkoxy groups having 1 to 6 carbon atoms such as halogen atoms such as chlorine and bromine, alkoxycarbonyl groups having 2 to 7 carbon atoms such as methoxycarbonyl group, ethoxycarbonyl group and cyclohexyloxycarbonyl group, cyano group, t- And carbonic acid ester groups such as butyl carbonate.

R ¹⁸ represents a single bond or an a1 + 1 valent linking group, and a1 represents 1 to 5. The linking group R ¹⁸ includes 1 to 100 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to 200 hydrogen atoms, and 0 to Groups comprising up to 20 sulfur atoms are included and may be unsubstituted or further substituted. R ¹⁸ is preferably an organic linking group.

Specific examples of R ¹⁸ include the following structural units or groups formed by combining the structural units.

When R ¹⁸ has a substituent, examples of the substituent include an alkyl group having 1 to 20 carbon atoms such as a methyl group and an ethyl group, and an aryl group having 6 to 16 carbon atoms such as a phenyl group and a naphthyl group. Group, hydroxyl group, amino group, carboxyl group, sulfonamido group, N-sulfonylamido group, acetoxy group and other C1-C6 acyloxy groups, methoxy group, ethoxy group and other C1-C6 alkoxy groups Halogen atoms such as chlorine and bromine, alkoxycarbonyl groups having 2 to 7 carbon atoms such as methoxycarbonyl group, ethoxycarbonyl group and cyclohexyloxycarbonyl group, carbonate groups such as cyano group and t-butyl carbonate, etc. It is done.

In the general formula (1), R ¹ represents an (m + n) -valent linking group. m + n satisfies 3-10.
Examples of the (m + n) -valent linking group represented by R ¹ include 1 to 100 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, and 1 to 200. Groups comprising up to 0 hydrogen atoms and 0 to 20 sulfur atoms are included, which may be unsubstituted or further substituted. R ¹ is preferably an organic linking group.

Specific examples of R ¹ include the structural units (t-1) to (t-34) or a group formed by combining the structural units (which may form a ring structure). be able to.

  When the linking group has a substituent, examples of the substituent include an alkyl group having 1 to 20 carbon atoms such as a methyl group and an ethyl group, and a carbon group having 6 to 16 carbon atoms such as a phenyl group and a naphthyl group. Alkyl groups having 1 to 6 carbon atoms such as aryl groups, hydroxyl groups, amino groups, carboxyl groups, sulfonamido groups, N-sulfonylamide groups, and acetoxy groups, alkoxy groups having 1 to 6 carbon atoms such as methoxy groups and ethoxy groups. Groups, halogen atoms such as chlorine and bromine, alkoxycarbonyl groups having 2 to 7 carbon atoms such as methoxycarbonyl group, ethoxycarbonyl group and cyclohexyloxycarbonyl group, carbonate groups such as cyano group and t-butyl carbonate, etc. Can be mentioned.

R ² represents a single bond or a divalent linking group. R ² includes 1 to 100 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to 200 hydrogen atoms, and 0 to 20 atoms. Group consisting of up to sulfur atoms is included, and may be unsubstituted or may further have a substituent. R ² is preferably an organic linking group.

Specific examples of R ² include the structural units of t-3, 4, 7-18, 22-26, 32, and 34, or groups configured by combining the structural units.

Among the above, when R ² has a substituent, examples of the substituent include an alkyl group having 1 to 20 carbon atoms such as a methyl group and an ethyl group, a carbon group having 6 to 16 carbon atoms such as a phenyl group and a naphthyl group. Up to 1 to 6 carbon atoms such as an acyloxy group, 1 to 6 carbon atoms such as an aryl group, a hydroxyl group, an amino group, a carboxyl group, a sulfonamide group, an N-sulfonylamide group and an acetoxy group, a methoxy group and an ethoxy group Alkoxy groups, halogen atoms such as chlorine and bromine, alkoxycarbonyl groups having 2 to 7 carbon atoms such as methoxycarbonyl group, ethoxycarbonyl group and cyclohexyloxycarbonyl group, carbonate groups such as cyano group and t-butyl carbonate, Etc.

In said general formula (1), m represents 1-8. As m, 1-5 are preferable, 1-3 are more preferable, and 1-2 are especially preferable.
N represents 2-9. As n, 2-8 are preferable, 2-7 are more preferable, and 3-6 are especially preferable.

In the general formula (1), P ¹ represents a polymer compound residue (hereinafter also referred to as a polymer skeleton), and can be selected from ordinary polymers according to the purpose and the like.
Among polymers, in order to constitute a polymer skeleton, a vinyl monomer polymer or copolymer, ester polymer, ether polymer, urethane polymer, amide polymer, epoxy polymer, silicone polymer, and these Modified product or copolymer [for example, polyether / polyurethane copolymer, copolymer of polyether / vinyl monomer, etc. (any of random copolymer, block copolymer, graft copolymer) May be included). Is preferably selected from the group consisting of vinyl monomer polymers or copolymers, ester polymers, ether polymers, urethane polymers, and modified products or copolymers thereof. At least one kind is more preferred, and a polymer or copolymer of vinyl monomers is particularly preferred.
Furthermore, the polymer is preferably soluble in an organic solvent. If the affinity with the organic solvent is low, for example, when used as a pigment dispersant, the affinity with the dispersion medium is weakened, and it may not be possible to secure a sufficient adsorption layer for stabilizing the dispersion.

  Among the polymer compounds represented by the general formula (1), the polymer compound represented by the following general formula (2) is more preferable.

In the general formula (2), A ² has the same meaning as A ¹ in the general formula (1), and the specific preferred embodiment thereof is also the same. As a specific example of the organic dye structure, a phthalocyanine compound, An azo lake compound, an anthraquinone compound, a dioxazine compound, a diketopyrrolopyrrole compound and the like are more preferable.As the heterocyclic ring, imidazole, triazole, pyridine, piperidine, morpholine, triazine, isoindoline, isoindolinone, benzimidazolone, benzothiazole, More preferred are succinimide, phthalimide, naphthalimide, hydantoin, indole, quinoline, carbazole, acridine, acridone, anthraquinone and the like.

Further, may have the same substitution group and A ^1, for the substituents are the same as in A ^1, preferred embodiment is also the same.
Furthermore, as A ^2, 1 monovalent organic group is preferably represented by the general formula (4), details and specific examples of the organic groups are the same for the preferred embodiment.

In the general formula (2), R ³ represents a (x + y) -valent linking group. Examples of the (x + y) -valent linking group represented by R ³ include 1 to 60 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, and 1 to 100. Groups comprising up to 0 hydrogen atoms and 0 to 20 sulfur atoms are included, which may be unsubstituted or may further have a substituent.

The (x + y) -valent linking group represented by R ³ has the same meaning as the (m + n) -valent linking group in R ¹ , and the preferred embodiments thereof are also the same. Further, specific examples include the same structural unit as described above or a group formed by combining the structural units.

Among these, the linking group represented by R ³ is preferably an organic linking group, and preferred specific examples [specific examples (r-1) to (r-17)] of the organic linking group are as follows. Show. However, the present invention is not limited to these.

  Among the above, from the viewpoint of availability of raw materials, ease of synthesis, and solubility in various solvents, the above (r-1), (r-2), (r-10), (r-11), ( The groups of r-16) and (r-17) are preferred.

When R ³ has a substituent, examples of the substituent include an alkyl group having 1 to 20 carbon atoms such as a methyl group and an ethyl group, and a carbon group having 6 to 16 carbon atoms such as a phenyl group and a naphthyl group. Up to 1 to 6 carbon atoms such as an acyloxy group, 1 to 6 carbon atoms such as an aryl group, a hydroxyl group, an amino group, a carboxyl group, a sulfonamide group, an N-sulfonylamide group and an acetoxy group, a methoxy group and an ethoxy group Alkoxy groups, halogen atoms such as chlorine and bromine, alkoxycarbonyl groups having 2 to 7 carbon atoms such as methoxycarbonyl group, ethoxycarbonyl group and cyclohexyloxycarbonyl group, carbonate groups such as cyano group and t-butyl carbonate, Etc.

In the general formula (2), R ⁴ and R ⁵ each independently represents a single bond or a divalent linking group.
The “divalent linking group” represented by R ⁴ and R ⁵ may be unsubstituted or substituted, and may be a linear, branched, or cyclic alkylene group, an arylene group, an aralkylene group, ^{and, -O -, - S -,} - C (= O) -, - N (R 19) -, - SO -, - SO 2 -, - CO 2 -, - N (R 20) SO 2 -, or it can be given a divalent group formed by combining two or more of these groups as preferred examples (wherein R ¹⁹ and R ²⁰ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. ). Of these, an organic linking group is preferred.

Examples of R ⁴ include linear and branched alkylene groups, aralkylene groups, and —O—, —C (═O) —, —N (R ¹⁹ ) —, —SO ₂ —, —CO ₂ —, — N (R ²⁰ ) SO ₂ — (wherein R ¹⁹ and R ²⁰ each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms), or a divalent group obtained by combining two or more of these groups Are more preferable, a linear or branched alkylene group, an aralkylene group, and —O—, —C (═O) —, —N (R ¹⁹ ) — (wherein R ¹⁹ represents a hydrogen atom or 1 to 4 carbon atoms). Each represents an alkyl group), —CO ₂ — or a divalent group in which two or more of these groups are combined is particularly preferable.

R ⁵ includes a single bond or a linear or branched alkylene group, an aralkylene group, and —O—, —C (═O) —, —N (R ¹⁹ ) —, —SO ₂ —, —CO _2. —, —N (R ²⁰ ) SO ₂ — (wherein R ¹⁹ and R ²⁰ each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms), or a combination of two or more of these groups And a linear or branched alkylene group, an aralkylene group, and —O—, —C (═O) —, —N (R ¹⁹ ) — (wherein R ¹⁹ represents a hydrogen atom or a carbon number). Represents 1 to 4 alkyl groups), —CO ₂ — or a divalent group in which two or more of these groups are combined is particularly preferable.

Moreover, when said R < ⁴ >, R < ⁵ > has a substituent, as this substituent, it is C6-C20, such as a C1-C20 alkyl group, such as a methyl group and an ethyl group, a phenyl group, a naphthyl group, for example. 1 to 16 carbon atoms such as aryl group, hydroxyl group, amino group, carboxyl group, sulfonamido group, N-sulfonylamido group, acetoxy group, etc. Carbon atoms such as alkoxy groups up to 6 carbon atoms, halogen atoms such as chlorine and bromine, alkoxycarbonyl groups up to 2 to 7 carbon atoms such as methoxycarbonyl group, ethoxycarbonyl group and cyclohexyloxycarbonyl group, cyano groups and t-butyl carbonate Group, and the like.

  In said general formula (2), y represents 1-8, 1-5 are preferable, 1-3 are more preferable, and 1-2 are especially preferable. Moreover, x represents 2-9, 2-8 are preferable, 2-7 are more preferable, and 3-6 are especially preferable.

P ² in the general formula (2) represents a polymer skeleton and can be selected from ordinary polymers according to the purpose and the like. The preferred embodiment of the polymer, has the same meaning as P ¹ in Formula (1), the same applies to its preferred embodiment.

Among the polymer compounds represented by the general formula (2), in particular, R ³ represents the specific examples (r-1), (r-2), (r-10), (r-11), (r -16) or (r-17), wherein R ⁴ is a single bond, a linear or branched alkylene group, an aralkylene group, —O—, —C (═O) —, —N (R ¹⁹ ). — (Wherein R ¹⁹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms), —CO ₂ —, or a divalent organic group in which two or more of these groups are combined, and R ⁵ but a single bond, an ethylene group, a propylene group, or a linking group represented by the following general formula (s-a) or (s-b), P ² is a polymer or a copolymer of a vinyl monomer, an ester-based A polymer, an ether-based polymer, a urethane-based polymer, or a modified product thereof, wherein y is 1 to 2, Polymeric compounds 3-6 are particularly preferred. In the following groups, R ²¹ represents a hydrogen atom or a methyl group, and l represents 1 or 2.

  The mass average molecular weight of the polymer compound is 1000 or more, but the mass average molecular weight is preferably 1000 to 500,000, more preferably 3000 to 100,000, still more preferably 5000 to 80000, and particularly preferably 7000 to 60000. When the mass average molecular weight is within the above range, the effects of the multiple functional groups introduced at the polymer ends are sufficiently exhibited, and the performance of adsorbing to a solid surface, micelle forming ability, and surface activity is excellent. To do. In particular, when the polymer compound according to the present invention is used as a pigment dispersant, good dispersibility and dispersion stability can be achieved.

The polymer compound represented by the general formula (1) (including those represented by the general formula (2)) is not particularly limited, but can be synthesized by the following method. Of the following synthesis methods, the following synthesis methods such as 2, 3, 4, 5 and the like are more preferable, and the following synthesis methods such as 3, 4, 5, and the like are particularly preferable because of ease of synthesis.
1. A polymer in which a functional group selected from a carboxyl group, a hydroxyl group, an amino group and the like is introduced at the terminal, an acid halide having a plurality of functional groups (A ¹ or A ² in the general formula), or a plurality of functional groups ( A method in which an alkyl halide having A ¹ or A ² ) in the general formula or an isocyanate having a plurality of functional groups (A ¹ or A ² in the general formula) is polymerized.
2. A method in which a polymer having a carbon-carbon double bond introduced at the terminal and a mercaptan having a plurality of functional groups (A ¹ or A ² in the above general formula) are subjected to a Michael addition reaction.
3. A method in which a polymer having a carbon-carbon double bond introduced at a terminal thereof and a mercaptan having a plurality of functional groups (A ¹ or A ² in the above general formula) are reacted in the presence of a radical generator.
4). A method of reacting a polymer having a plurality of mercaptans introduced at its terminal and a functional group having a carbon-carbon double bond introduced (A ¹ or A ² in the above general formula) in the presence of a radical generator.
5. A method of radical polymerization of a vinyl monomer using a mercaptan compound having a plurality of functional groups (A ¹ or A ² in the above general formula) as a chain transfer agent.

  Among the above, the polymer compound (preferably the polymer compound represented by the general formula (2)) used in the method for producing the pigment dispersion composition of the present invention is, for example, any one of the above 2, 3, 4, 5 However, it is more preferable to synthesize by the above method 5 because of ease of synthesis.

  More specifically, radical polymerization is preferably performed using a compound represented by the following general formula (3) as a chain transfer agent.

In the general formula (3), R ⁶ , R ⁷ , A ³ , g, and h are the same as R ³ , R ⁴ , A ² , x, and y in the general formula (2), respectively. The preferred embodiment is also the same.

  Although it does not restrict | limit especially as said vinyl monomer, For example, (meth) acrylic acid esters, crotonic acid esters, vinyl esters, maleic acid diesters, fumaric acid diesters, itaconic acid diesters, (meth) acrylamides , Vinyl ethers, esters of vinyl alcohol, styrenes, (meth) acrylonitrile and the like are preferable. Examples of such include the following compounds.

  Examples of the (meth) acrylate esters include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, and n- (meth) acrylate. Butyl, isobutyl (meth) acrylate, t-butyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, t-butylcyclohexyl (meth) acrylate, (meth) acrylic acid 2 -Ethylhexyl, t-octyl (meth) acrylate, dodecyl (meth) acrylate, octadecyl (meth) acrylate, acetoxyethyl (meth) acrylate, phenyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate , 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate , 2- (2-methoxyethoxy) ethyl (meth) acrylate, 3-phenoxy-2-hydroxypropyl (meth) acrylate, benzyl (meth) acrylate, diethylene glycol monomethyl ether (meth) acrylate, (meth) Acrylic acid diethylene glycol monoethyl ether, (meth) acrylic acid triethylene glycol monomethyl ether, (meth) acrylic acid triethylene glycol monoethyl ether, (meth) acrylic acid polyethylene glycol monomethyl ether, (meth) acrylic acid polyethylene glycol monoethyl ether , Β-phenoxyethoxyethyl (meth) acrylate, nonylphenoxypolyethylene glycol (meth) acrylate, dicyclopentenyl (meth) acrylate, disi (meth) acrylate Clopentenyloxyethyl, trifluoroethyl (meth) acrylate, octafluoropentyl (meth) acrylate, perfluorooctylethyl (meth) acrylate, dicyclopentanyl (meth) acrylate, tribromo (meth) acrylate Examples thereof include phenyl and tribromophenyloxyethyl (meth) acrylate.

  Examples of the crotonic acid esters include butyl crotonic acid and hexyl crotonic acid.

  Examples of the vinyl esters include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl methoxyacetate, vinyl benzoate and the like.

  Examples of the maleic acid diesters include dimethyl maleate, diethyl maleate, and dibutyl maleate.

  Examples of the fumaric acid diesters include dimethyl fumarate, diethyl fumarate, dibutyl fumarate and the like.

  Examples of the itaconic acid diesters include dimethyl itaconate, diethyl itaconate, and dibutyl itaconate.

  Examples of the (meth) acrylamides include (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N- n-butylacryl (meth) amide, Nt-butyl (meth) acrylamide, N-cyclohexyl (meth) acrylamide, N- (2-methoxyethyl) (meth) acrylamide, N, N-dimethyl (meth) acrylamide, Examples thereof include N, N-diethyl (meth) acrylamide, N-phenyl (meth) acrylamide, N-benzyl (meth) acrylamide, (meth) acryloylmorpholine, diacetone acrylamide and the like.

Examples of the styrenes include styrene, methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, isopropyl styrene, butyl styrene, hydroxy styrene, methoxy styrene, butoxy styrene, acetoxy styrene, chlorostyrene, dichlorostyrene, bromostyrene, chloro Examples thereof include methylstyrene, hydroxystyrene protected with a group deprotectable by an acidic substance (for example, t-Boc and the like), methyl vinylbenzoate, and α-methylstyrene.

  Examples of the vinyl ethers include methyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, and methoxyethyl vinyl ether.

In addition to the above compounds, (meth) acrylonitrile, heterocyclic groups substituted with vinyl groups (for example, vinylpyridine, vinylpyrrolidone, vinylcarbazole, etc.), N-vinylformamide, N-vinylacetamide, N-vinylimidazole, Vinyl caprolactone can also be used.
In addition to the above compounds, vinyl monomers having a functional group such as a urethane group, a urea group, a sulfonamide group, a phenol group, and an imide group can also be used. Such a monomer having a urethane group or a urea group can be appropriately synthesized using, for example, an addition reaction between an isocyanate group and a hydroxyl group or an amino group. Specifically, an addition reaction between an isocyanate group-containing monomer and a compound containing one hydroxyl group or a compound containing one primary or secondary amino group, or a hydroxyl group-containing monomer or primary or secondary amino group containing It can be appropriately synthesized by an addition reaction between a monomer and monoisocyanate.

The above vinyl monomers may be polymerized alone or in combination of two or more, and such radical polymers are prepared according to ordinary methods in the usual manner for the corresponding vinyl monomers. It is obtained by polymerizing.
For example, a method (solution polymerization method) in which these vinyl monomers and a chain transfer agent are dissolved in a suitable solvent, a radical polymerization initiator is added thereto and polymerized in a solution at about 50 ° C. to 220 ° C. It is obtained by using.

  Examples of suitable solvents used in the solution polymerization method can be arbitrarily selected depending on the monomers used and the solubility of the resulting copolymer. For example, methanol, ethanol, propanol, isopropanol, 1-methoxy-2-propanol, 1-methoxy-2-propyl acetate, acetone, methyl ethyl ketone, methyl isobutyl ketone, methoxypropyl acetate, ethyl lactate, ethyl acetate, acetonitrile, tetrahydrofuran, dimethyl Examples include formamide, chloroform, and toluene. These solvents may be used as a mixture of two or more.

  Examples of radical polymerization initiators include azo compounds such as 2,2′-azobis (isobutyronitrile) (AIBN) and 2,2′-azobis- (2,4′-dimethylvaleronitrile), benzoyl par Peroxides such as oxides, and persulfates such as potassium persulfate and ammonium persulfate can be used.

The compound represented by the general formula (3) can be synthesized by the following method or the like, but the following method 7 is more preferable because of ease of synthesis.
6). A method of converting a halide compound having a plurality of functional groups (A ¹ or A ² in the above general formula) into a mercaptan compound (a method of reacting with thiourea and hydrolyzing, a method of directly reacting with NaSH, CH ₃ COSNa and (For example, a method of reacting and hydrolyzing)
7). Addition of a compound having 3 to 10 mercapto groups in one molecule and a compound having a functional group (A ¹ or A ² in the above general formula) and a functional group capable of reacting with a mercapto group How to react

Suitable examples of the “functional group capable of reacting with a mercapto group” in Method 7 include acid halides, alkyl halides, isocyanates, and carbon-carbon double bonds.
It is particularly preferable that the “functional group capable of reacting with a mercapto group” is a carbon-carbon double bond, and the addition reaction is synthesized by a radical addition reaction. The carbon-carbon double bond is more preferably a mono- or di-substituted vinyl group in terms of reactivity with the mercapto group.

  Specific examples of the “compound having 3 to 10 mercapto groups in one molecule” include the following compounds.

  Among these, (u-1), (u-2), (u-10), (u-11), (u) from the viewpoint of availability of raw materials, ease of synthesis, and solubility in various solvents. -16) and (u-17) are preferable.

A functional group (A ¹ or A ² in the ^formula), and carbon - The compound having a carbon double bond is not particularly limited, include the following.

  For example, “the compound having 3 to 10 mercapto groups in one molecule” and the above “the acid group, the group having a basic nitrogen atom, the urea group, the urethane group, the group having a coordinating oxygen atom, carbon Radical addition with a compound having at least one functional group selected from a hydrocarbon group, an alkoxysilyl group, an epoxy group, an isocyanate group, and a hydroxyl group having a carbon number of 4 or more and having a carbon-carbon double bond Examples of the reaction product include the above-mentioned “compound having 3 to 10 mercapto groups in one molecule” and “acid group, group having basic nitrogen atom, urea group, urethane group, and coordinating oxygen atom. A group having at least one functional group selected from a hydrocarbon group having 4 or more carbon atoms, an alkoxysilyl group, an epoxy group, an isocyanate group, and a hydroxyl group, and a carbon-carbon double Obtained using the - (ene reaction method thiol) compound having a slip "was dissolved in a suitable solvent, here by adding a radical generator, at about 50 ° C. to 100 ° C., a method of adding.

  Examples of preferable solvents used in the above method include “compounds having 3 to 10 mercapto groups in one molecule”, “acidic groups, groups having basic nitrogen atoms, urea groups, urethane groups, and coordination. A functional group having at least one functional group selected from a group having a reactive oxygen atom, a hydrocarbon group having 4 or more carbon atoms, an alkoxysilyl group, an epoxy group, an isocyanate group, and a hydroxyl group, and capable of reacting with a mercapto group It can be arbitrarily selected depending on the solubility of the compound having a group (for example, a carbon-carbon double bond) and the radical addition reaction product to be generated. For example, methanol, ethanol, propanol, isopropanol, 1-methoxy-2-propanol, 1-methoxy-2-propyl acetate, acetone, methyl ethyl ketone, methyl isobutyl ketone, methoxypropyl acetate, ethyl lactate, ethyl acetate, acetonitrile, tetrahydrofuran, dimethyl Examples include formamide, chloroform, and toluene. These solvents may be used as a mixture of two or more.

  As the radical generator, azo compounds such as 2,2′-azobis (isobutyronitrile) (AIBN) and 2,2′-azobis- (2,4′-dimethylvaleronitrile), benzoyl peroxide And persulfates such as potassium persulfate and ammonium persulfate can be used.

  Specific examples of the compound represented by the general formula (1) preferably used in the method for producing the pigment dispersion composition of the present invention are shown below. However, the present invention is not limited to these specific examples.

Further, this polymer compound is preferably a polymer compound having an acidic group, more preferably a polymer compound having a carboxyl group, and (A) at least a repeating unit derived from the compound having a carboxyl group. A copolymer compound containing at least one repeating unit derived from one type and a compound having (B) a carboxylic acid ester group is particularly preferred.
The repeating unit derived from the compound (A) having a carboxyl group is preferably a repeating unit represented by the following general formula (I), preferably a repeating unit derived from acrylic acid or methacrylic acid. More preferably, the repeating unit derived from the compound (B) having a carboxylic acid ester group is preferably a repeating unit represented by the following general formula (II), and represented by the following general formula (IV). A repeating unit is more preferable, and a repeating unit derived from benzyl acrylate, benzyl methacrylate, phenethyl acrylate, phenethyl methacrylate, 3-phenylpropyl acrylate, or 3-phenylpropyl methacrylate is particularly preferable.

（Ｒ_１は水素原子又は炭素原子数１〜５のアルキル基を表す。）

(R ₁ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.)

（Ｒ_２は水素原子又は炭素原子数１〜５のアルキル基を表す。Ｒ_３は下記一般式（ＩＩＩ）で表される基を表す。）

(R ₂ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. R ₃ represents a group represented by the following general formula (III).)

（Ｒ_４は水素原子、炭素原子数１〜５のアルキル基、ヒドロキシ基、炭素原子数１〜５のヒドロキシアルキル基、又は炭素原子数６〜２０のアリール基を表す。Ｒ_５及びＲ_６はそれぞれ水素原子又は炭素原子数１〜５のアルキル基を表す。ｉは１〜５の数を表す。）

(R ₄ represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a hydroxy group, a hydroxyalkyl group having 1 to 5 carbon atoms, or an aryl group having 6 to 20 carbon atoms. R ₅ and R ₆ are And each represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, i represents a number of 1 to 5)

（Ｒ_７は水素原子又は炭素原子数１〜５のアルキル基を表す。Ｒ_８は下記一般式（Ｖ）で表される基を表す。）

(R ₇ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. R ₈ represents a group represented by the following general formula (V).)

（Ｒ_９は炭素原子数２〜５のアルキル基又は炭素原子数６〜２０のアリール基を表す。Ｒ_１０及びＲ_１１は水素原子又は炭素原子数１〜５のアルキル基を表す。ｊは１〜５の数を表す。）
また、（Ａ）カルボキシル基を有する化合物から導かれた繰り返し単位と、前記（Ｂ）カルボン酸エステル基を有する化合物から導かれた繰り返し単位との重合比率としていえば、繰り返し単位（Ａ）の全繰り返し単位数に対する数量比％が３〜４０であることが好ましく、５〜３５であることがより好ましい。
本発明の顔料分散組成物の製造方法において高分子の分子量とは、特に断らない限り、質量平均分子量をいう。高分子の分子量の測定方法としては、クロマトグラフィー法、粘度法、光散乱法、沈降速度法等が挙げられる。本発明では、特に断らない限りクロマトグラフィー法により測定した質量平均分子量を用いる。

(R ₉ represents an alkyl group having 2 to 5 carbon atoms or an aryl group having 6 to 20 carbon atoms. R ₁₀ and R ₁₁ represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. J represents 1 Represents a number of ~ 5.)
Further, in terms of the polymerization ratio of the repeating unit derived from the compound having (A) carboxyl group and the repeating unit derived from the compound having (B) carboxylate group, all of the repeating units (A) The quantity ratio% to the number of repeating units is preferably 3 to 40, more preferably 5 to 35.
In the method for producing a pigment dispersion composition of the present invention, the molecular weight of the polymer means a mass average molecular weight unless otherwise specified. Examples of the method for measuring the molecular weight of the polymer include a chromatography method, a viscosity method, a light scattering method, and a sedimentation rate method. In the present invention, a mass average molecular weight measured by a chromatography method is used unless otherwise specified.

The polymer compound may be water-soluble or oil-soluble, and may be water-soluble and oil-soluble.
The polymer compound may be added by a solution in an aqueous solvent or an organic solvent, a solid state, or a combination thereof. As a method of adding in a solution dissolved in a solvent, for example, a method of adding to an aggregated organic particle liquid in a state dissolved in a solvent similar to the solvent of the aggregated organic particle liquid, compatible with the solvent of the aggregated organic particle liquid, The method of adding in the state melt | dissolved in a different solvent is mentioned. The concentration of the polymer compound when added in a solution dissolved in a solvent is not particularly limited, but is preferably 1 to 70% by mass, more preferably 2 to 65% by mass, and particularly preferably 3 to 60% by mass.
The addition of the polymer compound can be performed during the formation of (or before or after) the organic nanoparticles by the reprecipitation method, during the extraction or concentration (or before or after), when the aggregated organic particles are dispersed (or before or after) after the concentration. After the process is completed, it may be added to any of these or a combination thereof. In the method for producing a pigment dispersion composition of the present invention, a polymer compound having a mass average molecular weight of 1000 or more may be contained in the composition as a binder described later. For example, after concentrating the organic particle reprecipitation liquid, the aggregated organic particles It is preferable to add at the time of fine dispersion.

The amount of the polymer compound added is preferably 0.1 to 1000 parts by mass, more preferably 5 to 500 parts by mass, and more preferably 10 to 300 parts by mass, when the organic particles contained in the aggregated organic particles are 100 parts by mass. Part is particularly preferred.
Examples of the polymer compound having a molecular weight of 1000 or more include, for example, polyvinylpyrrolidone, polyvinyl alcohol, polyvinyl methyl ether, polyethylene oxide, polyethylene glycol, polypropylene glycol, polyacrylamide, vinyl alcohol-vinyl acetate copolymer, and polyvinyl alcohol-partial formalized product. , Polyvinyl alcohol-partially butyralized product, vinylpyrrolidone-vinyl acetate copolymer, polyethylene oxide / propylene oxide block copolymer, polyamide, cellulose derivative, starch derivative and the like. In addition, natural polymer compounds such as alginate, gelatin, albumin, casein, gum arabic, tonganto gum and lignin sulfonate can also be used.
Examples of the polymer compound having an acidic group include polyvinyl sulfate and condensed naphthalene sulfonic acid.

Examples of the polymer compound having a carboxyl group include polyacrylic acid, polymethacrylic acid, and cellulose derivatives having a carboxyl group in the side chain. A copolymer compound containing (A) at least one repeating unit derived from a compound having a carboxyl group and (B) at least one repeating unit derived from a compound having a carboxylic ester group is disclosed in 59-44615, JP-B 54-34327, JP-B 58-12577, JP-B 54-25957, JP-A 59-53836, and JP-A 59-71048. Examples thereof include methacrylic acid copolymers, acrylic acid copolymers, itaconic acid copolymers, crotonic acid copolymers, maleic acid copolymers, and partially esterified maleic acid copolymers. Further, as particularly preferred examples, acrylic acid-acrylic acid ester copolymers, methacrylic acid-acrylic acid ester copolymers, acrylic acid-methacrylic acid ester copolymers, methacrylic acid-described in US Pat. No. 4,139,391 are described. Mention may be made of methacrylic acid ester copolymers, multi-component copolymers of acrylic acid or methacrylic acid, acrylic acid esters or methacrylic acid esters, and other vinyl compounds.
Examples of vinyl compounds include styrene or substituted styrene (eg, vinyl toluene, vinyl ethyl benzene), vinyl naphthalene or substituted vinyl naphthalene, acrylamide, methacrylamide, acrylonitrile, methacrylonitrile, and the like, with styrene being preferred.
These polymer compounds may be used alone or in combination of two or more, or may be used in combination with a compound having a molecular weight of less than 1000.

  In the present invention, the dispersion of organic nanoparticles preferably contains 60% by mass or more of an organic solvent, and more preferably 65% by mass or more. There is no restriction | limiting in particular as an organic solvent, It can select suitably from normal things. For example, an ester compound solvent, an alcohol compound solvent, an aromatic compound solvent, an aliphatic compound solvent, and a ketone compound solvent are preferable, and an ester compound solvent and a ketone compound solvent are particularly preferable. These may be used alone or in combination of two or more.

  Examples of the ester compound solvent include 2- (1-methoxy) propyl acetate, ethyl acetate, and ethyl lactate. Examples of the alcohol compound solvent include n-butanol and isobutanol. Examples of the aromatic compound solvent include benzene, toluene, xylene and the like. Examples of the aliphatic compound solvent include n-hexane and cyclohexane. Examples of the ketone compound solvent include methyl ethyl ketone, acetone, and cyclohexanone.

[Pigment dispersion composition]
Next, an embodiment in which the pigment dispersion of the present invention or the organic pigment nanoparticles thereof is used as a composition when used in, for example, a colored photosensitive resin composition or an inkjet ink used as a color filter will be described in detail. The organic nanoparticles can be used, for example, in a state dispersed in a vehicle. The vehicle refers to a portion of a medium in which a pigment is dispersed when it is in a liquid state, and a portion (binder) that is liquid and binds to the pigment to harden a coating film. And a component (organic solvent) to be dissolved and diluted. In the present invention, the binder used at the time of nanoparticle formation and the binder used for redispersion may be the same or different, and may be distinguished from each other as a nanoparticle formation binder and a redispersion binder, respectively. .
The concentration of the organic nanoparticles in the dispersion composition of the organic nanoparticles after redispersion is appropriately determined according to the purpose, but preferably the organic nanoparticles are 2 to 30% by mass with respect to the total amount of the dispersion composition. More preferably, it is 4-20 mass%, and it is especially preferable that it is 5-15 mass%. In the case of being dispersed by the vehicle as described above, the amount of the binder and the dissolved and diluted component is appropriately determined depending on the type of the organic material, etc. Preferably, it is 3-20 mass%, More preferably, it is 5-15 mass%. It is preferable that a dissolution dilution component is 5-80 mass%, and it is more preferable that it is 10-70 mass%.

In the concentrated and extracted nanoparticle liquid, as described above, in order to enable rapid filter filtration, the organic nanoparticles are preferably aggregated by concentration, and concentrated by centrifugation or drying. Aggregation is preferred.
As a method for finely dispersing such aggregated nanoparticles, for example, a dispersion method using ultrasonic waves or a method of applying physical energy can be used.
The ultrasonic irradiation device used preferably has a function capable of applying an ultrasonic wave of 10 kHz or higher, and examples thereof include an ultrasonic homogenizer and an ultrasonic cleaner. When the liquid temperature rises during ultrasonic irradiation, thermal aggregation of the nanoparticles occurs (see, for example, “Pigment Dispersion Technology—Surface Treatment and Use of Dispersing Agent and Dispersibility Evaluation—” Technical Information Association (1999)). The liquid temperature is preferably 1 to 100 ° C, more preferably 5 to 60 ° C. The temperature control method can be performed by controlling the dispersion temperature, controlling the temperature of the temperature adjusting layer that controls the temperature of the dispersion, or the like.
There are no particular restrictions on the disperser used to disperse the concentrated organic nanoparticles by applying physical energy, for example, kneader, roll mill, atrider, super mill, dissolver, homomixer, sand mill, etc. Machine. Further, a high-pressure dispersion method and a dispersion method using fine particle beads are also preferable.

<1> Dispersion Method As a preferred method for producing the organic nanoparticle dispersion composition, the viscosity at 25 ° C. after kneading and dispersing the colorant with the resin component is 10,000 mPa · s or more, preferably 100,000 mPa · s or more. So that the viscosity after the fine dispersion treatment is 1,000 mPa · s or less, preferably 100 mPa · s or less. A method of fine dispersion treatment is preferred.
The machines used in the kneading and dispersing treatment are two rolls, three rolls, ball mills, tron mills, dispersers, kneaders, kneaders, homogenizers, blenders, single and twin screw extruders, etc., which disperse while giving a strong shearing force. . Next, a solvent was added, and a vertical or horizontal sand grinder, a pin mill, a slit mill, an ultrasonic disperser, a high pressure disperser, etc. were used, and it was made of glass having a particle diameter of 0.1 to 1 mm, zirconia, or the like. Fine dispersion with beads. Furthermore, it is possible to perform a fine dispersion treatment using fine particle beads of 0.1 mm or less. It is also possible to omit the kneading and dispersing process. In that case, beads are dispersed with a pigment, a dispersant or a surface treatment agent, and the acrylic copolymer and solvent in the present invention.
It is also possible to disperse the main pigment and the complementary pigment separately, and then mix the dispersions of the two to add further dispersion treatment, or to disperse the main pigment and the complementary pigment together.
For details on kneading and dispersing, see T.W. C. It is also described in “Paint Flow and Pigment Dispersion” by Patton (published by John Wiley and Sons, 1964), and this method may be used.

<2> Examples of Dispersant To the organic nanoparticle dispersion composition, a normal pigment dispersant or surfactant can be added for the purpose of improving the dispersibility of the organic nanoparticles. As these dispersants, many types of compounds are used. For example, phthalocyanine derivatives (commercially available products EFKA-6745 (manufactured by Efka)), Solsperse 5000 (manufactured by Geneca), organosiloxane polymer KP341 ( Shin-Etsu Chemical Co., Ltd.), (meth) acrylic acid (co) polymer polyflow No. 75, no. 90, no. 95 (manufactured by Kyoeisha Yushi Chemical Co., Ltd.), W001 (manufactured by Yusho Co., Ltd.), and the like; polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl Nonionic surfactants such as ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester; anionic surfactants such as W004, W005, W017 (manufactured by Yusho); EFKA- 46, EFKA-47, EFKA-47EA, EFKA polymer 100, EFKA polymer 400, EFKA polymer 401, EFKA polymer 450 (manufactured by Morishita Sangyo Co., Ltd.), Disperse Aid 6, Polymer dispersants such as ISPER SIDE 8, DISPER SIDE 15, DISPER SIDE 9100 (manufactured by San Nopco); various sparses such as Solsperse 3000, 5000, 9000, 12000, 13240, 13940, 17000, 24000, 26000, 28000 Dispersant (manufactured by Zeneca); Adeka Pluronic L31, F38, L42, L44, L61, L64, F68, L72, P95, F77, P84, F87, P94, L101, P103, F108, L121, P-123 (Asahi Denka Co., Ltd.) and Isonet S-20 (Sanyo Kasei Co., Ltd.). Further, the pigment dispersant described in JP 2000-239554 A, the compound (C) described in JP-B-5-72943, the compound of Synthesis Example 1 described in JP 2001-31885 A, and the like are also suitable. Can be used.
It is also preferred to use again the compound shown in the section of [Dispersant] as a dispersant used for forming the organic nanoparticles during redispersion.

  In the organic nanoparticle-dispersed composition, the re-dispersed organic nanoparticles (primary particles) can be finely dispersed particles, and the particle size can be preferably 1 to 200 nm, and 2 to 100 nm. More preferred is 5 to 50 nm. Further, the Mv / Mn of the particles after redispersion is preferably 1.0 to 2.0, more preferably 1.0 to 1.8, and 1.0 to 1.5. Is particularly preferred.

The organic pigment nanoparticles contained in the pigment dispersion composition of the present invention and the colored photosensitive resin composition described later are concentrated and redispersed in spite of the minute particle size of nanometer size (for example, 10 to 100 nm). be able to. For this reason, when used in a color filter, the optical density is high, the uniformity of the filter surface is excellent, the contrast is high, and the noise of the image can be reduced.
Furthermore, since the organic pigment nanoparticles contained in the pigment dispersion composition and the colored photosensitive composition can be finely dispersed highly and uniformly, a high color density is exhibited with a thin film thickness. For example, a color filter or the like can be made thin.
In addition, the pigment dispersion composition and the colored photosensitive resin composition are excellent as an image forming material for producing, for example, a color proof or a color filter by containing a pigment having a clear color tone and high coloring power. .
Furthermore, for the alkaline developer used for exposure and development during the formation of a colored image, a pigment dispersion composition and a colored photosensitive resin composition that are soluble in an alkaline aqueous solution as a binder are used. Can meet environmental demands.
In addition, an organic solvent having an appropriate drying property can be used as a solvent (pigment dispersion medium) used in the pigment dispersion composition and the colored photosensitive resin composition, and satisfies the requirements in terms of drying after coating. Can do.

[Colored photosensitive resin composition]
The colored photosensitive resin composition of the present invention comprises at least (a) organic pigment nanoparticles, (b) a binder, (c) a polyfunctional monomer having two or more ethylenically unsaturated double bonds, and (d) light. Includes a polymerization initiator or photopolymerization initiator system. Hereinafter, each component of the colored photosensitive resin composition of the present invention will be described.

(A) Organic Pigment Nanoparticles The method for producing organic pigment nanoparticles has already been described in detail. The content of the organic pigment nanoparticles is 3 to 90% by mass with respect to the total solid content in the colored photosensitive resin composition (in the present invention, the total solid content refers to the total composition excluding the organic solvent). Is preferable, 20-80 mass% is more preferable, and 25-60 mass% is further more preferable. If this amount is too large, the viscosity of the dispersion increases, which may cause problems in production suitability. If the amount is too small, the coloring power is not sufficient. The organic pigment nanoparticles (pigment particles) functioning as a colorant preferably have a particle size of 0.1 μm or less, particularly 0.08 μm or less. Moreover, you may use it in combination with a normal pigment for toning. As the pigment, those described above can be used.

(B) Binder As the binder in the colored photosensitive resin composition, the above-described polymer compound having a mass average molecular weight of 1000 or more can be preferably used. As for content of a binder, 15-50 mass% is common with respect to the total solid of a colored photosensitive resin composition, and 20-45 mass% is preferable. If the amount is too large, the viscosity of the composition becomes too high, causing a problem in production suitability. If the amount is too small, there is a problem in forming a coating film.

(C) Polyfunctional monomer or oligomer having two or more ethylenically unsaturated double bonds As a polyfunctional monomer or oligomer having two or more ethylenically unsaturated double bonds to be contained in the colored photosensitive resin composition of the present invention Is a monomer or oligomer that has two or more ethylenically unsaturated double bonds and undergoes addition polymerization upon irradiation with light. Examples of such monomers and oligomers include compounds having at least one addition-polymerizable ethylenically unsaturated group in the molecule and having a boiling point of 100 ° C. or higher at normal pressure. Examples include monofunctional acrylates and monofunctional methacrylates such as dipentaerythritol hexa (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate and phenoxyethyl (meth) acrylate; polyethylene glycol di ( (Meth) acrylate, polypropylene glycol di (meth) acrylate, trimethylolethane triacrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane diacrylate, neopentylglycol di (meth) acrylate, pentaerythritol tetra (meth) acrylate, Pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipenta Rithritol penta (meth) acrylate, hexanediol di (meth) acrylate, trimethylolpropane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) isocyanurate, tri (acryloyloxyethyl) cyanurate, glycerin tri (meth) acrylate And polyfunctional acrylates and polyfunctional methacrylates such as those obtained by adding ethylene oxide or propylene oxide to a polyfunctional alcohol such as trimethylolpropane or glycerin and then (meth) acrylated. In addition, as described in JP-A-10-62986, general formulas (1) and (2), a compound obtained by adding ethylene oxide or propylene oxide to a polyfunctional alcohol and then (meth) acrylated is also suitable. As mentioned.

Further, urethane acrylates described in JP-B-48-41708, JP-B-50-6034 and JP-A-51-37193; JP-A-48-64183, JP-B-49-43191 And polyester acrylates described in Japanese Patent Publication No. 52-30490; polyfunctional acrylates and methacrylates such as epoxy acrylates which are reaction products of epoxy resin and (meth) acrylic acid.
Among these, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and dipentaerythritol penta (meth) acrylate are preferable.
In addition, “polymerizable compound B” described in JP-A-11-133600 can also be mentioned as a preferable example.

  These monomers or oligomers (monomers or oligomers having a molecular weight of 200 to 1000 are preferred) may be used alone or in admixture of two or more, and may be used for the total solid content of the colored photosensitive resin composition. The content is generally 5 to 50% by mass, and preferably 10 to 40% by mass. If this amount is too large, it becomes difficult to control the developability, which causes a problem in production suitability. If the amount is too small, the curing power at the time of exposure is insufficient.

(D) Photopolymerization initiator or photopolymerization initiator system Photopolymerization initiator or photopolymerization initiator system contained in the colored photosensitive resin composition of the present invention (in the present invention, the photopolymerization initiator system is a plurality of compounds) And a vicinal polyketaldonyl compound disclosed in US Pat. No. 2,367,660, which is described in US Pat. No. 2,448,828. An acyloin ether compound, an aromatic acyloin compound substituted with an α-hydrocarbon described in US Pat. No. 2,722,512, a polynuclear quinone compound described in US Pat. Nos. 3,046,127 and 2,951,758, A combination of a triarylimidazole dimer and a p-aminoketone described in US Pat. No. 3,549,367, Benzothiazole compounds and trihalomethyl-s-triazine compounds described in JP-A-48516, trihalomethyl-triazine compounds described in US Pat. No. 4,239,850, and US Pat. No. 4,221,976 A trihalomethyl oxadiazole compound etc. can be mentioned. In particular, trihalomethyl-s-triazine, trihalomethyloxadiazole, and triarylimidazole dimer are preferable.

  In addition, “polymerization initiator C” described in JP-A-11-133600, oxime-based compounds such as 1-phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) oxime, O— Benzoyl-4 '-(benzmercapto) benzoyl-hexyl-ketoxime, 2,4,6-trimethylphenylcarbonyl-diphenyl phosphonyl oxide, hexafluorophospho-trialkylphenyl phosphonium salt and the like may be mentioned as suitable ones. it can.

These photopolymerization initiators or photopolymerization initiator systems may be used singly or as a mixture of two or more, but it is particularly preferable to use two or more. When at least two kinds of photopolymerization initiators are used, display characteristics, particularly display unevenness, can be reduced.
The content of the photopolymerization initiator or the photopolymerization initiator system with respect to the total solid content of the colored photosensitive resin composition is generally 0.5 to 20% by mass, and preferably 1 to 15% by mass. If this amount is too large, the sensitivity becomes too high and control becomes difficult. If the amount is too small, the exposure sensitivity becomes too low. The radiation that can be used for exposure is particularly preferably ultraviolet rays such as g-line and i-line. Irradiation dose is preferably 5~1500mJ / cm ^2, more preferably ^{10~1000mJ / cm 2, 10~500mJ / cm} 2 is particularly preferred.

(Other additives)
〔solvent〕
In the colored photosensitive resin composition of the present invention, an organic solvent may be further used in addition to the above components. Examples of organic solvents include, but are not limited to, esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, Alkyl esters, methyl lactate, ethyl lactate, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-oxypropionate, -3-oxypropionic acid alkyl esters such as ethyl oxypropionate; methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 2-oxypropionic acid Chill, ethyl 2-oxypropionate, propyl 2-oxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate Methyl 2-oxy-2-methylpropionate, ethyl 2-oxy-2-methylpropionate, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, methyl pyruvate, pyrubin Ethyl acetate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, etc .; ethers such as diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ether Ren glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, propylene glycol methyl ether acetate, etc .; ketones such as methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, cyclohexanol, 2-heptanone, 3-heptanone, etc .; Aromatic hydrocarbons such as toluene, xyles and the like can be mentioned. Among these solvents, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, ethyl carbitol acetate, butyl carbitol Acetate, propylene glycol methyl ether acetate and the like are preferably used as the solvent in the present invention. These solvents may be used alone or in combination of two or more.

Moreover, the solvent whose boiling point is 180 to 250 degreeC can be used if needed. Examples of these high-boiling solvents include the following. Diethylene glycol monobutyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether, 3,5,5-trimethyl-2-cyclohexen-1-one, butyl lactate, dipropylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol di Acetate, propylene glycol-n-propyl ether acetate, diethylene glycol diethyl ether, 2-ethylhexyl acetate, 3-methoxy-3-methylbutyl acetate, γ-butyllactone, tripropylene glycol methyl ethyl acetate, dipropylene glycol-n-butyl acetate, Propylene glycol phenyl ether acetate, 1, - butanediol diacetate.
As for content of a solvent, 10-95 mass% is preferable with respect to the resin composition whole quantity.

[Surfactant]
Conventionally used color filters have a problem that the color of each pixel becomes dark in order to achieve high color purity, and the film thickness unevenness of the pixel is recognized as color unevenness as it is. For this reason, it has been demanded to improve the film thickness variation during the formation (application) of the photosensitive resin layer, which directly affects the pixel film thickness.
In the color filter of the present invention or the photosensitive resin transfer material of the present invention, the colored photosensitive resin can be controlled to have a uniform film thickness and effectively prevent coating unevenness (color unevenness due to film thickness fluctuation). It is preferable to include an appropriate surfactant in the composition.
Preferred examples of the surfactant include surfactants disclosed in JP-A Nos. 2003-337424 and 11-133600. The content of the surfactant is preferably 5% by mass or less with respect to the total amount of the resin composition.

(Thermal polymerization inhibitor)
The colored photosensitive resin composition of the present invention preferably contains a thermal polymerization inhibitor. Examples of the thermal polymerization inhibitor include hydroquinone, hydroquinone monomethyl ether, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4′-thiobis (3-methyl). -6-t-butylphenol), 2,2'-methylenebis (4-methyl-6-t-butylphenol), 2-mercaptobenzimidazole, phenothiazine and the like. The content of the thermal polymerization inhibitor is preferably 1% by mass or less based on the total amount of the resin composition.

[Additive dyes and pigments]
In addition to the said colorant (pigment), a colorant (dye, pigment) can be added to the colored photosensitive resin composition of this invention as needed. In the case of using a pigment among the colorants, it is desirable that the pigment is uniformly dispersed in the colored photosensitive resin composition. Therefore, the particle diameter is preferably 0.1 μm or less, particularly 0.08 μm or less.
Specific examples of the dye or pigment include the colorant described in JP-A-2005-17716 [0038] to [0040] and JP-A-2005-361447 [0068] to [0072]. And the colorants described in JP-A-2005-17521 [0080] to [0088] can be suitably used. The content of the auxiliary dye or pigment is preferably 5% by mass or less based on the total amount of the resin composition.

[Ultraviolet absorber]
The colored photosensitive resin composition of the present invention may contain an ultraviolet absorber as necessary. Examples of the UV absorber include salicylate-based, benzophenone-based, benzotriazole-based, cyanoacrylate-based, nickel chelate-based, hindered amine-based compounds, etc., in addition to the compounds described in JP-A-5-72724.
Specifically, phenyl salicylate, 4-t-butylphenyl salicylate, 2,4-di-t-butylphenyl-3 ′, 5′-di-t-4′-hydroxybenzoate, 4-t-butylphenyl salicylate 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2 '-Hydroxy-3'-t-butyl-5'-methylphenyl) -5-chlorobenzotriazole, ethyl-2-cyano-3,3-diphenyl acrylate, 2,2'-hydroxy-4-methoxybenzophenone, nickel Dibutyldithiocarbamate, bis (2,2,6,6-tetramethyl-4-pyridine) -Sebakei 4-t-butylphenyl salicylate, phenyl salicylate, 4-hydroxy-2,2,6,6-tetramethylpiperidine condensate, succinic acid-bis (2,2,6,6-tetramethyl-4-piperidenyl ) -Ester, 2- [2-hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole, 7-{[4-chloro-6- (diethylamino) -5-triazine- 2-yl] amino} -3-phenylcoumarin and the like. As for content of a ultraviolet absorber, 5 mass% or less is preferable with respect to the resin composition whole quantity.

  In addition, the colored photosensitive resin composition of the present invention may contain “adhesion aid” described in JP-A No. 11-133600, other additives and the like in addition to the above additives.

[Inkjet ink]
In addition to the color filter, the inkjet ink of the present invention may be a normal inkjet ink for image formation or the like. In particular, the inkjet ink for a color filter is preferable. The ink jet ink is not particularly limited as an embodiment in the present invention, but for example, a method described in JP-A-2002-201387 can be preferably used.
The ink-jet ink of the present invention is only required to use the organic pigment nanoparticles (a), and preferably contains a polyfunctional monomer or oligomer (c) having two or more ethylenically unsaturated bonds. . Here, as the polymerizable monomer and / or polymerizable oligomer (c), those described above for the colored photosensitive resin composition can be used. The inkjet ink of the present invention may further contain the binder (b), photopolymerization initiator or photopolymerization initiator system (d), and other additives. The content of each component ((a) to (d), other additives) may be the same as that described above for the colored photosensitive assembly. However, when the inkjet ink of the present invention is used as an ink for preparing a color filter, an embodiment that is not a photosensitive ink is preferable, and it is preferable not to use a photopolymerization initiator or a photopolymerization initiator system.

In the ink-jet ink of the present invention, it is preferable to control the ink temperature so that the fluctuation range of the viscosity is within ± 5%. The viscosity at the time of injection is preferably 5 to 25 mPa · s, more preferably 8 to 22 mPa · s, and particularly preferably 10 to 20 mPa · s (in the present invention, unless otherwise specified) It is a value at 25 ° C.). In addition to the setting of the injection temperature, the viscosity can be adjusted by adjusting the type and amount of components contained in the ink. The viscosity can be measured, for example, by a normal apparatus such as a conical plate type rotational viscometer or an E type viscometer.
The surface tension of the ink upon ejection is preferably 15 to 40 mN / m from the viewpoint of improving the flatness of the pixel (in the present invention, the surface tension is a value at 23 ° C. unless otherwise specified). ). More preferably, it is 20-35 mN / m, Most preferably, it is 25-30 mN / m. The surface tension can be adjusted by adding a surfactant or the type of solvent. The surface tension is measured using a known measuring instrument such as a surface tension measuring device (CBVP-Z, manufactured by Kyowa Interface Science Co., Ltd.) or a fully automatic balanced electro surface tension meter ESB-V (manufactured by Kyowa Scientific Co., Ltd.). And can be measured by a platinum plate method.

The inkjet ink spraying method of the present invention includes a method in which charged ink is continuously ejected and controlled by an electric field, a method in which ink is intermittently ejected using a piezoelectric element, and a method in which ink is heated and foamed. Various methods such as a method of intermittent injection can be employed.
As for the method of forming each pixel, a normal method such as a method of thermally curing ink, a method of photocuring, or a method of ejecting droplets after forming a transparent image receiving layer on a substrate in advance may be used. it can.

[Coating film of colored photosensitive resin composition]
The components contained in the coating film using the colored photosensitive resin composition of the present invention are the same as those already described in the section of [Colored photosensitive resin composition]. Moreover, although the thickness of the coating film using the colored photosensitive resin composition of this invention can be suitably determined with the use, it is preferable that it is 0.5-5.0 micrometers, and 1.0-3. More preferably, it is 0 μm. In the coating film using the colored photosensitive resin composition of the present invention, (c) the monomer or oligomer contained therein is polymerized to form a colored photosensitive resin composition polymer film, and a color filter having the same is prepared. (The production of the color filter will be described later). Polymerization of the polymerizable monomer or polymerizable oligomer can be carried out by allowing (d) a photopolymerization initiator or a photopolymerization initiator system to act upon irradiation with light.

(Slit nozzle)
In addition, although the said coating film can be formed by apply | coating and drying a colored photosensitive resin composition with a normal coating method, in this invention, it has a slit-shaped hole in the part which discharges a liquid. It is preferable to apply with a slit-like nozzle. Specifically, JP-A-2004-89851, JP-A-2004-17043, JP-A-2003-170098, JP-A-2003-164787, JP-A-2003-10767, JP-A-2002-79163. Slit nozzles and slit coaters described in Japanese Patent Laid-Open No. 2001-310147 and the like are preferably used.

  As a method for applying the colored photosensitive resin composition to the substrate, spin coating is excellent in that a thin film having a thickness of 1 to 3 μm can be uniformly and highly accurately applied, and can be widely used for manufacturing color filters. . However, in recent years, with the increase in size and mass production of liquid crystal display devices, slit coating suitable for coating a substrate that is wider and larger in area than spin coating has been used in order to increase manufacturing efficiency and manufacturing cost. It has come to be adopted in the production of. From the viewpoint of liquid-saving properties, slit coating is superior to spin coating, and a uniform coating film can be obtained with a smaller amount of coating liquid.

  In slit coating, a coating head having a slit (gap) with a width of several tens of microns at the tip and a length corresponding to the coating width of a rectangular substrate is maintained at a clearance (gap) of several tens to several hundreds of microns with the substrate. On the other hand, this is a coating method in which a coating liquid supplied from a slit is applied to a substrate with a predetermined discharge amount by giving a constant relative speed between the substrate and the coating head. This slit coating is (1) less liquid loss compared to spin coating, (2) cleaning process is reduced because there is no flying of the coating liquid, and (3) the scattered liquid components are applied to the coating film again. There is an advantage that there is no mixing, (4) the tact time can be shortened because there is no start-up stop time of rotation, and (5) application to a large substrate is easy. From these advantages, slit coating is suitable for producing a color filter for a large-screen liquid crystal display device, and is expected as an advantageous coating method for reducing the amount of coating liquid.

  Since slit coating forms a coating film with a much larger area than spin coating, it is necessary to maintain a certain relative speed between the coater and the object to be coated when discharging the coating liquid from the wide slit exit. is there. For this reason, good fluidity is required for the coating liquid used in the slit coating method. In addition, the slit coating is particularly required to keep the conditions of the coating solution supplied to the substrate from the slit of the coating head constant over the entire coating width. Insufficient liquid properties such as fluidity and viscoelastic properties of the coating liquid tend to cause coating unevenness, making it difficult to keep the coating thickness constant in the coating width direction and obtaining a uniform coating film. The problem of not being able to occur.

  For these reasons, many attempts have been made to improve the fluidity and viscoelastic properties of the coating solution in order to obtain a uniform coating film without unevenness. However, as mentioned above, the molecular weight of the polymer is reduced, a polymer with excellent solubility in the solvent is selected, various solvents are selected to control the evaporation rate, and a surfactant is used. Means have been proposed, but none were sufficient to improve the above problems.

[Photosensitive resin transfer material]
Next, the photosensitive resin transfer material of the present invention will be described.
The photosensitive resin transfer material of the present invention is preferably formed using the photosensitive resin transfer material described in JP-A-5-72724, that is, an integral film. As an example of the structure of the integral film, there is a structure in which a temporary support / thermoplastic resin layer / intermediate layer / photosensitive resin layer / protective film are laminated in this order. Is provided with a photosensitive resin by using the above-mentioned colored photosensitive resin composition of the present invention.

(Temporary support)
In the photosensitive resin transfer material of the present invention, the temporary support is required to be flexible and not to cause significant deformation, shrinkage or elongation even under pressure or under pressure and heating. is there. Examples of such a temporary support include a polyethylene terephthalate film, a cellulose triacetate film, a polystyrene film, a polycarbonate film, etc. Among them, a biaxially stretched polyethylene terephthalate film is particularly preferable.

(Thermoplastic resin layer)
As the component used for the thermoplastic resin layer, organic polymer substances described in JP-A-5-72724 are preferable, and the polymer softening point according to the Viker Vicat method (specifically, the American Material Testing Method ASTM D1 ASTM D1235). It is particularly preferred that the softening point by the measurement method is selected from organic polymer substances having a temperature of about 80 ° C. Specifically, polyolefins such as polyethylene and polypropylene, ethylene copolymers such as ethylene and vinyl acetate or saponified products thereof, ethylene and acrylic acid esters or saponified products thereof, polyvinyl chloride, vinyl chloride and vinyl acetate and saponified products thereof. Vinyl chloride copolymer such as fluoride, polyvinylidene chloride, vinylidene chloride copolymer, polystyrene, styrene copolymer such as styrene and (meth) acrylic acid ester or saponified product thereof, polyvinyl toluene, vinyl toluene and (meta ) Vinyl toluene copolymer such as acrylic ester or saponified product thereof, poly (meth) acrylic ester, (meth) acrylic ester copolymer such as butyl (meth) acrylate and vinyl acetate, vinyl acetate copolymer Combined nylon, copolymer nylon, N-alkoxyme Le nylon, and organic polymeric polyamide resins such as N- dimethylamino nylon.

(Middle layer)
In the photosensitive resin transfer material of the present invention, it is preferable to provide an intermediate layer for the purpose of preventing mixing of components during application of a plurality of application layers and during storage after application. As the intermediate layer, it is preferable to use an oxygen-blocking film having an oxygen-blocking function, which is described as “separation layer” in JP-A-5-72724. This reduces the time load and improves productivity.
The oxygen barrier film is preferably one that exhibits low oxygen permeability and is dispersed or dissolved in water or an aqueous alkali solution, and can be appropriately selected from ordinary ones. Among these, a combination of polyvinyl alcohol and polyvinyl pyrrolidone is particularly preferable.

(Protective film)
It is preferable to provide a thin protective film on the photosensitive resin layer in order to protect it from contamination and damage during storage. The protective film may be made of the same or similar material as the temporary support, but must be easily separated from the photosensitive resin layer. For example, silicone paper, polyolefin or polytetrafluoroethylene sheet is suitable as the protective film material.

(Method for producing photosensitive resin transfer material)
The photosensitive resin transfer material of the present invention is provided with a thermoplastic resin layer by applying a coating solution (a coating solution for a thermoplastic resin layer) in which an additive for a thermoplastic resin layer is dissolved on a temporary support, followed by drying. Then, an intermediate layer material solution made of a solvent that does not dissolve the thermoplastic resin layer is applied on the thermoplastic resin layer and dried, and then the photosensitive resin layer is applied and dried with a solvent that does not dissolve the intermediate layer. Can be produced.
Also, a sheet provided with the thermoplastic resin layer and the intermediate layer on the temporary support and a sheet provided with the photosensitive resin layer on the protective film are prepared, and the intermediate layer and the photosensitive resin layer are in contact with each other. In addition, a sheet provided with a thermoplastic resin layer on the temporary support and a sheet provided with a photosensitive resin layer and an intermediate layer on a protective film are prepared, and a thermoplastic resin layer is prepared. Can also be produced by bonding them so that the intermediate layer is in contact with each other.

  In the photosensitive resin transfer material of the present invention, the thickness of the photosensitive resin layer is preferably 1.0 to 5.0 μm, more preferably 1.0 to 4.0 μm, and particularly preferably 1.0 to 3.0 μm. preferable. Further, although not particularly limited, preferred film thicknesses of other layers are 15 to 100 μm for the temporary support, 2 to 30 μm for the thermoplastic resin layer, 0.5 to 3.0 μm for the intermediate layer, and protection. The film is generally preferably 4 to 40 μm.

  In addition, although application | coating in the said preparation method can be performed with a normal coating apparatus etc., in this invention, the slit-shaped nozzle already demonstrated in the term of the coating film of a coloring photosensitive resin composition was used. It is preferable to use a coating apparatus (slit coater). Preferred specific examples of the slit coater are the same as described above.

[Color filter]
The color filter of this invention can be used as a thing excellent in contrast. In the present invention, the contrast represents the ratio of the amount of transmitted light between two polarizing plates when the polarization axis is parallel and when it is vertical (“1990 Seventh Color Optical Conference, 512-color display 10.4. "Refer to" Color TFT for TFT-LCD, Ueki, Koseki, Fukunaga, Yamanaka "etc.).
The high contrast of the color filter means that the bright and dark discrimination when combined with the liquid crystal can be increased, which is a very important performance in order to replace the liquid crystal display with a CRT.

  When the color filter of the present invention is used for a television, the chromaticities of all the single colors of red (R), green (G), and blue (B) by the F10 light source are the values shown in the table below ( Hereinafter, in the present invention, the difference (ΔE) from the “target chromaticity”) is preferably in the range of 5 or less, more preferably 3 or less, and particularly preferably 2 or less.

x y Y
------------------------
R 0.656 0.336 21.4
G 0.293 0.634 52.1
B 0.146 0.088 6.90
------------------------

In the present invention, chromaticity is measured with a microspectrophotometer (manufactured by Olympus Optical Co., Ltd .; OSP100 or 200), calculated as a result of the F10 light source field of view of 2 degrees, and expressed as an xyY value in the xyz color system. Further, the difference from the target chromaticity is represented by a color difference of the La ^* b ^* color system.

(Photosensitive resin layer)
The color filter of the present invention can be produced by a method such as a method in which a photosensitive resin layer is formed on a substrate, and exposure and development are repeated for the number of colors. If necessary, the boundary may be divided by a black matrix.
In the above manufacturing method, as the method for forming the photosensitive resin layer on the substrate, (a) a method of applying each of the above colored photosensitive resin compositions with a normal coating apparatus or the like, and (b) the above-mentioned method Examples thereof include a method of using a photosensitive resin transfer material and pasting with a laminator.

(A) Application by coating device When producing the color filter of the present invention, a normal coating device can be used for coating the colored photosensitive resin composition. The slit coater described in the section of [Coating film] can be suitably used. The preferred specific example of the slit coater is the same as described above. When the photosensitive resin layer is formed by coating, the film thickness is preferably 1.0 to 3.0 μm, more preferably 1.0 to 2.5 μm, and particularly preferably 1.5 to 2.5 μm.

(B) Affixing with a laminator A photosensitive resin transfer material of the present invention is used to press-bond or bond a photosensitive resin layer formed in a film shape with a roller or flat plate heated and / or pressurized on a substrate to be described later. It can be attached by thermocompression bonding. Specific examples include laminators and laminating methods described in JP-A-7-110575, JP-A-11-77942, JP-A-2000-334836, and JP-A-2002-148794. From this point of view, it is preferable to use the method described in JP-A-7-110575. In addition, the preferable film thickness in the case of forming the photosensitive resin layer with the photosensitive resin transfer material of the present invention is the same as the preferable film thickness described in the section of [Photosensitive resin transfer material].

(substrate)
In the present invention, as the substrate on which the color filter is formed, for example, a transparent substrate is used, and a known glass plate such as a soda glass plate having a silicon oxide film on its surface, a low expansion glass, a non-alkali glass, a quartz glass plate, etc. Or a plastic film etc. can be mentioned.
Moreover, the said board | substrate can make favorable adhesion | attachment with a coloring photosensitive resin composition or the photosensitive resin transfer material by giving a coupling process previously. As the coupling treatment, a method described in JP 2000-39033 A is preferably used. In addition, although it does not necessarily limit, as a film thickness of a board | substrate, 700-1200 micrometers is generally preferable and 500-1100 micrometers is especially preferable.

(Oxygen barrier membrane)
In the color filter of the present invention, when the photosensitive resin layer is formed by applying a colored photosensitive resin composition, an oxygen-blocking film can be further provided on the photosensitive resin layer, thereby improving the exposure sensitivity. Can be up. Examples of the oxygen blocking film include those already described in the section of (Intermediate layer) of [Photosensitive resin transfer material]. Although not particularly limited, the thickness of the oxygen blocking film is generally preferably 0.5 to 3.0 μm.

(Exposure and development)
A predetermined mask is disposed above the photosensitive resin layer formed on the substrate, and then exposed from above the mask through the mask, the thermoplastic resin layer, and the intermediate layer, and then developed with a developer. By repeating this process for the number of colors, the color filter of the present invention can be obtained.
Here, the light source for the exposure can be appropriately selected and used as long as it can irradiate light in a wavelength region capable of curing the photosensitive resin layer (for example, 365 nm, 405 nm, etc.). Specifically, an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a metal halide lamp, etc. are mentioned. As an exposure amount, it is about 5-200 mJ / cm < ² > normally, Preferably it is about 10-100 mJ / cm < ² >.

Moreover, there is no restriction | limiting in particular as said developing solution, Normal developing solutions, such as a thing of Unexamined-Japanese-Patent No. 5-72724, can be used. The developer is preferably one in which the photosensitive resin layer exhibits a dissolution type development behavior. For example, a developer containing a compound having a pKa of 7 to 13 at a concentration of 0.05 to 5 mol / L is preferable. A small amount of a miscible organic solvent may be added.
Examples of organic solvents miscible with water include methanol, ethanol, 2-propanol, 1-propanol, butanol, diacetone alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-butyl ether, and benzyl alcohol. , Acetone, methyl ethyl ketone, cyclohexanone, ε-caprolactone, γ-butyrolactone, dimethylformamide, dimethylacetamide, hexamethylphosphoramide, ethyl lactate, methyl lactate, ε-caprolactam, N-methylpyrrolidone and the like. The concentration of the organic solvent is preferably 0.1% by mass to 30% by mass.
Further, a normal surfactant can be further added to the developer. The concentration of the surfactant is preferably 0.01% by mass to 10% by mass.

As a development method, methods such as paddle development, shower development, shower & spin development, and dip development can be used.
Here, the shower development will be described. The uncured portion can be removed by spraying a developer onto the exposed photosensitive resin layer by shower. In addition, it is preferable to spray an alkaline liquid having low solubility of the photosensitive resin layer by a shower or the like before development to remove the thermoplastic resin layer, the intermediate layer, or the like. Further, after the development, it is preferable to remove the development residue while spraying a cleaning agent or the like with a shower and rubbing with a brush or the like.
The liquid temperature of the developer is preferably 20 ° C. to 40 ° C., and the pH of the developer is preferably 8 to 13.

In addition, when manufacturing the color filter of the present invention, as described in JP-A No. 11-248922 and Japanese Patent No. 3255107, a base is formed by overlapping the colored photosensitive resin composition forming the color filter, It is preferable from the viewpoint of cost reduction to form a spacer by forming a transparent electrode thereon, and further overlapping projections for divisional alignment.
When the colored photosensitive resin composition is sequentially applied and stacked, the film thickness becomes thin each time the coating is performed due to the leveling of the coating solution. For this reason, it is preferable to overlap the four colors of K (black), R, G, and B, and further overlap the divisional alignment protrusions. On the other hand, in the case of using a transfer material having a thermoplastic resin layer, it is preferable that three or two colors be overlapped because the thickness is kept constant.
The size of the base is preferably 25 μm or more, and particularly preferably 30 μm or more, from the viewpoint of preventing deformation of the photosensitive resin layer when the transfer material is laminated and laminating and maintaining a certain thickness.

[Liquid Crystal Display]
The liquid crystal display device of the present invention uses the color filter of the present invention having excellent contrast, and is excellent in descriptive power such as black spots. It can also be suitably used as a large-screen liquid crystal display device such as a notebook personal computer display or a television monitor.

[CCD device]
The CCD device of the present invention comprises a color filter produced using the pigment nanoparticles. Hereinafter, the CCD device of the present invention will be described in detail.
Alkali-soluble resin The alkali-soluble resin used in the CCD device is preferably a linear organic polymer, soluble in an organic solvent, and developable with a weak alkaline aqueous solution. Examples of such linear organic high molecular polymers include polymers having a carboxylic acid in the side chain, such as JP-A-59-44615, JP-B-54-34327, JP-B-58-12777, and JP-B-54-25957. Methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, as described in JP-A Nos. 59-53836 and 59-71048, There are maleic acid copolymers, partially esterified maleic acid copolymers, and the like, and similarly there are acidic cellulose derivatives having a carboxylic acid in the side chain. In addition, a polymer obtained by adding an acid anhydride to a polymer having a hydroxyl group is also useful. Of these, benzyl (meth) acrylate / (meth) acrylic acid copolymers and multi-component copolymers with benzyl (meth) acrylate / (meth) acrylic acid / and other monomers are preferred. In addition, 2-hydroxyethyl methacrylate, polyvinyl pyrrolidone, polyethylene oxide, polyvinyl alcohol, and the like are also useful as the water-soluble polymer.

  Further, 2-hydroxypropyl (meth) acrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer, 2-hydroxy-3-phenoxypropyl acrylate / polymethyl methacrylate macromonomer / benzyl described in JP-A-7-140654 Methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene macromonomer / methyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer, etc. It is done. As addition amount in the curable composition of the said alkali-soluble resin, 5-90 mass% is preferable with respect to the composition total mass, More preferably, it is 10-60 mass%.

Polymerizable monomer The polymerizable monomer is preferably a compound having at least one addition-polymerizable ethylene group and having an ethylenically unsaturated group having a boiling point of 100 ° C. or higher under normal pressure.

  Compounds having at least one addition-polymerizable ethylenically unsaturated group and a boiling point of 100 ° C. or higher at normal pressure include polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, and phenoxyethyl (meth). Monofunctional acrylates and methacrylates such as acrylates; polyethylene glycol di (meth) acrylate, trimethylolethane tri (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra ( (Meth) acrylate, dipentaerythritol hexa (meth) acrylate, hexanediol (meth) acrylate, trimethylolpropane tri (acryloyloxypropyl) ether, (Acryloyloxyethyl) isocyanurate, polyfunctional alcohols such as glycerin and trimethylolethane, and then (meth) acrylate after addition of ethylene oxide or propylene oxide, Japanese Patent Publication No. 48-41708, Japanese Patent Publication No. 50-6034 And urethane acrylates as described in JP-A-51-37193, JP-A-48-64183, JP-B-49-43191, JP-B-52-30490 Polyfunctional acrylates and methacrylates such as polyester acrylates and epoxy acrylates which are reaction products of epoxy resin and (meth) acrylic acid can be mentioned. Furthermore, the Japan Adhesion Association Vol. 20, no. 7, what is introduced as a photocurable monomer and oligomer on pages 300 to 308 can also be used.

  Moreover, the compound shown by the following general formula (B-1) or (B-2) can also be used.

{Wherein (B-1), (B -2), B are each _{independently, - (CH 2 CH 2 O} ) - and _{- (CH 2 CH (CH 3} ) O) - represents one of; X each independently represents any of an acryloyl group, a methacryloyl group and a hydrogen atom, and, in the formula (B-1), the total of the acryloyl group and the methacryloyl group is 5 or 6, and the formula (B -2) is 3 or 4; n is each independently an integer of 0-6, and the sum of each n is 3-24; m is each independently 0-6 It represents an integer, and the total of each m is 2-16. }

  These polymerizable monomers can be used in any ratio as long as they can form a coating film having adhesiveness upon irradiation with radiation. The amount used is usually 5 to 90% by mass, preferably 10 to 50% by mass, based on the total solid content of the composition.

Colorant As the colorant, various conventionally known dyes, inorganic pigments or organic pigments can be used singly or in combination.

  There is no restriction | limiting in particular in dye, A well-known dye can be used for color filters conventionally. For example, Japanese Patent Application Laid-Open No. 64-90403, Japanese Patent Application Laid-Open No. 64-91102, Japanese Patent Application Laid-Open No. 1-94301, Japanese Patent Application Laid-Open No. 6-11614, No. 2592207, US Pat. No. 4,808,501, US Pat. No., U.S. Pat. No. 505950, U.S. Pat. No. 5,667,920, JP-A-5-333207, JP-A-6-35183, JP-A-6-51115, JP-A-6-194828, etc. Can be used. As chemical structures, dyes such as pyrazole azo, anilino azo, triphenyl methane, anthraquinone, benzylidene, oxonol, pyrazolotriazole azo, pyridone azo, cyanine, phenothiazine, pyrrolopyrazole azomethine are used. it can. In particular, since the curable composition can be cured at a relatively low temperature, even a dye that is inferior in heat resistance compared to a pigment can be used at a high temperature during post-baking to impart durability to the cured film. It is possible to reduce problems such as decomposition even when exposed to water.

  Examples of inorganic pigments are metal compounds such as metal oxides and metal complex salts. Specifically, metal oxides such as iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, and antimony And composite oxides of the above metals.

  Examples of organic pigments include C.I. I. Pigment Yellow 11, 24, 31, 53, 83, 85, 99, 108, 109, 110, 138, 139, 150, 151, 154, 167, 185, C.I. I. Pigment Orange 36, 38, 43, 71, C.I. I. Pigment Red 105, 122, 149, 150, 155, 171, 175, 176, 177, 209, 224, 242, 254, C.I. I. Pigment Violet 19, 23, 32, 39, C.I. I. Pigment Blue 1, 2, 15, 16, 22, 60, 66, 15: 3, 15: 6, C.I. I. Pigment Green 7, 36, 37, C.I. I. Pigment Brown 25, 28, C.I. I. Pigment Black 1, 7, carbon black and the like.

  These organic pigments can be used alone or in various combinations in order to increase color purity. Specific examples are shown below. As the red pigment, an anthraquinone pigment, perylene pigment alone or a mixture of at least one of them with a disazo yellow pigment or an isoindoline yellow pigment is used. For example, as an anthraquinone pigment, C.I. I. Pigment Red 177 and perylene pigments include C.I. I. Pigment Red 155, and C.I. I. Pigment yellow 83 or C.I. I. Good mixing with Pigment Yellow 139. The mass ratio of the red pigment to the yellow pigment is preferably from 100: 5 to 100: 50. In this range, the light transmittance from 400 nm to 500 nm can be suppressed, and the color purity can be increased, which is preferable.

  As the green pigment, a halogenated phthalocyanine pigment alone or a mixture with a disazo yellow pigment, a quinophthalone yellow dye or an isoindoline yellow pigment is used. I. Pigment Green 7, 36, 37 and C.I. I. Mixing with pigment yellow 83, 138, 139 is preferred. The mass ratio of the green pigment to the yellow pigment is preferably 100: 5 to 100: 100. Within this range, light transmittance from 400 nm to 450 nm can be suppressed, and good color purity can be obtained.

  As the blue pigment, a phthalocyanine pigment alone or a mixture with a dioxazine purple pigment is used. I. Pigment blue 15: 6 and C.I. I. Mixing with pigment violet 23 is preferred. The mass ratio of the blue pigment to the violet pigment is preferably 100: 0 to 100: 50. Within this range, the light transmittance from 400 nm to 420 nm can be suppressed and the color purity can be increased.

  Further, a pigment-containing photosensitive resin having good dispersibility and dispersion stability by using a powdered processed pigment in which the above pigment is finely dispersed in an acrylic resin, a maleic acid resin, a vinyl chloride-vinyl acetate copolymer, an ethyl cellulose resin, or the like. Can be obtained.

  Further, as the pigment for the black matrix, carbon, titanium oxide, iron oxide, alone or a mixture thereof is used, and the case of carbon and titanium oxide is preferable. The mass ratio is preferably in the range of 100: 5 to 100: 40. Within this range, the light transmittance at long wavelengths is small, and the dispersion stability is also good.

Solvents Solvents include esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, alkyl esters, methyl lactate, Such as ethyl lactate, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-oxypropionate, ethyl 3-oxypropionate 3-oxypropionic acid alkyl esters; methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-oxypropionate, 2-oxypropionate Ethyl onate, propyl 2-oxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, 2-oxy- Methyl 2-methylpropionate, ethyl 2-oxy-2-methylpropionate, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate, pyruvate Propyl, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, etc .: ethers such as diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl Ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, etc .; ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone, and the like; aromatic hydrocarbons such as toluene and xylene.

  Of these, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, ethyl carbitol acetate, butyl Carbitol acetate, propylene glycol methyl ether acetate and the like are preferably used. The addition amount of the solvent is usually 60 to 90% by mass, preferably 70 to 90% by mass in the composition.

  These solvents may be used alone or in combination of two or more.

  Furthermore, a sensitizer can be used in combination. Specific examples thereof include 9-fluorenone, 2-chloro-9-fluorenone, 2-methyl-9-fluorenone, 9-anthrone, 2-bromo-9-anthrone, 2-ethyl-9-anthrone, and 9,10-anthraquinone. 2-ethyl-9,10-anthraquinone, 2-t-butyl-9,10-anthraquinone, 2,6-dichloro-9,10-anthraquinone, benzyl, dibenzalacetone, p- (dimethylamino) phenylstyryl Examples thereof include ketones, p- (dimethylamino) phenyl-p-methylstyryl ketone, benzoanthrone, and benzothiazole compounds described in Japanese Patent Publication No. 51-48516.

  It can be prepared by mixing and dispersing the above main components and other additives used as necessary using various mixers and dispersers.

  A general manufacturing method of a color filter used in a CCD device is as follows. The step of applying and drying the composition (color resist solution) of the present invention on a substrate, the step of pattern exposure of the resulting dry coating film with an i-line stepper, the step of alkali development after exposure, and the step of heat treatment A color filter is obtained by sequentially performing the above steps and successively repeating the above steps for each color (three colors or four colors) to produce a cured film.

  More specifically, the above curable composition is applied onto a suitable substrate by a spinner or the like so that the film thickness upon drying is generally 0.1 to 5 μm, preferably 0.2 to 2 μm. And left in an oven at 85 ° C. for 2 minutes to obtain a smooth coating film.

  The substrate is not particularly limited, but is a glass plate, a plastic plate, an aluminum plate, a base material for electronic parts such as a silicon wafer for an image pickup device, a transparent resin plate, a resin film, a cathode ray tube display surface, a light receiving surface for image sensing feeling. Wafers with solid-state image sensors such as CCD, BBD, CID, BASIS, contact image sensors using thin film semiconductors, liquid crystal display surfaces, color electrophotographic photoreceptors, substrates for electrochromy (EC) display devices Etc. Further, it is preferable to perform a high adhesion treatment to improve the adhesion to the color filter layer on the substrate. Specifically, a pattern of the curable composition may be formed after thinly coating with a silane coupling agent or the like on the substrate in advance, or a silane coupling agent may be included in the curable composition in advance.

  In addition, when there exists a level | step difference on a board | substrate, after applying the planarization film | membrane for eliminating the level | step difference and smoothing a coating surface on a board | substrate, the curable composition of this invention can be apply | coated. . For example, an image sensor such as a CCD is composed of a photoelectric conversion unit (photodiode) that generates electrons on a silicon substrate according to the amount of received light, and a read gate unit for outputting the generated electrons. If light hits the gate part, it causes noise and accurate data is not output.Therefore, a light shielding film layer is formed on the top of the readout gate part, and there is a step between the photodiode part without the light shielding film layer. It may have occurred. When a color resist is applied on such a step and a color filter is directly formed, the optical path length becomes long, so that the image becomes dark and the light condensing property becomes inferior. In order to improve this, it is preferable to form a transparent flattening film between the CCD and the color filter in order to fill the step. Examples of the material for the flattening film include a photo-curable resist solution as in the present invention, and an acrylic or epoxy thermosetting resin.

  After applying the photocurable composition, pre-baking is usually performed to evaporate the solvent and obtain a dry coating film. Examples of the pre-baking method include reduced-pressure drying, indirect heating drying using high-temperature air, direct heating drying using a hot plate or the like (about 80 to 140 ° C., 50 to 200 seconds), and the like. In addition, post-baking is performed in order to sufficiently cure the pattern obtained after development to increase the mechanical strength and form a permanent film. For example, when a three-color filter is manufactured, the first formed pattern is then subjected to application, exposure, and development of another color resist solution twice. At this time, post-baking is performed so as not to cause pattern omission due to color mixing with the applied resist solution, exposure, and development. This post-baking uses the same method as pre-baking, but is performed at a higher temperature and for a longer time than the pre-baking conditions. For example, in the case of indirect heating by an oven, the heating is performed at about 180 to 250 ° C. for about 0.5 to 2 hours, and in the case of direct heating by a hot plate, the heating is performed at about 180 to 250 ° C. for about 2 to 10 minutes.

  Although the light source for exposure is not particularly limited, i-line of a mercury lamp can be cited as a light source that has a remarkable effect on the pattern forming property. The feature of the present invention is particularly remarkable in the production of a color filter for an image sensor in which i-line, which is one of the line spectrum of a mercury lamp, is used from an appropriate aspect of the process, but it can also be used for an LCD. Of course.

  There is no restriction | limiting in particular in the developing solution used for image development of a curable composition, A conventionally well-known developing solution can be used. Among them, an organic alkaline developer of a quaternary ammonium salt such as tetramethylammonium hydroxide (TMAH) is preferable for achieving the object of the present invention.

Polymerization initiator As the polymerization initiator, a normal photopolymerization initiator can be used. Specifically, the vicinal polykettle aldonyl compound described in US Pat. No. 2,367,660, the α described in US Pat. Nos. 2,367,661 and 2,367,670 Carbonyl compounds, acyloin ethers described in US Pat. No. 2,448,828, aromatic acyloin compounds substituted with α-hydrocarbons described in US Pat. No. 2,722,512, US Polynuclear quinone compounds described in Patent Nos. 3,046,127 and 2,951,758, and triallylimidazole dimer / p-aminophenyl ketone described in US Pat. No. 3,549,367. Combinations, benzothiazole compounds / trihalomethyl-s-triazine compounds described in JP-B 51-48516, and the like can be mentioned.

  The content of the photopolymerization initiator (including the above-described ordinary photopolymerization initiator) in the dye-containing negative curable composition is 0.01 to 50 with respect to the solid content (mass) of the radical polymerizable monomer. % By mass is preferable, 1 to 30% by mass is more preferable, and 1 to 20% by mass is particularly preferable. When the content is in the above range, sufficient polymerization and curing can be performed, and the polymerization does not proceed easily, and the polymerization rate increases but the molecular weight does not decrease and the film strength does not decrease.

Further, a sensitizer and a light stabilizer can be used in combination with the above photopolymerization initiator.
Specific examples thereof include benzoin, benzoin methyl ether, 9-fluorenone, 2-chloro-9-fluorenone, 2-methyl-9-fluorenone, 9-anthrone, 2-bromo-9-anthrone, 2-ethyl-9-anthrone. 9,10-anthraquinone, 2-ethyl-9,10-anthraquinone, 2-t-butyl-9,10-anthraquinone, 2,6-dichloro-9,10-anthraquinone, xanthone, 2-methylxanthone, 2- Methoxyxanthone, 2-ethoxyxanthone, thioxanthone, 2,4-diethylthioxanthone, acridone, 10-butyl-2-chloroacridone, benzyl, dibenzalacetone, p- (dimethylamino) phenylstyryl ketone, p- (dimethyl Amino) phenyl-p-methylstyryl ketone Examples include benzophenone, p- (dimethylamino) benzophenone (or Michler's ketone), p- (diethylamino) benzophenone, benzoanthrone, benzothiazole compounds described in Japanese Patent Publication No. 51-48516, tinuvin 1130, 400, and the like. It is done.

The present invention will be described below in more detail based on examples, but the present invention is not limited thereto.
(Example 1)
To 1000 ml of dimethyl sulfoxide, 33.3 ml of 28% methanol solution of sodium methoxide, pigment C.I. I. Pigment Red 254: trade name Irgafore Red BT-CF Ciba Specialty Chemicals Co., Ltd.) 100 g and polyvinyl pyrrolidone 150 g were added to prepare a pigment solution A. Separately, 1000 ml of water containing 16 ml of 1 mol / l hydrochloric acid was prepared as a poor solvent.
Here, NP-KX-500 manufactured by Nippon Seimitsu Chemical Co., Ltd. was added to 1000 ml of poor solvent water which was temperature-controlled at 18 ° C. and stirred at 500 rpm with a GK-0222-10 type Lamond Stirrer manufactured by Fujisawa Pharmaceutical Co., Ltd. Organic pigment particles were formed by injecting 100 ml at a flow rate of 100 ml / min using a large-capacity non-pulsating pump to prepare pigment dispersion A.
The obtained pigment dispersion A is concentrated for 90 minutes at 4000 rpm using an H-112 type centrifugal filter manufactured by Kokusan Co., Ltd. and a P89C type filter cloth manufactured by Shikishima Canvas Co., Ltd. to obtain a dispersion (dispersion A). .)
By adding 50.0 ml of ethyl lactate to 16.0 g of the pigment nanoparticle preparation paste, stirring at 1500 rpm for 60 minutes with a dissolver, and then filtering using a FP-010 type filter manufactured by Sumitomo Electric Fine Polymer Co., Ltd. Concentrated pigment liquid A (nanopigment concentration 30 mass%) was obtained.
[Preparation of pigment dispersion composition]
Using the paste, a pigment dispersion composition A having the following composition was prepared.
21.3 g of the paste-like concentrated pigment liquid A
Pigment dispersant A (the dispersant, exemplified compound 7.) 0.6 g
3.2 g of polymer compound C-16 used in the present invention
1-methoxy-2-propyl acetate 45.3g
The pigment dispersant A was synthesized according to Japanese Patent Laid-Open No. 2000-239554.
The pigment dispersion composition A having the above composition was dispersed with a motor mill M-50 (manufactured by Eiger Japan) for 1 hour at a peripheral speed of 9 m / s using zirconia beads having a diameter of 0.65 mm.
When the particle size of the obtained pigment dispersion composition A was measured using Nanotrack UPA-EX150 manufactured by Nikkiso Co., Ltd., the average particle size was 31 nm, and the particle size distribution was 5% of particles less than 15 nm. The proportion of particles exceeding 60 nm was 7%. Further, the water content of the pigment dispersion composition A was measured according to the Karl Fischer method (Experimental Chemistry Course 15 (below) Analytical Chemistry p241 or lower) (the same applies to the following Examples and Comparative Examples).
(Example 2)
When the pigment dispersion A obtained in Example 1 was concentrated with an H-112 type centrifugal filter manufactured by Kokusan Co., Ltd., a pigment dispersion composition B was prepared in exactly the same manner as in Example 1 except that the speed was 5000 rpm. .
(Example 3)
When the pigment dispersion A obtained in Example 1 is concentrated with an H-112 centrifugal filter manufactured by Kokusan Co., Ltd., the pigment dispersion composition C is exactly the same as in Example 1 except that it is 300 minutes at 5000 rpm. Was prepared.
(Comparative Example 1)
When the pigment dispersion A obtained in Example 1 is concentrated with an H-112 type centrifugal filter manufactured by Kokusan Co., Ltd., the pigment dispersion composition D is exactly the same as in Example 1 except that it is 100 minutes at 3400 rpm. Was prepared.
(Comparative Example 2)
A pigment dispersion composition E having the following composition was prepared as follows.
Pigment (Pigment Red 254) 6.4g
Sodium chloride 64.0g
3.2 g of compound C-16 used in the present invention

Sodium chloride, a pigment (Pigment Red 254) powder, and the compound C-16 used in the present invention were charged into a 1-methoxy-2-propyl acetate solution in a double-arm kneader and kneaded at 80 ° C. for 10 hours. After kneading, it is taken out in 500 parts by weight of 1% hydrochloric acid aqueous solution at 80 ° C., stirred for 1 hour, filtered, washed with hot water to remove sodium chloride and solvent, dried at 65 ° C. for 14 hours, pulverized, and 1 g of pulverized product 2.4 g of 1-methoxy-2-propyl acetate was added and mixed.
The pigment composition was dispersed with a motor mill M-50 (manufactured by Eiger Japan) for 1 hour at a peripheral speed of 9 m / s using zirconia beads having a diameter of 0.65 mm. A pigment dispersion composition E was obtained. The particle diameter measured by processing in the same manner as in Example 1 was 53 nm, the particle size distribution was 18% of particles less than 15 nm, and the ratio of particles exceeding 60 nm was 24%. .
(Comparative Example 3)
A pigment dispersion composition F was prepared in exactly the same manner as in Comparative Example 2, except that the drying conditions after filtration and washing in hot water in Comparative Example 2 were changed to 80 ° C. for 48 hours.

[Contrast measurement]
The obtained pigment dispersion compositions A to F were each coated on a glass substrate so as to have a thickness of 2 μm, thereby preparing samples. As the backlight unit, a three-wavelength cold cathode tube light source (FWL18EX-N manufactured by Toshiba Lighting & Technology Co., Ltd.) with a diffusion plate installed was used, and two polarizing plates (polarizing plates HLC2-2518 manufactured by Sanritsu Co., Ltd.) were used. ), The amount of transmitted light when the polarization axis is parallel and vertical is measured, and the ratio is defined as the contrast (“1990 Seventh Color Optical Conference, 512-color display 10. 4 ”size TFT-LCD color filter, planting, Koseki, Fukunaga, Yamanaka etc.). A color luminance meter (BM-5 manufactured by Topcon Corporation) was used for the measurement of chromaticity. Two polarizing plates, a sample, and a color luminance meter are installed at a position where the polarizing plate is 13 mm from the backlight, and a cylinder having a diameter of 11 mm and a length of 20 mm is installed at a position of 40 mm to 60 mm. Was measured on a color luminance meter installed at a position of 400 mm through a polarizing plate installed at a position of 100 mm. The measurement angle of the color luminance meter was set to 2 °. The amount of light of the backlight was set so that the luminance when the two polarizing plates were installed in parallel Nicol was 1280 cd / m ² without the sample being installed.
The sample was irradiated with a 90 mW / cm ² high-pressure mercury lamp for 24 hours, and the color difference before and after the irradiation was measured to provide an index of light resistance. In the present invention, the chromaticity is measured with a microspectrophotometer (manufactured by Olympus Optical Co., Ltd .; OSP100 or 200), calculated as a result of the F10 light source field of view of 2 degrees, and expressed as an xyY value in the xyz color system. The difference in chromaticity is represented by the color difference of the La ^* b ^* color system. The smaller the color difference, the better.

  Table 1 shows the measurement results of the moisture content, contrast, and light resistance of the samples obtained from the pigment dispersion compositions A to F.

As shown in Table 1, the pigment dispersion composition of the present invention exhibited extremely excellent contrast and light resistance as compared with the comparative example.
(Example 4-1)
The pigment dispersion composition A was mixed with other components so as to have the composition shown in Table 2 below to prepare a colored photosensitive resin composition A for color filters.

<Binder 1>
-Polymer (benzyl methacrylate / methacrylic acid / methyl methacrylate = 38/25/37 molar ratio random copolymer, molecular weight 40,000) 27 parts by mass-propylene glycol monomethyl ether acetate 73 parts by mass <DPHA solution>
Dipentaerythritol hexaacrylate (polymerization inhibitor MEHQ 500 ppm
Contained, Nippon Kayaku Co., Ltd., trade name: KAYARAD DPHA) 76 parts by mass / propylene glycol monomethyl ether acetate 24 parts by mass <Surfactant 1>
-The following compound 1 30 mass parts-Methyl ethyl ketone 70 mass parts

Colored photosensitive resin compositions B to F for color filters were prepared in the same manner as described above except that the pigment dispersion compositions B to F were used instead of the pigment dispersion composition A, respectively.
The colored photosensitive composition for producing the color filter was applied on a glass substrate using a spin coater and dried at 100 ° C. for 2 minutes to form a film having a thickness of about 2 μm. Next, the film was exposed to an ultrahigh pressure mercury lamp under a nitrogen stream, and then developed with a 1% aqueous sodium carbonate solution. Table 3 below shows the results of measuring the contrast and light resistance of the R component of each film obtained in the same manner as in [Measurement of contrast].

As shown in Table 3, the colored photosensitive resin composition of the present invention exhibited extremely superior contrast and light resistance as compared with the comparative example.
(Example 4-2)
[Preparation of color filter (preparation by application using slit-shaped nozzle)]
[Formation of black (K) image]
The alkali-free glass substrate was cleaned with a UV cleaning apparatus, then brush-cleaned with a cleaning agent, and further ultrasonically cleaned with ultrapure water. The substrate was heat-treated at 120 ° C. for 3 minutes to stabilize the surface state.
After cooling the substrate and adjusting the temperature to 23 ° C., the composition described in Table 4 below is applied on a glass substrate coater (manufactured by FS Asia Co., Ltd., trade name: MH-1600) having a slit-like nozzle. A colored photosensitive resin composition K1 was applied. Subsequently, a part of the solvent was dried by VCD (vacuum drying apparatus; manufactured by Tokyo Ohka Kogyo Co., Ltd.) for 30 seconds to eliminate the fluidity of the coating layer, and then pre-baked at 120 ° C. for 3 minutes to obtain a film thickness of 2. A 4 μm photosensitive resin layer K1 was obtained.

In a proximity type exposure machine (manufactured by Hitachi High-Tech Electronics Engineering Co., Ltd.) having an ultra-high pressure mercury lamp, with the substrate and mask (quartz exposure mask having an image pattern) standing vertically, the exposure mask surface and the mask The distance between the photosensitive resin layers was set to 200 μm, and pattern exposure was performed at an exposure amount of 300 mJ / cm ² .
Next, after spraying pure water with a shower nozzle to uniformly wet the surface of the photosensitive resin layer K1, a KOH developer (KOH, containing nonionic surfactant, trade name: CDK-1, (Fujifilm Electronics Materials Co., Ltd.) was subjected to shower development at 23 ° C. for 80 seconds and a flat nozzle pressure of 0.04 MPa to obtain a patterning image. Subsequently, ultrapure water was sprayed at a pressure of 9.8 MPa with an ultrahigh pressure washing nozzle to remove the residue, and a black (K) image K was obtained. Subsequently, heat treatment was performed at 220 ° C. for 30 minutes.

[Formation of red (R) pixels]
A heat-treated pixel R was formed in the same process as the formation of the black (K) image using a colored photosensitive resin composition R1 having the composition shown in Table 5 below on the substrate on which the image K was formed.
The film thickness of the photosensitive resin layer R1 and the coating amount of pigments (CIPR 254 and CIPR 177) are shown below.
Photosensitive resin film thickness (μm) 1.60
Pigment coating amount (g / m ² ) 1.00
C. I. P. R. 254 coating amount (g / m ² ) 0.80
C. I. P. R. 177 coating amount (g / m ² ) 0.20

[Formation of green (G) pixels]
Using the colored photosensitive resin composition G1 having the composition shown in Table 6 below on the substrate on which the image K and the pixel R are formed, the heat-treated pixel G is formed in the same process as the formation of the black (K) image. Formed. The film thickness of the photosensitive resin layer G1 and the coating amounts of pigments (CIPG36 and CIPY150) are shown below.
Photosensitive resin film thickness (μm) 1.60
Pigment application amount (g / m ² ) 1.92
C. I. P. G. 36 coating amount (g / m ² ) 1.34
C. I. P. Y. 150 coating amount (g / m ² ) 0.58

[Formation of blue (B) pixels]
A colored photosensitive resin composition B1 having the composition shown in Table 7 below is used on the substrate on which the image K, the pixel R, and the pixel G are formed, and is heat-treated in the same process as the formation of the black (K) image. Pixel B was formed, and the target color filter A was obtained.
The film thickness of the photosensitive resin layer B1 and the coating amounts of pigments (CIPB15: 6 and CIPVV23) are shown below.
Photosensitive resin film thickness (μm) 1.60
Pigment application amount (g / m ² ) 0.75
C. I. P. B. 15: 6 coating amount (g / m ² ) 0.705
C. I. P. V. 23 coating amount (g / m ² ) 0.045

Here, the preparation of the colored photosensitive resin compositions K1, R1, G1, and B1 described in Tables 4 to 7 will be described in more detail.
The colored photosensitive resin composition K1 is first weighed in the amounts of K pigment dispersion 1 and propylene glycol monomethyl ether acetate listed in Table 4, mixed at a temperature of 24 ° C. (± 2 ° C.), and stirred at 150 rpm for 10 minutes. Then, methyl ethyl ketone, binder 2, hydroquinone monomethyl ether, DPHA solution, 2,4-bis (trichloromethyl) -6- [4 '-(N, N-bisethoxycarbonylmethyl) amino- in the amounts shown in Table 4 3′-Bromophenyl] -s-triazine and Surfactant 1 are weighed out, added in this order at a temperature of 25 ° C. (± 2 ° C.), and stirred at a temperature of 40 ° C. (± 2 ° C.) at 150 rpm for 30 minutes. Obtained by

In addition, the composition was shown below about the following component among the compositions of Table 4.
<K pigment dispersion 1>
・ Carbon black (trade name: Nipex 35, manufactured by Degussa Japan Co., Ltd.)
13.1 parts by mass / dispersant (compound 2J below) 0.65 parts by mass / polymer (benzyl methacrylate / methacrylic acid = 72/28 molar ratio
Random copolymer of, molecular weight 37,000) 6.72 parts by mass / propylene glycol monomethyl ether acetate 79.53 parts by mass

<Binder 2>
・ Polymer (benzyl methacrylate / methacrylic acid = 78/22 molar ratio
Random copolymer, molecular weight 38,000) 27 parts by mass / propylene glycol monomethyl ether acetate 73 parts by mass

  The colored photosensitive resin composition R1 was first weighed in the amounts of R pigment dispersion A, R pigment dispersion 2, and propylene glycol monomethyl ether acetate shown in Table 5, and mixed at a temperature of 24 ° C. (± 2 ° C.). Stir at 150 rpm for 10 minutes, then the amounts of methyl ethyl ketone, binder 1, DPHA solution, 2-trichloromethyl-5- (p-styrylstyryl) -1,3,4-oxadiazole in the amounts listed in Table 5, 4-Bis (trichloromethyl) -6- [4 ′-(N, N-bisethoxycarbonylmethyl) amino-3′-bromophenyl] -s-triazine and phenothiazine are weighed out and the temperature is 24 ° C. (± 2 ° C.). Were added in this order and stirred at 150 rpm for 30 minutes, and the amount of surfactant 1 listed in Table 5 was weighed and added at a temperature of 24 ° C. (± 2 ° C.) for 30 r. Stirred for 5 minutes at m, it was obtained by filtering with a nylon mesh # 200.

Of the compositions shown in Table 5, the R pigment dispersion A was obtained in the same manner as the pigment dispersion composition A of Example 1, and was prepared such that the composition was the following parts by mass. Is.
<R pigment dispersion A>
-23 parts by mass of paste-like concentrated pigment liquid A (CIPR 254) of Example 1-0.8 parts by mass of dispersant (compound 2J)-Polymer (benzyl methacrylate / methacrylic acid = 72 / 28 molar ratio
Random copolymer, molecular weight 30,000) 8 parts by mass Propylene glycol monomethyl ether acetate 68.2 parts by mass <R pigment dispersion 2>
・ C. I. P. R. 177 (Product name: Chromophthal Red A2B,
Ciba Specialty Chemicals Co., Ltd.) 18 parts by mass Polymer (benzyl methacrylate / methacrylic acid = 72/28 molar ratio)
Random copolymer, molecular weight 30,000) 12 parts by mass / 70 parts by mass of propylene glycol monomethyl ether acetate

  The colored photosensitive resin composition G1 is first weighed in the amounts of G pigment dispersion 1, Y pigment dispersion 1, and propylene glycol monomethyl ether acetate in the amounts shown in Table 6, and mixed at a temperature of 24 ° C. (± 2 ° C.). Stir at 150 rpm for 10 minutes, then the amount of methyl ethyl ketone, cyclohexanone, binder 2, DPHA solution, 2-trichloromethyl-5- (p-styrylstyryl) -1,3,4-oxadiazole in the amounts listed in Table 6; 2,4-bis (trichloromethyl) -6- [4 ′-(N, N-bisethoxycarbonylmethyl) amino-3′-bromophenyl] -s-triazine and phenothiazine were weighed out and the temperature was 24 ° C. (± 2 And in this order, the mixture was stirred at 150 rpm for 30 minutes, and the surfactant 1 in the amount shown in Table 6 was weighed and the temperature was 24 ° C. (± 2 ° C.). In added and stirred for 5 minutes at 30 rpm, was obtained by filtering with a nylon mesh # 200.

  In addition, among the compositions described in Table 6, “trade name: GT-2” manufactured by FUJIFILM Electronics Materials Co., Ltd. was used as the G pigment dispersion 1. As the Y pigment dispersion 1, “trade name: CF erotic-EX3393” manufactured by Mikuni Color Co., Ltd. was used.

  The colored photosensitive resin composition B1 is first weighed out in amounts of B pigment dispersion 1, B pigment dispersion 2, and propylene glycol monomethyl ether acetate as shown in Table 7, and mixed at a temperature of 24 ° C. (± 2 ° C.). Stirred at 150 rpm for 10 minutes, then methyl ethyl ketone, binder 3, DPHA solution, 2-trichloromethyl-5- (p-styrylstyryl) -1,3,4-oxadiazole in the amounts listed in Table 2-5, The phenothiazine was weighed out and added in this order at a temperature of 25 ° C. (± 2 ° C.), stirred at a temperature of 40 ° C. (± 2 ° C.) for 30 minutes at 150 rpm, and the surfactants in the amounts shown in Table 2-5 1 was weighed out, added at a temperature of 24 ° C. (± 2 ° C.), stirred at 30 rpm for 5 minutes, and filtered through nylon mesh # 200.

  Of the compositions shown in Table 7, “Brand Name: CF Bull-EX3357” manufactured by Mikuni Color Co., Ltd. was used as the B pigment dispersion 1. As the B pigment dispersion 2, “trade name: CF Bull-EX3383” manufactured by Mikuni Color Co., Ltd. was used.

The composition of the binder 3 is as follows.
<Binder 3>
・ Polymer (benzyl methacrylate / methacrylic acid / methyl methacrylate = 36/22/42 molar ratio random copolymer, molecular weight 38,000) 27 parts by mass-propylene glycol monomethyl ether acetate 73 parts by mass

Instead of the concentrated pigment liquid A used in the R pigment dispersion A, the concentrated pigment liquids obtained in Examples 2 and 3 and Comparative Examples 1 to 3 (hereinafter simply referred to as “concentrated pigment liquids B to F”), respectively. R pigment dispersions B to F were prepared. Then, the color filters B to F were prepared in the same manner as the method for manufacturing the color filter A except that the R pigment dispersions B to F were used instead of the R pigment dispersion A, respectively.
Table 8 shows the results of measuring the contrast and light resistance of each color filter in the same manner as in [Measurement of contrast].

From the above results, it can be seen that the color filter of the present invention exhibits extremely high contrast and light resistance compared to the comparative example. If the color difference is different by 2 or more, it can be distinguished depending on the viewer. This difference is further enlarged by long-term use (for example, one year or more), and becomes a significant difference on the display screen. The color filters of the present invention were all good color filters with high contrast. On the other hand, the color filter of the comparative example has a low contrast and a level that does not satisfy practical requirements.
(Example 4-3)
[Production and Evaluation of Liquid Crystal Display]
A liquid crystal display device was produced using the color filters A to F, and the display characteristics were evaluated.
(Formation of ITO electrode)
The glass substrate on which the color filter is formed is put into a sputtering apparatus, and 1300 mm thick ITO (indium tin oxide) is vacuum-deposited on the entire surface at 100 ° C., and then annealed at 240 ° C. for 90 minutes to crystallize the ITO. A transparent electrode was formed.
(Spacer formation)
A spacer was formed on the ITO transparent electrode produced above by the same method as the spacer forming method described in [Example 1] of JP-A-2004-240335.
(Formation of liquid crystal alignment control protrusions)
A liquid crystal alignment control protrusion was formed on the ITO transparent electrode on which the spacer was formed, using the following positive photosensitive resin layer coating solution.
However, the following methods were used for exposure, development, and baking.
A proximity exposure machine (manufactured by Hitachi High-Tech Electronics Engineering Co., Ltd.) is arranged so that the predetermined photomask is at a distance of 100 μm from the surface of the photosensitive resin layer, and the irradiation energy is 150 mJ / Proximity exposure was performed at cm ² .
Subsequently, a 2.38% tetramethylammonium hydroxide aqueous solution was developed by spraying the substrate at 33 ° C. for 30 seconds on a shower type developing device. In this way, by removing the unnecessary portion (exposed portion) of the photosensitive resin layer by developing and removing the liquid crystal, the liquid crystal alignment control protrusions made of the photosensitive resin layer patterned into a desired shape are formed on the color filter side substrate. A display device substrate was obtained.
Next, the liquid crystal display device substrate on which the liquid crystal alignment control protrusions were formed was baked at 230 ° C. for 30 minutes to form cured liquid crystal alignment control protrusions on the liquid crystal display device substrate.
<Positive photosensitive resin layer coating formulation>
・ Positive resist solution (FUJIFILM Electronics
FH-2413F manufactured by Materials Co., Ltd.): 53.3 parts by mass / methyl ethyl ketone: 46.7 parts by mass / Megafac F-780F (manufactured by Dainippon Ink & Chemicals, Inc.): 0.04 parts by mass ( Creation of liquid crystal display device)
An alignment film made of polyimide was further provided on the liquid crystal display substrate obtained above.
After that, an epoxy resin sealant is printed at a position corresponding to a black matrix outer frame provided around the pixel group of the color filter, and MVA mode liquid crystal is dropped and bonded to the counter substrate. The bonded substrate was heat treated to cure the sealant. A polarizing plate HLC2-2518 manufactured by Sanritsu Co., Ltd. was attached to both surfaces of the liquid crystal cell thus obtained. Next, a backlight of a three-wavelength cold-cathode tube light source (FWL18EX-N manufactured by Toshiba Lighting & Technology Co., Ltd.) was constructed and placed on the back side of the liquid crystal cell provided with the polarizing plate to obtain a liquid crystal display device. .

  Compared to the liquid crystal display device using the color filter of the comparative example, the liquid crystal display device using the color filter of the present invention is excellent in blackness and red descriptive power and exhibits good display characteristics without display unevenness. confirmed.

(Example 5-1)
[Production of color filter (production by lamination of photosensitive resin transfer material)]
[Production of photosensitive resin transfer material]
On a 75 μm thick polyethylene terephthalate film temporary support, a coating solution for a thermoplastic resin layer having the following formulation H1 was applied and dried using a slit nozzle. Next, an intermediate layer coating solution having the following formulation P1 was applied and dried. Furthermore, the colored photosensitive resin composition K1 is applied and dried, and a thermoplastic resin layer having a dry film thickness of 14.6 μm, an intermediate layer having a dry film thickness of 1.6 μm, A photosensitive resin layer having a film thickness of 2.4 μm was provided, and a protective film (12 μm thick polypropylene film) was pressure-bonded.
Thus, a photosensitive resin transfer material K1 in which the temporary support, the thermoplastic resin layer, the intermediate layer (oxygen barrier film), and the black (K) photosensitive resin layer were integrated was produced.

<Coating liquid for thermoplastic resin layer: Formulation H1>
Methanol 11.1 parts by mass Propylene glycol monomethyl ether acetate 6.36 parts by mass Methyl ethyl ketone 52.4 parts by mass Methyl methacrylate / 2-ethylhexyl acrylate / benzyl
Methacrylate / methacrylic acid copolymer (copolymerization composition ratio (molar ratio) = 55 / 11.7 / 4.5 / 28.8,
Molecular weight: 90,000, Tg: about 70 ° C.) 5.83 parts by mass. Styrene / acrylic acid copolymer (copolymerization composition ratio (molar ratio))
= 63/37, molecular weight: 10,000, Tg: about 100 ° C.) 13.6 parts by mass. Compound obtained by dehydration condensation of 2 equivalents of bisphenol A and pentaethylene glycol monomethacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.,
Product name: 2,2-bis [4- (methacryloxypolyethoxy)
Phenyl] propane) 9.1 parts by mass / surfactant 1 0.54 parts by mass

<Intermediate layer coating solution: Formulation P1>
・ PVA205 (polyvinyl alcohol, manufactured by Kuraray Co., Ltd.,
Degree of saponification = 88%, degree of polymerization 550) 32.2 parts by mass / polyvinylpyrrolidone (manufactured by ASP Japan Co., Ltd.)
K-30) 14.9 parts by mass, 524 parts by mass of distilled water, 429 parts by mass of methanol

  Next, the colored photosensitive resin composition K1 used in the production of the photosensitive resin transfer material K1 is changed to the following colored photosensitive resin compositions R101, G101 and B101 having the compositions shown in Tables 9 to 11 below. Otherwise, photosensitive resin transfer materials R101, G101 and B101 were produced by the same method as described above. In addition, the preparation method of colored photosensitive resin composition R101, G101, and B101 is based on the preparation method of the said colored photosensitive resin composition R1, G1, and B1, respectively.

  In addition, among the compositions described in Table 9, the additive 1 used was a phosphate ester special activator (Takamoto Kasei Co., Ltd., trade name: HIPLAAD ED152).

[Formation of black (K) image]
The alkali-free glass substrate was washed with a rotating brush having nylon hair while spraying a glass detergent solution adjusted to 25 ° C. for 20 seconds by showering, and after washing with pure water shower, silane coupling solution (N-β (aminoethyl)) A 0.3% by mass aqueous solution of γ-aminopropyltrimethoxysilane, trade name: KBM603, manufactured by Shin-Etsu Chemical Co., Ltd.) was sprayed for 20 seconds with a shower, and washed with pure water. This substrate was heated at 100 ° C. for 2 minutes with a substrate preheating device and sent to the next laminator.
After peeling off the protective film of the photosensitive resin transfer material K1, a substrate heated to 100 ° C. using a laminator (manufactured by Hitachi Industries, Ltd. (Lamic II type)), a rubber roller temperature of 130 ° C., linear pressure Lamination was performed at 100 N / cm ² and a conveyance speed of 2.2 m / min.
After the temporary support is peeled off at the interface with the thermoplastic resin layer, the substrate and mask (quartz exposure mask with image pattern) are used with a proximity type exposure machine (manufactured by Hitachi High-Tech Electronics Engineering Co., Ltd.) having an ultra-high pressure mercury lamp. ) Was set vertically, the distance between the exposure mask surface and the thermoplastic resin layer was set to 200 μm, and pattern exposure was performed at an exposure amount of 70 mJ / cm ² .

Next, at 30 ° C. with a triethanolamine developer (containing 2.5% triethanolamine, nonionic surfactant, polypropylene antifoam, trade name: T-PD1, manufactured by Fuji Photo Film Co., Ltd.) The thermoplastic resin layer and the intermediate layer were removed by shower development for 50 seconds with a flat nozzle pressure of 0.04 MPa.
Subsequently, sodium carbonate developer (0.06 mol / liter sodium bicarbonate, sodium carbonate of the same concentration, 1% sodium dibutylnaphthalene sulfonate, anionic surfactant, antifoaming agent, stabilizer contained, trade name: T -CD1, manufactured by Fuji Photo Film Co., Ltd.), shower development was performed at 29 ° C. for 30 seconds and a cone type nozzle pressure of 0.15 MPa to develop the photosensitive resin layer to obtain a patterning image.
Continuing detergent (phosphate, silicate, nonionic surfactant, antifoam, stabilizer, trade name "T-SD1 (Fuji Photo Film)" or sodium carbonate / phenoxyoxyethylene surfactant Using a product name “T-SD2 (Fuji Photo Film Co., Ltd.)”), the residue is removed with a rotating brush having a shower and nylon hair at 33 ° C. for 20 seconds and a cone type nozzle pressure of 0.02 MPa. An image of K) was obtained. Thereafter, the substrate was further post-exposed with light of 500 mJ / cm ^{2 with} an ultrahigh pressure mercury lamp from the resin layer side, and then heat treated at 220 ° C. for 15 minutes.
The substrate on which this image K was formed was again cleaned with a brush as described above, and after pure water shower cleaning, the silane coupling solution was not used and was sent to a substrate preheating device.

[Formation of red (R) pixels]
Using the photosensitive resin transfer material R101, heat-treated red (R) pixels R were obtained in the same process as the photosensitive resin transfer material K1. However, the exposure amount was 40 mJ / cm ² , and development with a sodium carbonate developer was 35 ° C. for 35 seconds. The film thickness of the photosensitive resin layer R101 and the coating amount of pigments (CIPR 254 and CIPR 177) are shown below.
Photosensitive resin film thickness (μm) 2.00
Pigment coating amount (g / m ² ) 1.00
C. I. P. R. 254 coating amount (g / m ² ) 0.80
C. I. P. R. 177 coating amount (g / m ² ) 0.20
The substrate on which the image K and the pixel R were formed was again cleaned with a brush as described above, and after pure water shower cleaning, the silane coupling liquid was not used and the substrate was sent to a substrate preheating device.

[Formation of green (G) pixels]
Using the photosensitive resin transfer material G101, heat-treated green (G) pixels G were obtained in the same process as the photosensitive resin transfer material R101. However, the exposure amount was 40 mJ / cm ² , and development with a sodium carbonate developer was 34 ° C. and 45 seconds. The film thickness of the photosensitive resin layer G101 and the coating amounts of pigments (CIPG36 and CIPY150) are shown below.
Photosensitive resin film thickness (μm) 2.00
Pigment application amount (g / m ² ) 1.92
C. I. P. G. 36 coating amount (g / m ² ) 1.34
C. I. P. Y. 150 coating amount (g / m ² ) 0.58
The substrate on which the image K, the pixel R, and the pixel G were formed was again cleaned with a brush as described above, and after pure water shower cleaning, the silane coupling liquid was not used and the substrate was sent to a substrate preheating device.

[Formation of blue (B) pixels]
Using the photosensitive resin transfer material B101, heat-treated blue (B) pixels B were obtained in the same process as the photosensitive resin transfer material R101. However, the exposure amount was 30 mJ / cm ² , and development with a sodium carbonate developer was 36 ° C. for 40 seconds. The film thickness of the photosensitive resin layer B101 and the coating amounts of pigments (CIPB15: 6 and CIPVV23) are shown below.
Photosensitive resin film thickness (μm) 2.00
Pigment application amount (g / m ² ) 0.75
C. I. P. B. 15: 6 coating amount (g / m ² ) 0.705
C. I. P. V. 23 coating amount (g / m ² ) 0.045
The substrate on which the pixel R, the pixel G, the pixel B, and the image K were formed was baked at 240 ° C. for 50 minutes to obtain a color filter A1.

  The R pigment dispersion A was changed to R pigment dispersions B to F, respectively, to the above color filter A1 production method, and color filters B1 to F1 were produced.

When the same evaluation as in Example 4-2 was performed on the contrast and color difference of the obtained color filters A1 to F1, the effects of the present invention were similarly exhibited.
(Example 5-2)
[Production and Evaluation of Liquid Crystal Display]
When the liquid crystal display device was produced by using the color filters A1 to F1 in the same manner as in Example 4-3 and the display characteristics were evaluated, the effects of the present invention were similarly exhibited.
(Example 6)
[Production of liquid crystal display devices with different display methods]
In Examples 4-3 and 5-2, an MVA liquid crystal display device was manufactured, but a liquid crystal display device was also manufactured in the following method using the same color filter.

-Production of liquid crystal display device for PVA mode A transparent electrode of ITO (Indium Tin Oxide) was further formed by sputtering on the R pixel, G pixel, B pixel and black matrix of the color filter substrate obtained above. Next, according to Example 1 of Japanese Patent Application Laid-Open No. 2006-64921, a spacer was formed in a portion corresponding to the upper part of the black matrix on the ITO film formed as described above.
Separately, a glass substrate was prepared as a counter substrate, and patterning was performed for the PVA mode on the transparent electrode and the counter substrate of the color filter substrate, respectively, and an alignment film made of polyimide was further provided thereon.
After that, a UV curable resin sealant is applied by a dispenser method at a position corresponding to the outer periphery of the black matrix provided around the pixel group of the color filter, and a liquid crystal for PVA mode is dropped and attached to the counter substrate. After bonding, the bonded substrate was irradiated with UV, and then heat-treated to cure the sealant. A polarizing plate HLC2-2518 manufactured by Sanritsu Co., Ltd. was attached to both surfaces of the liquid crystal cell thus obtained. Next, FR1112H (chip type LED manufactured by Stanley Co., Ltd.) as a red (R) LED, DG1112H (chip type LED manufactured by Stanley Co., Ltd.) as a green (G) LED, and DB1112H (Stanley (as a blue (B) LED) A side light type backlight was constructed using a chip type LED manufactured by Co., Ltd., and was placed on the back side of the liquid crystal cell provided with the polarizing plate to obtain a liquid crystal display device. When the same evaluation as in Examples 4-3 and 5-2 was performed using this display device, the effects of the present invention were similarly exhibited.

-Production of liquid crystal display device for IPS mode A transparent electrode of ITO (Indium Tin Oxide) was further formed by sputtering on the R pixel, G pixel, B pixel and black matrix of the color filter substrate obtained above. Next, according to Example 1 of Japanese Patent Application Laid-Open No. 2006-64921, a spacer was formed in a portion corresponding to the upper part of the black matrix on the ITO film formed as described above.
Polyimide was applied to the color filter substrate with spacers obtained above and rubbed to form an alignment film.
Furthermore, a liquid crystal display element was produced by combining a drive side substrate and a liquid crystal material with the color filter substrate obtained above. That is, an IPS TFT substrate in which TFTs and comb-shaped pixel electrodes (conductive layers) are arrayed is prepared as a drive-side substrate, and the surface of the TFT substrate on which the pixel electrodes and the like are provided is obtained from the above. In addition, the color filter substrate was arranged so as to face the surface on the side where the colored pixel layer was formed, and fixed with a gap by the spacer formed as described above. A liquid crystal material was sealed in the gap to provide a liquid crystal layer for image display. A polarizing plate HLC2-2518 manufactured by Sanritsu Co., Ltd. was attached to both surfaces of the liquid crystal cell thus obtained. Next, a backlight of a cold cathode tube was constructed and placed on the back side of the liquid crystal cell provided with the polarizing plate to obtain a liquid crystal display device. When the same evaluation as in Examples 4-3 and 5-2 was performed using this display device, the effect of the present invention on the comparative example was exhibited in the same manner as described above, although the degree was smaller than that described above.

(Example 7)
[Production of CCD device]
(Preparation of pigment dispersion for CCD)
Pigment dispersion liquid (1)... Green G, (2)... Blue B, (3)... Red R using concentrated pigment liquid A obtained in Example 1 with the following formulation Was made.

Pigment dispersion (1) C.I. I. P. G. 36 90 parts by mass
・ C. I. P. G. 7 25 parts by mass
・ C. I. P. Y. 139 40 parts by mass
・ PLAAD ED151 20 parts by mass
(Enomoto Kasei Co., Ltd.)
・ 25 parts by mass of benzyl methacrylate / methacrylic acid copolymer
(Copolymerization molar ratio 70:30, mass average molecular weight 30,000)
・ Propylene glycol monomethyl ether acetate 625 parts by mass

(2)-C.I. I. P. B. 15: 6 125 parts by mass
・ C. I. P. V. 23 25 parts by mass
・ PLAAD ED151 40 parts by mass
(Enomoto Kasei Co., Ltd.)
・ 25 parts by mass of benzyl methacrylate / methacrylic acid copolymer
(Copolymerization molar ratio 70:30, mass average molecular weight 30,000)
-785 parts by mass of propylene glycol monomethyl ether acetate

(3) Concentrated pigment dispersion A 235 parts by mass
-Compound C-16 used in the present invention 40 parts by mass
・ 25 parts by mass of benzyl methacrylate / methacrylic acid copolymer
(Copolymerization molar ratio 70:30, mass average molecular weight 30,000)
・ 750 parts by mass of propylene glycol monomethyl ether acetate

(Preparation of colored resin composition)
The following composition was uniformly mixed with a stirrer for each 200 parts by mass of the pigment dispersion of each color obtained from the above to prepare a colored resin composition for a color filter for each color.
<Composition>
・ 35 parts by mass of benzyl acrylate / methacrylic acid copolymer (copolymerization molar ratio = 70/30, mass average molecular weight 30,000)
-38 parts by mass of dipentaerythritol pentaacrylate-120 parts by mass of propylene glycol monomethyl ether acetate-40 parts by mass of ethyl-3-ethoxypropionate-4 parts by mass of halomethyltriazine initiator (photopolymerization initiator product name TAZ107 Midori Chemical Co., Ltd.)

(Production of color filters and CCD devices)
The following composition was mixed with a stirrer to prepare a planarizing film resist solution.
〔composition〕
165 parts by mass of benzyl acrylate / methacrylic acid copolymer (copolymerization molar ratio = 70/30, mass average molecular weight 30,000)
・ 65 parts by mass of dipentaerythritol pentaacrylate
・ Propylene glycol monomethyl ether acetate 138 mass parts ・ Ethyl-3-ethoxypropionate 123 mass parts ・ Halomethyltriazine initiator 3 mass parts
(Photopolymerization initiator, product name: TAZ107, manufactured by Midori Chemical Co., Ltd.)
The obtained flattening resist solution was uniformly applied by spin coating onto a 6-inch silicon wafer on which photodiodes were formed. In spin coating, the coating rotation speed was adjusted so that the film thickness was about 1.5 μm when the surface temperature of the coating film was heated using a hot plate under the condition of 100 ° C. × 120 seconds after coating.
Then, it was placed in an oven at 220 ° C. for 1 hour to cure the coating film, and a planarizing film was formed so as to uniformly cover the surface of the photodiode formed on the silicon wafer.
Next, for each color, in order of G, R, and B, the above-described colored resin composition for color filter is applied onto the flattening film, and 100 parts by mass is applied to the flattening film resist solution preparation and dried (prebaked). Pattern exposure, alkali development, rinsing, and curing drying (post-baking) were performed to form a colored resin film, and a color filter was produced on a silicon wafer with a photodiode.

The pattern exposure was performed at 500 mJ / cm ² using an i-line stepper (trade name: FPA-3000i5 +, manufactured by Canon Inc.) through a 2 μm mask pattern.
Moreover, for alkali development, after performing paddle development for 60 seconds at room temperature using a 40 mass% aqueous solution of organic alkaline developer (trade name: CD-2000, manufactured by Fuji Film Electronics Materials Co., Ltd.), It rinsed with the pure water in the 20 second spin shower, and also washed with the pure water. Thereafter, water droplets were blown with high-temperature air, the substrate was naturally dried to obtain a pattern, and then post-baked on a hot plate at a surface temperature of 200 ° C. for 5 minutes.

When the CCD device obtained as described above was mounted on a digital camera and an image obtained by photographing a color chart with a KODAK gray scale under the same light source was observed on a monitor, a vivid reproduction image was obtained by the invention. .
(Example 8)
[Preparation of inkjet ink]
With reference to Example 1 of JP-A-2002-201387, R ink 1 was prepared using pigment dispersion composition A with the following formulation, and G ink 1 and B ink 1 were also prepared in the same manner.
Then, R inks 2 to 6 were produced in the same manner as the production method of R ink 1 except that pigment dispersion compositions B to F were used in place of the pigment dispersion composition A of R ink 1.

  Regarding the mixing of each component in Table 12, the pigment and the polymer dispersant were first charged and mixed in a part of the solvent, and stirred using a three roll and bead mill to obtain a pigment dispersion. On the other hand, other blending components were added to the remainder of the solvent, and dissolved and dispersed by stirring to obtain a binder solution. Then, the pigment dispersion was added little by little to the binder solution and sufficiently stirred with a dissolver to prepare an inkjet ink.

[Pixel formation]
The R ink 1, G ink 1, and B ink 1 obtained above were first ejected into a recess surrounded by a light-shielding partition as follows using a piezo type head. And the color filter 1 of this invention was obtained as follows.
The head has a nozzle density of 150 per 25.4 mm, and has 318 nozzles. By fixing these two nozzles in the nozzle row direction with a shift of 1/2 the nozzle interval, 25 heads are arranged on the substrate in the nozzle array direction. . 300 drops per 4 mm.
The head and ink are controlled so that the vicinity of the ejection portion is 50 ± 0.5 ° C. by circulating hot water in the head.
Ink ejection from the head is controlled by a piezo drive signal applied to the head, and ejection of 6 to 42 pl per drop is possible. In this embodiment, the head is moved while the glass substrate is conveyed at a position 1 mm below the head. More drops. The conveyance speed can be set in the range of 50 to 200 mm / s. The piezo drive frequency can be up to 4.6 KHz, and the droplet ejection amount can be controlled by these settings.

In this example, the transfer speed and drive frequency are controlled so that the coating amount of the pigment is 1.1, 1.8, and 0.75 g / m ^{2 for} each of R, G, and B. R, G, and B inks were ejected onto the recesses corresponding to G and B.
The ejected ink is conveyed to an exposure unit and exposed by an ultraviolet light emitting diode (UV-LED). In this example, NCCA033 manufactured by Nichia Corporation was used as the UV-LED. This LED outputs ultraviolet light having a wavelength of 365 nm from one chip. When a current of about 500 mA is applied, light of about 100 mW is emitted from the chip. A plurality of these are arranged at intervals of 7 mm, and a power of 0.3 W / cm ² can be obtained on the surface. The exposure time after the droplet ejection and the exposure time can be changed according to the transport speed of the medium and the distance between the head and the LED in the transport direction. In this example, after landing, the film was dried at 100 degrees for 10 minutes and then exposed.
Depending on the setting of the distance and the conveyance speed, the exposure energy on the medium can be adjusted between 0.01 and 15 J / cm ² . In this embodiment, the exposure energy is adjusted according to the conveyance speed.
For the measurement of the exposure power and exposure energy, a spectroradiometer URS-40D manufactured by USHIO INC. Was used, and a value obtained by integrating the wavelength between 220 nm and 400 nm was used.
The glass substrate after droplet ejection was baked in an oven at 230 ° C. for 30 minutes, so that both the light-shielding partition and each pixel were completely cured.

Then, color filters 2 to 6 were produced in the same manner as the production method for R ink 1 except that R inks 2 to 6 were used instead of R ink 1.
Table 13 below shows the results of measuring the contrast of each color filter in the same manner as [Measurement of contrast].

[Production of liquid crystal display devices]
A liquid crystal display device was produced using the produced color filters 1 to 6 and the display characteristics were evaluated.
(Formation of ITO electrode)
The glass substrate on which the color filter is formed is put into a sputtering apparatus, and 1300 mm thick ITO (indium tin oxide) is vacuum-deposited on the entire surface at 100 ° C., and then annealed at 240 ° C. for 90 minutes to crystallize the ITO. A transparent electrode was formed.
(Spacer formation)
A spacer was formed on the ITO transparent electrode produced above by the same method as the spacer forming method described in [Example 1] of JP-A-2004-240335.
(Formation of liquid crystal alignment control protrusions)
A liquid crystal alignment control protrusion was formed on the ITO transparent electrode on which the spacer was formed, using the following positive photosensitive resin layer coating solution.
However, the following methods were used for exposure, development, and baking.
A proximity exposure machine (manufactured by Hitachi High-Tech Electronics Engineering Co., Ltd.) is arranged so that the predetermined photomask is at a distance of 100 μm from the surface of the photosensitive resin layer, and the irradiation energy is 150 mJ / Proximity exposure was performed at cm ² .
Subsequently, a 2.38% tetramethylammonium hydroxide aqueous solution was developed by spraying the substrate at 33 ° C. for 30 seconds on a shower type developing device. In this way, by removing the unnecessary portion (exposed portion) of the photosensitive resin layer by developing and removing the liquid crystal, the liquid crystal alignment control protrusions made of the photosensitive resin layer patterned into a desired shape are formed on the color filter side substrate. A display device substrate was obtained.
Next, the liquid crystal display device substrate on which the liquid crystal alignment control protrusions were formed was baked at 230 ° C. for 30 minutes to form cured liquid crystal alignment control protrusions on the liquid crystal display device substrate.
<Positive photosensitive resin layer coating formulation>
・ Positive resist solution (FUJIFILM Electronics
FH-2413F manufactured by Materials Co., Ltd.): 53.3 parts by mass / methyl ethyl ketone: 46.7 parts by mass / Megafac F-780F (manufactured by Dainippon Ink & Chemicals, Inc.): 0.04 parts by mass ( Creation of liquid crystal display device)
An alignment film made of polyimide was further provided on the liquid crystal display substrate obtained above.
After that, an epoxy resin sealant is printed at a position corresponding to a black matrix outer frame provided around the pixel group of the color filter, and MVA mode liquid crystal is dropped and bonded to the counter substrate. The bonded substrate was heat treated to cure the sealant. A polarizing plate HLC2-2518 manufactured by Sanritsu Co., Ltd. was attached to both surfaces of the liquid crystal cell thus obtained. Next, a backlight of a three-wavelength cold-cathode tube light source (FWL18EX-N manufactured by Toshiba Lighting & Technology Co., Ltd.) was constructed and placed on the back side of the liquid crystal cell provided with the polarizing plate to obtain a liquid crystal display device. .
It was confirmed that the liquid crystal display device using the filter of the present invention was excellent in blackness and red descriptive power as compared with the comparative example.
From the above, it can be seen that the effect of the present invention is not only remarkable, but also has a greater effect by relatively simple means such as centrifugal separation conditions and enhanced drying in the production process.

It is sectional drawing which shows schematically the preferable embodiment of the manufacturing apparatus used for manufacture of the pigment dispersion composition of this invention. It is sectional drawing which shows schematically another preferable embodiment of the manufacturing apparatus used for manufacture of the pigment dispersion composition of this invention. FIG. 3 is an enlarged partial cross-sectional view schematically showing a mixing chamber in a partial cross section as one embodiment of the manufacturing apparatus of FIG. 2. FIG. 3 is an enlarged partial cross-sectional view schematically showing a mixing chamber in a partial cross section as another embodiment of the manufacturing apparatus of FIG. 2. It is sectional drawing which shows schematically another preferable embodiment of the manufacturing apparatus used for manufacture of the pigment dispersion composition of this invention. It is sectional drawing which shows schematically still another preferable embodiment of the manufacturing apparatus used for manufacture of the pigment dispersion composition of this invention. It is a front view which shows roughly an example of the dissolver stirring blade used for manufacture of the pigment dispersion composition of this invention. FIG. 8 is a drawing-substituting photograph of the dissolver stirring blade shown in FIG. 7. 1 schematically shows an example of a stirring unit composed of a rotatable turbine unit used for the production of the pigment dispersion composition of the present invention and a fixed stator unit positioned with a slight gap around the turbine unit. It is sectional drawing. It is explanatory drawing which shows one structural example of the ultrafiltration apparatus used for manufacture of the pigment dispersion composition of this invention.

Explanation of symbols

11 Container 11a Liquid tank (solvent)
11b Liquid level 12 Stirring blade 13 Mixing chamber 14 Supply pipe 14a Supply pipe opening 15 Shaft 16 Motor 17 Casing (mixing chamber wall)
18 holes (circular holes)
19a, 19b Stirring blade 21 Container (outer wall of stirring tank)
21a stirring tank 22 stirring blade 23 discharge pipe 24a, 24b supply pipe 25 shaft 50 stirring device 32, 33 supply port 36 discharge port 40 seal plate 41, 42 stirring blade 46 external magnet 48, 49 motor 61 disk part 62 blade 63 shaft 74 Rotating turbine section 75 Stabilized stator section 81 Container for storing dispersion 82 Circulating pump 83 Ultrafiltration module 84 Replenishment pure measurement flow meter 85 Permeate measurement flow meter 86 Backwash pump

Claims (13)

  A pigment dispersion composition comprising organic pigment nanoparticles and an organic solvent, wherein the proportion of particles having a primary particle size of less than 15 nm in the organic pigment nanoparticles is less than 10% (number%) and exceeds 60 nm The pigment dispersion composition is characterized by having a ratio of less than 10% (number%) and a water content of 0.01% by mass to 5% by mass.   2. The organic pigment nanoparticles are nanoparticles formed by mixing a solution in which an organic pigment is dissolved in a good solvent and a poor solvent for the organic pigment that is compatible with the solvent. The pigment dispersion composition described in 1.   The pigment dispersion composition according to claim 1 or 2, wherein the water content is 3% by mass or less.   The pigment dispersion composition according to claim 1 or 2, wherein the water content is 1% by mass or less. The pigment dispersion composition according to any one of claims 1 to 4, comprising a compound represented by the following general formula (1).

[Wherein, R ¹ represents a (m + n) -valent linking group, and R ² represents a single bond or a divalent linking group. A ¹ is an acidic group, a group having a basic nitrogen atom, a urea group, a urethane group, a group having a coordinating oxygen atom, a hydrocarbon group having 4 or more carbon atoms, an alkoxysilyl group, an epoxy group, an isocyanate group, and A monovalent organic group having a group selected from the group consisting of a hydroxyl group, or a monovalent organic group containing an organic dye structure or a heterocyclic ring which may have a substituent. However, n pieces of A ¹ may be the same as or different from each other. m represents a number of 1 to 8, n represents a number of 2 to 9, and m + n satisfies 3 to 10. P ¹ represents a polymer compound residue. ]   A pigment dispersion composition according to any one of claims 1 to 5, a polyfunctional monomer having two or more ethylenically unsaturated double bonds, and a photopolymerization initiator or a photopolymerization initiator system. A colored photosensitive resin composition characterized by the above.   A photosensitive resin transfer material, wherein a photosensitive resin layer containing at least the colored photosensitive resin composition according to claim 6 is provided on a temporary support.   An ink-jet ink comprising the pigment dispersion composition according to any one of claims 1 to 5.   The ink-jet ink according to claim 8, further comprising a monomer having two or more ethylenically unsaturated double bonds and used for producing a color filter.   A color filter produced using the colored photosensitive resin composition according to claim 6, the photosensitive resin transfer material according to claim 7, and / or the inkjet ink according to claim 9.   A liquid crystal display device comprising the color filter according to claim 10.   The liquid crystal display device according to claim 11, wherein the liquid crystal display device is a VA system.   A CCD device comprising the color filter according to claim 10.

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