JP2007262378A - Manufacturing method of organic nanoparticle, organic nanoparticle prepared thereby, colored photosensitive resin composition and photosensitive resin transfer material containing the same, and color filter and liquid crystal display using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a manufacturing method of organic nanoparticles; to provide a method for efficiently manufacturing in a dispersion liquid organic nanoparticles not causing cohesion and having high dispersion stability; to provide organic nanoparticles having a nanosize and a sharp peak in the particle size distribution, and a manufacturing method thereof; to provide a coloring photosensitive resin composition and a photosensitive resin transfer material using the above organic nanoparticles; and to provide a color filter and a display device using them, having high contrast and exhibiting excellent display characteristics. <P>SOLUTION: The manufacturing method of the organic nanoparticles wherein a dispersion liquid of organic nanoparticles is prepared by mixing a solution of an organic material dissolved in a good solvent and a solvent that is compatible with the above good solvent and makes a poor solvent to the above organic material and by allowing the organic material to be produced as fine particles having nanosizes, characterized in that a polymeric compound having a weight average mol.wt. of ≥1,000 is contained in the dispersion liquid. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a method for producing organic nanoparticles used in color filters and the like, and organic nanoparticles obtained thereby, and more specifically, a colored photosensitive composition, a photosensitive resin transfer material using the same, and use thereof. The present invention relates to a color filter and a liquid crystal display device.

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 possessed by 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 the pigment ink has an 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 monodispersity 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 that are monodisperse and stable at the nanometer size level.

  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 a 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 addition, in order to increase 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, refer to Patent Document 4). However, these methods do not satisfy the requirements because dispersion takes time and the viscosity increases.

In addition, an example in which dispersibility is improved using pigment particles prepared by the liquid phase method has been reported. Patent Document 5 describes an example in which a pigment particle aqueous dispersion is prepared by a liquid phase method. However, this method is a method of finally providing as an aqueous dispersion, and no mention is made of a method of providing as an organic solvent dispersion.
Patent Document 6 describes an example in which pigment particles prepared by a liquid phase method are used and provided as an organic solvent dispersion. In Patent Document 6, a pigment is precipitated by dissolving the pigment in a basic compound and / or a basic solution, and then adding a liquid neutral compound and / or an acidic compound, or a neutral liquid and / or an acidic liquid. Is described. However, the organic pigment particles obtained by this method have a large primary particle size, and have not fully met the demand for fine particles.

JP-A-11-237760 JP-A-6-79168 JP 2004-91560 A JP 2000-239554 A JP 2004-43776 A JP 2004-123853 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 method for producing organic nanoparticles, and also to provide a method for efficiently producing organic nanoparticles having high dispersion stability that do not cause aggregation in a dispersion. Furthermore, the present invention aims to provide organic nanoparticles having a nano size and a sharp particle size distribution peak, and a method for producing the same, and further, a colored photosensitive resin composition and a photosensitive resin transfer material using the organic nanoparticles described above. It is another object of the present invention to provide a color filter and a display device having high contrast and exhibiting excellent display characteristics.

The above problems have been achieved by the following means.
(1) A solution of an organic material dissolved in a good solvent and a solvent compatible with the good solvent and a poor solvent for the organic material are mixed to form the organic material as nano-sized fine particles. A method for producing organic nanoparticles, characterized in that a polymer compound having a weight average molecular weight of 1000 or more is contained in the dispersion when preparing a dispersion of organic nanoparticles to be produced.
(2) The method for producing organic nanoparticles according to (1), wherein the dispersion is concentrated.
(3) The method for producing organic nanoparticles according to (1) or (2), wherein the solvent in the dispersion is removed.
(4) The method for producing organic nanoparticles according to any one of (1) to (3), wherein the nanoparticles in the dispersion liquid are redispersible flocs.
(5) The method for producing organic nanoparticles according to any one of (1) to (4), wherein the polymer compound is represented by the following general formula (1).

〔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、ｎは２〜９の数を表し、ｍ＋ｎは３〜１０を満たす。Ｐ^１は高分子骨格を表す。〕
（６）前記高分子化合物が下記一般式（２）で表されることを特徴とする（１）〜（５）のいずれか１項に記載の有機ナノ粒子の製造方法。

[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 from 1 to 8, n represents a number from 2 to 9, and m + n satisfies 3 to 10. P ¹ represents a polymer backbone. ]
(6) The method for producing organic nanoparticles according to any one of (1) to (5), wherein the polymer compound is represented by the following general formula (2).

〔式中、Ｒ^３は、（ｘ＋ｙ）価の連結基を表す。Ｒ^４およびＲ^５は、各々独立に単結合または２価の連結基を表す。Ａ^２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、ｘ個のＡ^２は互いに同一であっても、異なっていてもよい。ｙは１〜８の数を表し、ｘは２〜９の数を表し、ｘ＋ｙは３〜１０を満たす。Ｐ^２は高分子骨格を表す。〕
（７）前記Ａ^１または前記Ａ^２が、酸性基、塩基性窒素原子を有する基、ウレア基、および炭素数４以上の炭化水素基からなる群より選ばれる基を有する１価の有機基であることを特徴とする（５）または（６）に記載の有機ナノ粒子の製造方法。
（８）前記Ｐ^１または前記Ｐ^２で表される高分子骨格が、ビニルモノマーの重合体もしくは共重合体、エステル化合物ポリマー、エーテル化合物ポリマー、ウレタン化合物ポリマー、アミド化合物ポリマー、エポキシ化合物ポリマー、シリコーン化合物ポリマー、並ぶにこれらの変性物及び共重合体からなる群より選ばれる少なくとも一種に由来するものであることを特徴とする（５）〜（７）のいずれか１項に記載の有機ナノ粒子の製造方法。
（９）前記高分子化合物が、酸性基を有する高分子化合物であることを特徴とする（１）〜（８）のいずれか１項に記載の有機ナノ粒子の製造方法。
（１０）前記高分子化合物の酸性基が、カルボキシル基であることを特徴とする（９）に記載の有機ナノ粒子の製造方法。
（１１）前記高分子化合物の重量平均分子量が３０００〜１０００００であることを特徴とする（１）〜（１０）のいずれか１項に記載の有機ナノ粒子の製造方法。
（１２）前記有機ナノ粒子を含有する分散液を調製するに当り、いずれかの工程でアミノ基を有する顔料分散剤を共存させることを特徴とする（１）〜（１１）のいずれか１項に記載の有機ナノ粒子の製造方法。
（１３）前記有機ナノ粒子を含有する分散液を調製するに当り、一般式（Ｄ１）、（Ｄ３）、および式（Ｄ４）のいずれかで表される化合物の少なくとも１種を含有させることを特徴とする（１）〜（１２）のいずれか１項に記載の有機ナノ粒子の製造方法。

[Wherein R ³ represents a (x + y) -valent linking group. R ⁴ and R ⁵ each independently represents a single bond or a divalent linking group. A ² 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, x A ² may be the same or different. y represents a number of 1 to 8, x represents a number of 2 to 9, and x + y satisfies 3 to 10. P ² represents a polymer skeleton. ]
(7) The A ¹ or the A ² is a monovalent organic group having a group selected from the group consisting of an acidic group, a group having a basic nitrogen atom, a urea group, and a hydrocarbon group having 4 or more carbon atoms. The method for producing organic nanoparticles according to (5) or (6), which is characterized in that it exists.
(8) The polymer skeleton represented by P ¹ or P ² is a polymer or copolymer of vinyl monomer, ester compound polymer, ether compound polymer, urethane compound polymer, amide compound polymer, epoxy compound polymer, silicone The organic nanoparticle according to any one of (5) to (7), wherein the organic nanoparticle is derived from at least one selected from the group consisting of a compound polymer and a modified product and a copolymer thereof Manufacturing method.
(9) The method for producing organic nanoparticles according to any one of (1) to (8), wherein the polymer compound is a polymer compound having an acidic group.
(10) The method for producing organic nanoparticles according to (9), wherein the acidic group of the polymer compound is a carboxyl group.
(11) The method for producing organic nanoparticles according to any one of (1) to (10), wherein the polymer compound has a weight average molecular weight of 3000 to 100,000.
(12) In preparing the dispersion containing the organic nanoparticles, any one of (1) to (11), wherein a pigment dispersant having an amino group is allowed to coexist in any step. The manufacturing method of the organic nanoparticle of description.
(13) In preparing the dispersion liquid containing the organic nanoparticles, the dispersion liquid contains at least one compound represented by any one of the general formulas (D1), (D3), and (D4). The method for producing organic nanoparticles according to any one of (1) to (12), which is characterized.

（一般式（Ｉ）中、Ａは、Ｘ−Ｙとともにアゾ色素を形成しうる成分を表す。Ｘは単結合又は下記式（ｉ）〜（ｖ）の構造式のいずれかで表される二価の連結基から選択される基を表す。Ｙは下記一般式（Ｄ２）で表される基を表し、あるいはｎが１の場合−ＮＨ−Ｘ_１−Ｑでもよい。）

(In general formula (I), A represents a component capable of forming an azo dye together with X—Y. X represents a single bond or a structural formula represented by any of the following formulas (i) to (v). Represents a group selected from a valent linking group, Y represents a group represented by the following general formula (D2), or when n is 1, it may be —NH—X ₁ -Q.

（一般式（Ｄ２）中、Ｚは低級アルキレン基を表す。−ＮＲ_２１は、低級アルキルアミノ基又は窒素原子を含む５乃至６員飽和ヘテロ環を表す。ａは１又は２を表す。）

(In General Formula (D2), Z represents a lower alkylene group. —NR ₂₁ represents a lower alkylamino group or a 5- to 6-membered saturated heterocyclic ring containing a nitrogen atom. A represents 1 or 2.)

（一般式（Ｄ３）中、Ｑはアントラキノン化合物色素、アゾ化合物色素、フタロシアニン化合物色素、キナクリドン化合物色素、ジオキサジン化合物色素、アントラピリミジン化合物色素、アンサンスロン化合物色素、インダンスロン化合物色素、フラバンスロン化合物色素、ピランスロン化合物色素、ペリノン化合物色素、ペリレン化合物色素、及びチオインジゴ化合物色素から選ばれる有機色素残基を表す。Ｘ_１は−ＣＯＮＨ−Ｙ_２−、−ＳＯ_２ＮＨ−Ｙ_２−、又は−ＣＨ_２ＮＨＣＯＣＨ_２ＮＨ−Ｙ_２−を表し、Ｙ_２は置換基を有してもよいアルキレン基又はアリーレン基を表す。Ｒ_１１およびＲ_１２はそれぞれ独立に置換もしくは無置換のアルキル基またはＲ_１１とＲ_１２とで少なくとも窒素原子を含むヘテロ環を形成してもよい。Ｙ_１は−ＮＨ−又は−Ｏ−を表し、Ｚ_１は水酸基又は一般式（Ｄ３ａ）で表される基を表し、あるいはｎ１が１の場合−ＮＨ−Ｘ_１−Ｑでもよい。ｍ１は１〜６の整数を表し、ｎ１は１〜４の整数を表す。）

(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 , An organic dye residue selected from a pyranthrone compound dye, a perinone compound dye, a perylene compound dye, and a thioindigo compound dye, wherein X ₁ is —CONH—Y ₂ —, —SO ₂ NH—Y ₂ —, or —CH _2. NH ₂ represents NHCOCH ₂ NH—Y ₂ —, Y ₂ represents an alkylene group or an arylene group which may have a substituent, and R ₁₁ and R ₁₂ are each independently a substituted or unsubstituted alkyl group or R ₁₁ and R heterocycle to form containing at least nitrogen atom at the ₁₂ Which may .Y ₁ represents -NH- or -O-, _{Z 1} represents a group represented by a hydroxyl group or formula (D3a), or n1 is good even if _-NH-X 1 -Q 1. m1 represents an integer of 1 to 6, and n1 represents an integer of 1 to 4.)

（一般式（Ｄ３ａ）中、Ｙ_３は−ＮＨ−又は−Ｏ−を表し、ｍ１、Ｒ_１１、およびＲ_１２は一般式（Ｄ３）と同じである。）

(In General Formula (D3a), Y ₃ represents —NH— or —O—, and m 1, R ₁₁ , and R ₁₂ are the same as in General Formula (D3).)

（式（Ｄ４）中、Ｍｅメチル基を表す。）
（１４）前記有機材料の貧溶媒が、水性溶媒、アルコール化合物溶媒、ケトン化合物溶媒、エーテル化合物溶媒、エステル化合物溶媒、またはこれらの混合物であることを特徴とする（１）〜（１３）のいずれか１項に記載の有機ナノ粒子の製造方法。
（１５）前記有機材料の良溶媒が、水性溶媒、アルコール化合物溶媒、ケトン化合物溶媒、エーテル化合物溶媒、スルホキシド化合物溶媒、エステル化合物溶媒、アミド化合物溶媒、またはこれらの混合物であることを特徴とする（１）〜（１４）のいずれか１項に記載の有機ナノ粒子の製造方法。
（１６）前記有機ナノ粒子の分散液を調製するに当り、前記有機材料溶液と貧溶媒とを混合して有機ナノ粒子を生成させ、これを濃縮した後、前記高分子化合物を添加することを特徴とする（１）〜（１５）のいずれか１項に記載の有機ナノ粒子の製造方法。
（１７）前記有機材料が、有機顔料であることを特徴とする（１）〜（１６）のいずれか１項に記載の有機ナノ粒子の製造方法。
（１８）前記有機顔料がピロロピロール化合物顔料であることを特徴とする（１７）に記載の有機ナノ粒子の製造方法。
（１９）前記ピロロピロール化合物顔料が下記式（Ｖ）で表される顔料であることを特徴とする（１８）に記載の有機ナノ粒子の製造方法。

(In formula (D4), Me represents a methyl group.)
(14) The poor solvent of the organic material is an aqueous solvent, an alcohol compound solvent, a ketone compound solvent, an ether compound solvent, an ester compound solvent, or a mixture thereof, any one of (1) to (13) The manufacturing method of the organic nanoparticle of Claim 1.
(15) The good solvent of the organic material is an aqueous solvent, an alcohol compound solvent, a ketone compound solvent, an ether compound solvent, a sulfoxide compound solvent, an ester compound solvent, an amide compound solvent, or a mixture thereof ( The manufacturing method of the organic nanoparticle of any one of 1)-(14).
(16) In preparing the dispersion of the organic nanoparticles, the organic material solution and the poor solvent are mixed to form organic nanoparticles, and after the concentration, the polymer compound is added. The method for producing organic nanoparticles according to any one of (1) to (15), which is characterized.
(17) The method for producing organic nanoparticles according to any one of (1) to (16), wherein the organic material is an organic pigment.
(18) The method for producing organic nanoparticles according to (17), wherein the organic pigment is a pyrrolopyrrole compound pigment.
(19) The method for producing organic nanoparticles according to (18), wherein the pyrrolopyrrole compound pigment is a pigment represented by the following formula (V).

（２０）前記ピロロピロール化合物顔料が下記式（Ｚ）で表される顔料であることを特徴とする（１８）に記載の有機ナノ粒子の製造方法。

(20) The method for producing organic nanoparticles according to (18), wherein the pyrrolopyrrole compound pigment is a pigment represented by the following formula (Z).

（２１）前記ピロロピロール化合物顔料が下記式（Ｗ）で表される顔料であることを特徴とする（１８）に記載の有機ナノ粒子の製造方法。

(21) The method for producing organic nanoparticles according to (18), wherein the pyrrolopyrrole compound pigment is a pigment represented by the following formula (W).

（２２）前記有機顔料がジオキサジン化合物顔料であることを特徴とする（１７）に記載の有機ナノ粒子の製造方法。
（２３）前記ジオキサジン化合物顔料がＣ．Ｉ．ピグメント・バイオレット３７である（２０）に記載の有機ナノ粒子の製造方法。
（２４）前記ジオキサジン化合物顔料がＣ．Ｉ．ピグメント・バイオレット２３である（２２）に記載の有機ナノ粒子の製造方法。
（２５）前記有機材料溶液と貧溶媒とを混合して有機ナノ粒子を生成させるに当り、前記貧溶媒の混合量が１０Ｌ以上のスケールでナノ粒子を生成させることを特徴とする（１）〜（２４）のいずれか１項に記載の有機ナノ粒子の製造方法。
（２６）（１）〜（２５）のいずれか１項に記載の方法で製造された有機ナノ粒子。
（２７）（２６）に記載の有機ナノ粒子と、バインダーと、モノマーもしくはオリゴマーと、光重合開始剤もしくは光重合開始剤系とを少なくとも含む着色感光性樹脂組成物。
（２８）仮支持体上に、少なくとも、（２７）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。
（２９）（２７）に記載の着色感光性樹脂組成物及び／又は（２８）に記載の感光性樹脂転写材料を用いたことを特徴とするカラーフィルタ。
（３０）（２９）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。

(22) The method for producing organic nanoparticles according to (17), wherein the organic pigment is a dioxazine compound pigment.
(23) The dioxazine compound pigment is C.I. I. The method for producing organic nanoparticles according to (20), which is CI Pigment Violet 37.
(24) The dioxazine compound pigment is C.I. I. The method for producing organic nanoparticles according to (22), which is CI Pigment Violet 23.
(25) When the organic material solution and the poor solvent are mixed to generate organic nanoparticles, the mixed amount of the poor solvent generates nanoparticles on a scale of 10 L or more (1) to The method for producing organic nanoparticles according to any one of (24).
(26) Organic nanoparticles produced by the method according to any one of (1) to (25).
(27) A colored photosensitive resin composition comprising at least the organic nanoparticles according to (26), a binder, a monomer or an oligomer, and a photopolymerization initiator or a photopolymerization initiator system.
(28) A photosensitive resin transfer material, wherein a photosensitive resin layer containing at least the colored photosensitive resin composition according to (27) is provided on a temporary support.
(29) A color filter using the colored photosensitive resin composition according to (27) and / or the photosensitive resin transfer material according to (28).
(30) A liquid crystal display device comprising the color filter according to (29).

  According to the production method of the present invention, it is possible to efficiently obtain organic nanoparticles miniaturized to a nanometer size, and further to obtain organic nanoparticles having a nano size and high monodispersity. Further, according to the production method of the present invention, when preparing an organic particle dispersion by reprecipitation, it is possible to obtain nanoparticles by concentrating as necessary. Organic nanoparticles that can be well dispersed can be obtained. Furthermore, according to the production method of the present invention, organic nanoparticles suitable for color filter coating liquids and inkjet inks and dispersions thereof can be produced on an industrial scale. In addition, the color filter using the organic nanoparticles of the present invention has the desired color purity and high contrast, is excellent in weather resistance, and its liquid crystal display device is black and has good reproducibility and improved display unevenness. There is an excellent effect of being able to.

Hereinafter, the manufacturing method of the organic nanoparticle of this invention is demonstrated.
[Organic materials]
The organic material used in the method for producing organic nanoparticles of the present invention is not particularly limited as long as particles can be formed by a reprecipitation method. For example, polymers such as organic pigments, organic dyes, fullerenes, polydiacetylenes, and polyimides are used. Examples include particles made of organic materials, aromatic hydrocarbons or aliphatic hydrocarbons (for example, oriented aromatic hydrocarbons or aliphatic hydrocarbons, or sublimable aromatic hydrocarbons or aliphatic hydrocarbons). Organic pigments, organic dyes or polymeric organic materials are preferred, and organic pigments are particularly preferred. Further, the organic particles may be used alone, or a plurality of organic particles may be used in combination.

  The organic pigment is not limited in terms of hue. , 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 typified 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 No. 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 production method of 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 production method 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 method for producing organic nanoparticles 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.

[Generation of organic particles]
Next, a method for generating organic particles will be described.
In the present invention, the organic nanoparticles are an organic material solution in which an organic material is dissolved in a good solvent, a solvent that is compatible with the good solvent and a poor solvent for the organic material (hereinafter referred to as this solvent). The solvent is also referred to as [poor solvent of organic material], or simply [poor solvent].) (Hereinafter referred to as “reprecipitation method”). The resulting dispersion containing organic nanoparticles is sometimes referred to as “organic particle reprecipitation liquid”.
The poor solvent for the organic material is not particularly limited as long as it is compatible with or uniformly mixed with a good solvent for dissolving the organic material. As a poor solvent for the organic material, the solubility of the organic material 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 material in the poor solvent, 0.000001% by mass or more is practical in consideration of a commonly used organic material. 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 aqueous solvents (for example, water or hydrochloric acid, aqueous sodium hydroxide), alcohol compound solvents, ketone compound solvents, ether compound solvents, aromatic compound solvents, carbon disulfide solvents, aliphatic compound solvents, 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 that dissolves the organic material will be described.
The good solvent is not particularly limited as long as it can dissolve the organic material to be used and is compatible with or uniformly mixed with the poor solvent. The solubility of the organic material in a good solvent is such that the solubility of the organic material 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 material in the good solvent, it is practical that it is 50% by mass or less in consideration of a commonly used organic material. 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 material solution in which the organic material is dissolved in the good solvent is preferably a saturated concentration of the organic material with respect to the good solvent in the dissolution condition or a range of about 1/100 of this.
The conditions for preparing the organic material solution are not particularly limited, 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 material must be uniformly dissolved in a good solvent, but it is also preferable that the organic material be dissolved 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 relative to the organic material, more preferably 1 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, more preferably 5.0 to 100 molar equivalents, still more preferably 20 to 100 molar equivalents relative to the organic material.

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 material, and is not particularly limited. Regardless of inorganic acid or organic acid, it is preferably 3 to 500 molar equivalents, more preferably 10 to 500 molar equivalents, still more preferably 30 to 200 molar equivalents relative to the organic material.

  When mixing an alkali or acid with an organic solvent and using it as a good solvent for an organic material, the solvent has a 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 material 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 material solution and the poor solvent, either of them may be added and mixed, but it is preferable to add the organic material solution to the poor solvent and mix, and the poor solvent is stirred at that time. It is preferable to be in the state. 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 volume ratio of the mixing ratio of the organic material solution and the poor solvent (good solvent / poor solvent ratio in the organic particle reprecipitation liquid) is preferably 1/50 to 2/3, more preferably 1/40 to 1/2. / 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 particles are preferably in the range of 10 to 40000 mg, more preferably in the range of 20 to 30000 mg with respect to 1000 ml of the dispersion solvent. Yes, particularly preferably in the range of 50 to 25000 mg.
Moreover, the preparation scale at the time of producing | generating an organic nanoparticle is although it does not specifically limit, It is preferable that the mixing amount of a poor solvent is a 10-2000L preparation scale, and it is more preferable that it is a 50-1000L preparation scale.

Regarding the particle size of organic particles, there is a method of expressing the average size of the population by quantifying by a measurement method, but the mode diameter indicating the maximum value of the distribution and the median value of the integral distribution curve are often used Median diameter, various average diameters (number average, length average, area average, weight average, volume average, etc.), etc. in the present invention, unless otherwise specified, the average particle diameter is the number average. The diameter. The average particle size of the organic particles (primary particles) is nanometer size, the average particle size is preferably 1 nm to 1 μm, more preferably 1 to 200 nm, further preferably 2 to 100 nm, A thickness of 5 to 80 nm is particularly preferable. The particles formed by the production method 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 organic particle concentration method, that is, Mv / Mn, is preferably 1.0 to 2.0, and 1.0 to 1. 8 is more preferable, and 1.0 to 1.5 is particularly preferable.
Examples of the method for measuring the particle size of organic particles include microscopy, gravimetric method, light scattering method, light blocking method, electrical resistance method, acoustic method, and dynamic light scattering method. 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.

[Dispersant]
In the method for producing organic nanoparticles of the present invention, it is preferable to contain a dispersant when preparing the organic nanoparticle dispersion. The step of containing the dispersant is not particularly limited, but it is preferable to add the dispersant to the organic material solution and / or 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.

  In the production method of the present invention, when preparing an organic material solution dissolved in a good solvent, it is preferable to coexist a pigment dispersant containing an amino group. 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 production method of the present invention is not limited thereto, but is selected from the compounds represented by the following general formulas (D1), (D3), and (D4). 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, pyranthrone compound dye, perinone compound It represents an organic dye residue selected from a dye, a perylene compound dye, and a thioindigo compound dye. Among them, an azo compound dye or a dioxazine compound dye is preferable, and an azo compound dye is more preferable.
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.

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 organic nanoparticles 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.
As a weight average molecular weight (Mw) of the said graft copolymer, 3000-100000 are preferable and 5000-50000 are more preferable. When the weight average molecular weight (Mw) is less than 3000, aggregation of the organic nanoparticles cannot be prevented, and the viscosity may increase. , The viscosity may increase. The weight average molecular weight is a polystyrene equivalent weight 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 the 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 is 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, 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 (3), 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 (4), 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 Suitable 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 alkyl aryl 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 weight% is preferable, for example. When the content is less than 5% by weight, the physical properties of the coating film may not be controlled, and when it exceeds 70% by weight, 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.

  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 mass, more preferably 100 parts by mass of the organic particles. Is in the range of 1 to 500 parts by weight, more preferably in the range of 5 to 20 parts by weight. If the amount is less than 0.1 parts by mass, the dispersion stability of the organic nanoparticles may not be improved.

[Manufacturing equipment]
In the production method of the present invention, a preferred embodiment of the production apparatus used for forming the organic nanoparticles will be described, but the present invention is not construed as being limited thereto.

(Manufacturing device example 1)
FIG. 1-1 is a schematic view of a production apparatus used as an embodiment in the production method 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. 1-2 is a schematic view of a production apparatus used as another more preferable embodiment of the present invention. In the production apparatus of FIG. 1-1, a mixing chamber (stirring region) 13 is provided in a container 11. 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).

  1-3 is an enlarged partial cross-sectional view schematically showing the mixing chamber 13 in an enlarged manner as an embodiment of the manufacturing apparatus of FIG. 1-2. 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 when exposed 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.

  1-4 is an enlarged partial cross-sectional view of a mixer having two stirring blades (mixing stirring blade 19a and discharging stirring blade 19b) in the mixing chamber as another embodiment of the manufacturing apparatus of FIG. 1-2. is there. 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. 2 is a cross-sectional view schematically showing another embodiment of the production apparatus used in the production method of the present invention. In FIG. 2, 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. 3 is a sectional view schematically showing still another embodiment of the apparatus used in the production method of the present invention. In the manufacturing apparatus of FIG. 3, the stirring device 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.

A pair of stirring blades 41 and 42 arranged opposite to each other in the tank 38 allows the stirring flows having different directions to flow into the tank 38 as indicated by the wavy arrow (X) and the solid 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 method of the present invention, the production apparatus having these configurations can be used to produce organic nanoparticles not only in a batch method but also in a continuous flow method, 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 a device used in the production method 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 section that can be used in the present invention is not particularly limited as long as it can be subjected to a high shearing 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. 4-1, and a drawing substitute photograph is shown in FIG. 4-2.
Further, an apparatus having a stirring unit composed of a rotatable turbine unit as shown in FIG. 5 and a fixed stator unit positioned with a slight gap around the turbine unit 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 organic nanoparticles of the present invention, it is possible to produce a concentrated solution suitable for color filter coating liquid and ink-jet ink on an industrial scale by desalting and concentrating the organic nanoparticle dispersion liquid. It is.
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 make a concentrated nanoparticle solution, the organic nanoparticle is precipitated and concentrated by centrifugation, the salt is concentrated by ultrafiltration, and the solvent is sublimated by vacuum freeze-drying. A method of concentrating, a method of drying and concentrating the solvent by heating or reduced pressure, and the like are preferable. Or a combination thereof is very preferably used.
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.

Hereinafter, a method of concentration extraction will be described.
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. 6 shows a configuration example of an apparatus for performing ultrafiltration. As shown in FIG. 6, 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 isolate | separate the dispersion | distribution solvent and concentrated extract of organic nanoparticle dispersion liquid, it is preferable to filter-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 lyophilized 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, monocooling 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.
[Fine dispersion]
According to the production method of the present invention, the organic particles in an agglomerated state can be finely dispersed, for example, by concentration or the like, if necessary (in the present invention, fine dispersion means the particles in the dispersion liquid). It means to release the agglomeration and increase the degree of 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, the aggregated organic particle means an aggregate of organic particles such as an aggregate 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 weight 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 substance containing the agglomerated organic particles in the liquid, and even if it is a dispersion, a concentrated liquid, a paste, a slurry, etc., the agglomerated organic particles are included. Good.)

Next, a polymer compound used in the method for producing organic nanoparticles of the present invention (in the present invention, “polymer compound” refers to an organic compound having a weight average molecular weight of 1000 or more, and there is no particular upper limit, but a weight average molecular weight of 300 It is practical that it is 1,000 or less, preferably 100,000 or less, more preferably 50,000 or less.).
The polymer compound used in the method for producing organic nanoparticles of the present invention has a weight 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. It represents 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. .

  Further, the organic dye structure or the 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.

Among the above, when having a substituent R ¹⁸ , 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. Aryl group, hydroxyl group, amino group, carboxyl group, sulfonamido group, N-sulfonylamido group, acetoxy group and the like, such as acyloxy group having 1 to 6 carbon atoms, methoxy group, ethoxy group and the like having 1 to 6 carbon atoms 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. Is mentioned.

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, 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 sulfonamido group, an N-sulfonylamido group and an acetoxy group, a methoxy group and an ethoxy group An alkoxy group of 2 to 7 carbon atoms such as a methoxycarbonyl group, an ethoxycarbonyl group, a cyclohexyloxycarbonyl group, a cyano group, a carbonate ester group such as 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 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 polymer or copolymer of vinyl monomers, ester polymers, ether polymers, urethane polymers, amide polymers, epoxy polymers, silicone polymers, and these Modified product or copolymer [eg, 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 or copolymers thereof. At least one kind is more preferable, and a polymer or copolymer of vinyl monomers is particularly preferable.
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. 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 these, (r1), (r2), (r-10), (r-11), (r-16) from the viewpoints of availability of raw materials, ease of synthesis, and solubility in various solvents. , (R-17) is 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 An alkoxy group of 2 to 7 carbon atoms such as a methoxycarbonyl group, an ethoxycarbonyl group, a cyclohexyloxycarbonyl group, a cyano group, a carbonate ester group such as 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 preferred.

Examples of R ⁵ include 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.

  Although the weight average molecular weight of the polymer compound used in the production method of the present invention is 1000 or more, the weight average molecular weight is preferably 3000 to 100,000, more preferably 5000 to 80000, and particularly preferably 7000 to 60000. When the weight average molecular weight is within the above range, the effects of the multiple functional groups introduced at the polymer ends are fully exhibited, and the performance of adsorbing to the 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 production method of the present invention is synthesized, for example, by any one of the above methods 2, 3, 4, and 5. However, from the viewpoint of ease of synthesis, it is more preferable to synthesize by the above method 5.

  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 each represented by the general formula (
It is synonymous with R < ³ >, R < ⁴ >, A < ² >, x, and y in 2), The preferable aspect 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 include methylstyrene, hydroxystyrene protected with a group that can be deprotected 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 polymerization is performed 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" [specific examples (18) to (34)] include the following compounds.

  Among these, (u-18), (u-19), (u-27), (u-28), (u) from the viewpoint of availability of raw materials, ease of synthesis, and solubility in various solvents. -33) and (u-34) 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 production method 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。Ｘ１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, X1 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。Ｙ１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、重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重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. Y 1 represents 1 Represents a number of ~ 5.)
Further, in terms of the polymerization ratio of the repeating unit derived from the compound having (A) a carboxyl group and the repeating unit derived from the compound having the (B) carboxylic ester group, all of the repeating units (A) can be obtained. The quantity ratio% to the number of repeating units is preferably 3 to 40, more preferably 5 to 35.
In the production method of the present invention, the molecular weight of the polymer means a weight 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 weight 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 in a solution in an aqueous solvent or an organic solvent, in 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 the same solvent as 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 when the organic nanoparticles are formed (or before and after) by reprecipitation, during extraction or concentration (or before or after), when the aggregated organic particles are dispersed (or before or after) after concentration. After the process is completed, it may be added to any of these or a combination thereof. In the production method of the present invention, a polymer compound having a weight average molecular weight of 1000 or more may be contained in the composition as a binder to be described later. For example, after the organic particle reprecipitation liquid is concentrated, the agglomerated organic particles are finely dispersed. Sometimes it is preferred to add.

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 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, and styrene is 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 method for producing organic nanoparticles of 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.

[Organic nanoparticle dispersion composition]
Next, the method for producing the organic nanoparticles according to the present invention and the organic nanoparticles obtained thereby will be described in detail when used as, for example, a color filter, an inkjet ink or the like. The organic nanoparticles of the present invention can be used, for example, in a dispersed state 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, a portion that is liquid and binds to the pigment to harden a coating film (binder). 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 as a nanoparticle forming binder and a redispersed 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 kind of the organic material and the like, but the binder is 1 to 30% by mass with respect to the total amount of the dispersion composition. 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 Non-Patent Document 1). Therefore, 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. In addition, 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, desirably 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 process 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 Dispersing Agent A normal pigment dispersant or surfactant can be added to the organic nanoparticle dispersion composition 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.

According to the production method of the present invention, for example, pigment particles contained in an organic nanoparticle dispersion composition or a colored photosensitive resin composition to be described later are reduced to a nanometer size (for example, 10 to 100 nm). Regardless, it can be concentrated and redispersed. 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, the organic nanoparticles contained in the organic nanoparticle dispersion composition and the colored photosensitive composition can be finely dispersed in a highly and uniform manner, so that a high color density can be achieved with a thin film thickness. For example, a color filter or the like can be thinned.
In addition, the organic nanoparticle 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 including a pigment exhibiting a clear color tone and high coloring power. ing.
Furthermore, for an alkaline developer used for exposure / development in the formation of a colored image, an organic nanoparticle dispersion composition, a colored photosensitive resin composition, a binder (binder) that is soluble in an alkaline aqueous solution It can be used and can meet environmental requirements.
In addition, organic solvents with appropriate drying properties can be used as the solvent (dispersion medium for pigments) used in the organic nanoparticle dispersion composition and the colored photosensitive resin composition, and satisfy the requirements in terms of drying after coating. can do.

[Colored photosensitive resin composition]
The colored photosensitive resin composition of the present invention contains at least (a) organic nanoparticles, (b) a binder, (c) a monomer or oligomer, and (d) a photopolymerization initiator or photopolymerization initiator system. Hereinafter, each component of the colored photosensitive resin composition of the present invention will be described.

(A) Organic nanoparticles The method for producing organic nanoparticles has already been described in detail. The content of the organic 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). Preferably, 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 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 weight 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) Monomer or oligomer The monomer or oligomer 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 by light irradiation. It is preferable. 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, neopentyl glycol 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 polyfunctional alcohols such as trimethylolpropane and 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 The 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 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, JP-B 51-4 Benzothiazole compounds and trihalomethyl-s-triazine compounds described in US Pat. No. 516, trihalomethyl-triazine compounds described in US Pat. No. 4,239,850, trihalomethyl described in US Pat. No. 4,221,976 An 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 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 it is too small, the exposure sensitivity will be too low.

(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 -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 that directly affects the film thickness of the pixel.
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 colorant (pigment), a colorant (dye or pigment) can be added to the colored photosensitive resin composition of the present invention as necessary. 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 ultraviolet absorber include salicylate-based, benzophenone-based, benzotriazole-based, cyanoacrylate-based, nickel chelate-based, hindered amine-based compounds and the like 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.

[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. An example of the structure of the integral film 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 preferable that the softening point by the measurement method is selected from organic polymer substances having a temperature of about 80 ° C. or less. 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 the present invention can be used as one having excellent 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 size 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, and this 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, 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. 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 production method, the method for forming the photosensitive resin layer on the substrate includes (a) a method of applying each of the colored photosensitive resin compositions with a normal coating apparatus or the like, and (b) the above-described method. Examples thereof include a method of using a photosensitive resin transfer material and affixing 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. Note that preferred specific examples of the slit coater are 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 The photosensitive resin transfer material of the present invention is used to press-fit 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 (Interlayer) 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 solution 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, and 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.

The present invention will be described below in more detail based on examples, but the present invention is not limited thereto.
(Example / Comparative Example 1)
(Example 1-1)
A pigment solution was prepared by dissolving pigment (Pigment Red 254) at 15 mmol / L in a solution prepared by mixing 1-methyl-2-pyrrolidone and 1 mol / L sodium hydroxide aqueous solution at 6: 1. Separately from this, water was prepared as a poor solvent.
Here, the temperature was controlled at 1 ° C., and the pigment solution was added to 1000 ml of poor solvent water stirred at 500 rpm with a GK-0222-10 type Lamond Stirrer manufactured by Fujisawa Pharmaceutical Co., Ltd. NP-KX-500 manufactured by Nippon Seimitsu Chemical Co., Ltd. An organic pigment particle dispersion was prepared by injecting 100 ml at a flow rate of 50 ml / min using a large capacity non-pulsating pump.
The prepared organic particle dispersion was measured using Nanotrack UPA-EX150 manufactured by Nikkiso Co., Ltd., and the particle size and monodispersity were evaluated. The number average particle size was 31 nm and the monodispersion was 1.40.
To the prepared organic pigment particle dispersion (pigment particle concentration of about 0.05% by mass), 500 ml of 2- (1-methoxy) propyl acetate was added, stirred at 25 ° C. for 10 minutes at 500 rpm, and allowed to stand for 1 day. The pigment particles were extracted into a 2- (1-methoxy) propyl acetate phase to obtain a concentrated extract.
The concentrated extract obtained by extracting the pigment particles is filtered using an FP-010 filter manufactured by Sumitomo Electric Fine Polymer Co., to obtain a pasty concentrated pigment solution [I] (pigment particle concentration of 30% by mass). It was.

An organic particle dispersion liquid [I] of the present invention having the following composition was prepared using the paste-like concentrated pigment liquid [I].
Paste-like concentrated pigment liquid [I] 21.3 g
Pigment dispersant A (Exemplary compound (7.) of the compound represented by formula (D1)) 0.6 g
Methacrylic acid / benzyl methacrylate copolymer * 15.8 g
1-methoxy-2-propyl acetate 42.3 g
* Copolymerization molar ratio 28/72, weight average molecular weight: 30,000, 40 mass% 1-methoxy-2-propyl acetate solution

The organic particle dispersion [I] having the above composition was stirred with a motor mill M-50 (manufactured by Eiger) at a peripheral speed of 9 m / s using zirconia beads having a diameter of 0.65 mm. The liquids of stirring time, 1 hour, 3 hours, 5 hours, 9 hours, and 15 hours were used as sample pigment liquids (1) to (5), respectively.
In order to evaluate the performance of the sample pigment solution, a membrane sample was prepared. The sample pigment solutions (1) to (5) obtained as described above were applied to a 75 mm × 75 mm glass substrate with a spin coater 1H-D7 manufactured by Mikasa, and dried at 100 ° C. for 2 minutes on a hot plate to form a film. Samples (1) to (5) were prepared.

(Example 1-2)
A pigment solution was prepared by dissolving pigment (Pigment Red 254) at 150 mmol / L in a solution in which dimethyl sulfoxide and an 8 mol / l potassium hydroxide aqueous solution were mixed at a ratio of 6: 1. Separately from this, water was prepared as a poor solvent.
Here, the temperature was controlled at 1 ° C., and the pigment solution was added to 1000 ml of poor solvent water stirred at 500 rpm with a GK-0222-10 type Lamond Stirrer manufactured by Fujisawa Pharmaceutical Co., Ltd. NP-KX-500 manufactured by Nippon Seimitsu Chemical Co., Ltd. An organic pigment particle dispersion was prepared by injecting 100 ml at a flow rate of 50 ml / min using a large capacity non-pulsating pump.
The prepared organic particle dispersion was measured using Nanotrack UPA-EX150 manufactured by Nikkiso Co., Ltd., and the particle size and monodispersity were evaluated. The number average particle size was 32 nm and the monodispersion was 1.41.
To the prepared organic pigment particle dispersion (pigment particle concentration of about 0.5% by mass), 500 ml of 2- (1-methoxy) propyl acetate was added, stirred at 25 ° C. for 10 minutes at 500 rpm, and allowed to stand for 1 day. The pigment particles were extracted into a 2- (1-methoxy) propyl acetate phase to obtain a concentrated extract.
The concentrated extract from which the pigment particles have been extracted is filtered using a FP-010 filter manufactured by Sumitomo Electric Fine Polymer Co. to obtain a paste-like concentrated pigment solution [II] (pigment particle concentration 35% by mass). It was.

Paste concentrated pigment liquid [II] 18.3 g
Pigment dispersant A 0.6g
Methacrylic acid / benzyl methacrylate copolymer * 15.8 g
1-methoxy-2-propyl acetate 45.3 g
* Copolymerization molar ratio 28/72, weight average molecular weight: 30,000, 40 mass% 1-methoxy-2-propyl acetate solution

  Sample pigment liquids (6) to (10) were obtained from the organic particle dispersion liquid [II] of the present invention having the above composition in the same manner as in Example 1-1. Membrane samples (6) to (10) were produced from the obtained sample pigment solutions (6) to (10) in the same manner as in Example 1-1.

(Example 1-3)
In Example 1-1, methacrylic acid / benzyl methacrylate copolymer was converted to 15.8 g of methacrylic acid / benzyl methacrylate / styrene copolymer (molar ratio 27:60:13, weight average molecular weight: 28,000, 40). Sample pigment solutions (11) to (15) were prepared in the same manner as in Example 1-1 except that (mass% 1-methoxy-2-propyl acetate solution) was used.
Membrane samples (11) to (15) were produced from the obtained sample pigment solutions (11) to (15) in the same manner as in Example 1-1.

(Example 1-4)
In Example 1-1, methacrylic acid / benzyl methacrylate copolymer was converted to 15.8 g of methacrylic acid / propyl methacrylate / styrene copolymer (molar ratio 26:62:12, weight average molecular weight: 29,000, 40). Sample pigment solutions (16) to (20) were prepared in the same manner as in Example 1-1 except that (mass% 1-methoxy-2-propyl acetate solution) was used.
Membrane samples (16) to (20) were produced from the obtained sample pigment solutions (16) to (20) in the same manner as in Example 1-1.

(Example 1-5)
In Example 1-1, methacrylic acid / benzyl methacrylate copolymer was converted to 15.8 g of methacrylic acid / methyl methacrylate / styrene copolymer (molar ratio 25:62:13, weight average molecular weight: 30,000, 40% by mass). A sample pigment solution (21) to (25) was prepared in the same manner as in Example 1-1 except that (1-methoxy-2-propyl acetate solution) was used.
Membrane samples (21) to (25) were produced from the obtained sample pigment solutions (21) to (25) in the same manner as in Example 1-1.

(Example 1-6)
In Example 1-1, except that methacrylic acid / benzyl methacrylate copolymer was changed to 15.8 g of polyacrylic acid (weight average molecular weight: 33,000, 40 mass% 1-methoxy-2-propyl acetate solution). Sample pigment solutions (26) to (30) were prepared in the same manner as in Example 1-1.
Membrane samples (26) to (30) were produced from the obtained sample pigment solutions (26) to (30) in the same manner as in Example 1-1.

(Example 1-7)
In Example 1-1, except that methacrylic acid / benzyl methacrylate copolymer was changed to 15.8 g of polyvinyl sulfate (weight average molecular weight: 32,000, 40 mass% 1-methoxy-2-propyl acetate solution), Sample pigment solutions (31) to (35) were prepared in the same manner as in Example 1-1.
Membrane samples (31) to (35) were produced from the obtained sample pigment solutions (31) to (35) in the same manner as in Example 1-1.

(Example 1-8)
In Example 1-1, except that the methacrylic acid / benzyl methacrylate copolymer was changed to 15.8 g of polyvinyl alcohol (weight average molecular weight: 31,000, 40 mass% 1-methoxy-2-propyl acetate solution). Sample pigment solutions (36) to (40) were prepared in the same manner as in Example 1-1.
Membrane samples (36) to (40) were produced from the obtained sample pigment solutions (36) to (40) in the same manner as in Example 1-1.

(Example 1-9)
In Example 1-1, sample pigment solutions (41) to (45) were prepared in the same manner as in Example 1-1 except that pigment dispersant A was not added.
Membrane samples (41) to (45) were produced from the obtained sample pigment solutions (41) to (45) in the same manner as in Example 1-1.

(Example 1-10)
In Example 1-1, the methacrylic acid / benzyl methacrylate copolymer was converted into a methacrylic acid / benzyl methacrylate copolymer (copolymerization molar ratio 28/72, weight average molecular weight 10,000, 40 mass% 1-methoxy. A sample pigment solution (46) to (50) was prepared in the same manner as in Example 1-1 except that the solution was changed to 2-propyl acetate solution.
Membrane samples (46) to (50) were prepared in the same manner as in Example 1-1 using the obtained sample pigment solutions (46) to (50).

(Example 1-11)
In Example 1-1, the methacrylic acid / benzyl methacrylate copolymer was changed to a methacrylic acid / benzyl methacrylate copolymer (copolymerization molar ratio 28/72, weight average molecular weight: 4,000, 40 mass% 1-methoxy). Sample pigment solutions (51) to (55) were prepared in the same manner as in Example 1-1 except that the solution was changed to (2-propyl acetate solution).
Membrane samples (51) to (55) were produced from the obtained sample pigment solutions (51) to (55) in the same manner as in Example 1-1.

(Comparative Example 1-1)
In Example 1-1, except that 6.4 g of Pigment Red 254 (powder sample) was used instead of the paste-like concentrated pigment liquid [I], the amount of 1-methoxy-2-propyl acetate was changed to 57.2 g. Sample pigment solutions (56) to (60) were prepared in the same manner as in Example 1-1. Membrane samples (56) to (60) were produced from the obtained sample pigment solutions (56) to (60) in the same manner as in Example 1-1.

(Comparative Example 1-2)
In Example 1-1, sample pigment solutions (61) to (65) were prepared in the same manner as in Example 1-1 except that the methacrylic acid / benzyl methacrylate copolymer was not added. Production of film samples (61) to (65) was attempted from the obtained sample pigment liquids (61) to (65) in the same manner as in Example 1-1, but a sample was obtained without forming a film. There wasn't.

(Comparative Example 1-3)
In Example 1-1, the methacrylic acid / benzyl methacrylate copolymer was converted into a methacrylic acid / benzyl methacrylate copolymer (copolymerization molar ratio 28/72, weight average molecular weight: 800, 40 mass% 1-methoxy- Sample pigment solutions (66) to (70) were prepared in the same manner as in Example 1-1 except that the 2-propyl acetate solution was used.
Membrane samples (66) to (70) were produced from the obtained sample pigment solutions (66) to (70) in the same manner as in Example 1-1.

  The viscosities of the sample pigment solutions (1) to (70) were measured using an E-type viscometer (VISCONIC-ELD, manufactured by Toki Sangyo Co., Ltd.). The results are shown in Tables 1-1 and 1-2.

(Test Example 1)
Membrane samples (1) to (70) are observed with an optical microscope (500 times), a portion of 175 μm × 130 μm is taken, the image is divided into 1.22 million pixels, and variation in density is represented by a coefficient of variation (= standard for density) Deviation / average concentration). Further, the scattering of the film sample was measured by measuring the absorbance with an Agilent 8453 type spectrophotometer and evaluated by the absorbance at 700 nm. Absorbance of 0.02 or less was evaluated as ◯, 0.02 to 0.05 as Δ, and 0.05 or higher as X. The results are shown in Tables 1-3 and 1-4.

From the above results, it can be seen that according to the method for producing organic nanoparticles of the present invention, nanoparticles capable of forming a film having a uniform concentration and a dispersion thereof can be obtained.
In the dispersion liquid obtained by a dispersion method using various dispersing machines (roll mill, ball mill, attritor, etc.), which is a conventional organic pigment dispersion method, the pigment particles are undesirably refined in the dispersion. As a result, the viscosity rises, making it difficult to take out from the disperser, making it impossible to transport by pipeline, or gelling during storage, making it unusable. That is, in the conventional method, it has been difficult to provide a pigment dispersion capable of forming a film having a uniform concentration.
In contrast, according to the method for producing organic nanoparticles of the present invention, it is possible to achieve a state in which organic particles are miniaturized and a state in which fluidity is excellent at the same time, and the increase in viscosity does not occur. Nanoparticles capable of forming a transparent film and dispersions thereof can be provided. Furthermore, a film having a uniform concentration could be obtained in an extremely short time, which is half or less of the conventional film. This shows that a significant increase in production efficiency can be achieved. Furthermore, it turns out that the efficiency of particle production can be further improved by using a polymer compound having a desired molecular weight of 1000 or more.

The details of the reagents used in the above (Example / Comparative Example 1) are as follows.
Reagent Manufacturer ------------------------------------- Pigment Red 254 (Irgaphor Red B- CF)
Ciba Specialty Chemicals Polyvinylpyrrolidone K-30 Wako Pure Chemical Industries 2- (1-methoxy) propyl acetate Wako Pure Chemical Industries dimethyl sulfoxide Wako Pure Chemical Industries 1 mol / l Sodium hydroxide aqueous solution Wako Pure Chemical Industries Sodium methoxide 28% methanol solution Wako Pure Chemical Industries, Ltd. ------------------------------------ −−

(Example / Comparative Example 2)
(Example 2-1)
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.) 50 g and polyvinyl pyrrolidone 100.0 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. When the particle diameter and monodispersity of this pigment dispersion were measured using Nanotrack UPA-EX150 manufactured by Nikkiso Co., Ltd., the number average particle diameter was 29 nm and Mv / Mn was 1.29.
The pigment nanoparticle dispersion prepared by the above method was centrifuged with Hitachi Koki Co., Ltd. high-speed centrifugal cooler HIMAC SCR20B at 3500 rpm (2000 G) for 1 hour, and the supernatant was discarded and settled. The particle concentrated paste was collected. The pigment content of the paste was measured using an Agilent 8453 type spectrophotometer and found to be 12.5% by mass.
By adding 50.0 cc 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 (nano pigment concentration 33 mass%) was obtained.
[Preparation of pigment dispersion composition]
Using the paste, a pigment dispersion composition A having the following composition was prepared.
19.5 g of the paste-like concentrated pigment liquid A
Pigment dispersant A 0.6g
Methacrylic acid / benzyl methacrylate copolymer * 6.4 g
1-methoxy-2-propyl acetate 45.3 g
The pigment dispersant A was synthesized according to Japanese Patent Laid-Open No. 2000-239554.
* Mole ratio 28/72, weight average molecular weight: 30,000, 40% 1-methoxy-2-propyl acetate solution The pigment dispersion composition having the above composition was measured with a motor mill M-50 (manufactured by Eiger Japan) with a diameter of 0. 65 mm zirconia beads were used and dispersed for 1 hour at a peripheral speed of 9 m / s.

(Example 2-2)
In Pigment Dispersion Composition A of Example 2-1, Pigment Dispersant A used at the time of nano pigment particle formation was Pigment Dispersant B (Exemplary Compound (c) of the Compound Represented by Formula (D3)). Except for the above, a pigment solution B, a pigment dispersion B, a paste-like concentrated pigment solution B, and a pigment dispersion composition B were prepared in the same manner as in Example 2-1. The particle diameter and monodispersity measured by the same treatment as in Example 2-1 were a number average particle diameter of 33 nm and Mv / Mn of 1.34. The pigment dispersant B was synthesized according to Japanese Patent Publication No. 5-72943.

(Example 2-3)
In the pigment dispersion composition A of Example 2-1, Example 2- In the same manner as in Example 1, a pigment solution C, a pigment dispersion C, a paste-like concentrated pigment solution C, and a pigment dispersion composition C were prepared. The particle diameter and monodispersity measured by the same treatment as in Example 2-1 were a number average particle diameter of 32 nm and Mv / Mn 1.33. The compound (pigment dispersant C) was synthesized according to Synthesis Example 1 of JP-A-2001-31885.

(Example 2-4)
In the pigment dispersion composition A of Example 2-1, the pigment solution D, the pigment dispersion D, and the paste form were the same as in Example 2-1, except that the pigment dispersant used when forming the nano pigment particles was not used. Concentrated pigment liquid D and pigment dispersion composition D were prepared. The particle diameter and monodispersity measured by the same treatment as in Example 2-1 were a number average particle diameter of 31 nm and Mv / Mn 1.33.

(Example 2-5)
In Example 2-1 except that 6.4 g of the methacrylic acid / benzyl methacrylate copolymer was replaced with 3.2 g of the polymer compound (C-18) in the pigment dispersion composition A of Example 2-1, Similarly, a pigment solution E, a pigment dispersion E, a paste-like concentrated pigment solution E, and a pigment dispersion composition E were prepared. The particle diameter and monodispersity measured by the same treatment as in Example 2-1 were a number average particle diameter of 33 nm and Mv / Mn 1.31.

(Example 2-6)
In Example 2-2, except that 6.4 g of the methacrylic acid / benzyl methacrylate copolymer was replaced with 3.2 g of the polymer compound (C-18) in the pigment dispersion composition B of Example 2-2, Similarly, a pigment solution F, a pigment dispersion liquid F, a paste-like concentrated pigment liquid F, and a pigment dispersion composition F were prepared. The particle diameter and monodispersity measured by the same treatment as in Example 2-2 were a number average particle diameter of 30 nm and Mv / Mn of 1.29.

(Example 2-7)
In Example 2-3, except that 6.4 g of the methacrylic acid / benzyl methacrylate copolymer was replaced with 3.2 g of the polymer compound (C-18) in the pigment dispersion composition C of Example 2-3, Similarly, a pigment solution G, a pigment dispersion G, a paste-like concentrated pigment solution G, and a pigment dispersion composition G were prepared. The particle diameter and monodispersity measured by treating in the same manner as in Example 2-3 were a number average particle diameter of 32 nm and Mv / Mn 1.33.

(Example 2-8)
Example 2-4 except that 6.4 g of the methacrylic acid / benzyl methacrylate copolymer was replaced with 3.2 g of the polymer compound (C-18) in the pigment dispersion composition D of Example 2-4. Similarly, a pigment solution H, a pigment dispersion H, a paste-like concentrated pigment solution H, and a pigment dispersion composition H were prepared. The particle diameter and monodispersity measured by processing in the same manner as in Example 2-4 were a number average particle diameter of 30 nm and Mv / Mn of 1.28.

(Comparative Example 2-1)
A pigment dispersion composition I having the following composition was prepared using a bead disperser as described below.
Pigment (Pigment Red 254) 6.4g
Pigment dispersant A 0.6g
6 g of polyvinyl pyrrolidone (manufactured by Wako Pure Chemical Industries, Ltd., K30, molecular weight 40,000)
Methacrylic acid / benzyl methacrylate copolymer * 6.4 g
1-methoxy-2-propyl acetate 45.3 g
* Mole ratio 28/72, weight average molecular weight: 30,000, 40% 1-methoxy-2-propyl acetate solution

  Into a 1-methoxy-2-propyl acetate solution, a powder of pigment (Pigment Red 254), 6 g of polyvinylpyrrolidone, and a methacrylic acid / benzyl methacrylate copolymer were added and stirred to obtain a mixed solution. Next, this mixed liquid was dispersed with a motor mill M-50 (manufactured by Eiger Japan) for 9 hours at a peripheral speed of 9 m / s using zirconia beads having a diameter of 0.65 mm. The particle diameter and monodispersity measured by the same treatment as in Example 2-1 were a number average particle diameter of 82 nm and Mv / Mn 1.56.

(Comparative Example 2-2)
A pigment dispersion composition J having the following composition was prepared as follows.
Pigment (Pigment Red 254) 6.4g
Sodium chloride 64.0g
Methacrylic acid / benzyl methacrylate copolymer * 6.4 g
* Mole ratio 28/72, weight average molecular weight: 30,000, 40% 1-methoxy-2-propyl acetate solution

  Sodium chloride, a pigment (Pigment Red 254) powder, and a methacrylic acid / benzyl methacrylate copolymer were charged in 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 to 500 parts by weight of 1% hydrochloric acid aqueous solution at 80 ° C., stirred for 1 hour, filtered, washed with hot water, dried and pulverized. did. 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 J was obtained. The particle diameter and monodispersity measured by the same treatment as in Example 2-1 were a number average particle diameter of 63 nm and Mv / Mn of 1.88.

In addition, the following reagent was used for preparation of the said pigment dispersion composition AJ.
Reagent Manufacturer ------------------------------------
Pigment Red 254 (Irga Fore Red BT-CF)
Ciba Specialty Chemicals 1-methyl-2-pyrrolidone Wako Pure Chemical Industries dimethyl sulfoxide Wako Pure Chemical Industries 2- (1-methoxy) propyl acetate Wako Pure Chemical Industries 1 mol / l Hydrochloric acid aqueous solution Wako Pure Chemical Industries 8 mol / l aqueous potassium hydroxide Wako Pure Chemical Industries, Ltd. ----------------------------------

(Test Example 2-1)
The obtained pigment dispersion compositions A to J were each applied on a glass substrate so as to have a thickness of 2 μm, thereby preparing samples. As a 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 13 mm from the backlight, a polarizing plate at a position 40 mm to 60 mm, a cylinder 11 mm in diameter and 20 mm in length, and light transmitted through this. 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.
This 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.
The measurement results of contrast and light resistance of the samples obtained from the pigment dispersion compositions A to J are shown in Table 2-A.
[Table 2-A]
Sample Contrast Light resistance (color difference) Remarks ----------------------------------
Pigment Dispersion Composition A 15000 2.2 Present Invention Pigment Dispersion Composition B 14900 2.3 Present Invention Pigment Dispersion Composition C 14600 2.1 Present Invention Pigment Dispersion Composition D 13000 2.5 Present Invention Pigment Dispersion Composition E 16500 2.0 Invention Pigment Dispersion Composition F 16000 2.1 Present Invention Pigment Dispersion Composition G 15000 2.0 Present Invention Pigment Dispersion Composition H 16000 1.8 Present Invention Pigment Dispersion Composition I 7200 2.8 Comparative Example Pigment Dispersion composition J 7500 4.5 Comparative example ----------------------------------

  As shown in Table 2-A, the dispersion in which organic particles were dispersed and formed as nano-sized particles by the production method of the present invention showed extremely superior contrast and light resistance as compared with the comparative example.

(Example 2-9)
The pigment dispersion composition A was mixed with other components so as to have the composition shown in Table 2-1 below to prepare a colored photosensitive resin composition A for color filters.

＜バインダー１＞
・ポリマー（ベンジルメタクリレート／メタクリル酸／メチルメタクリレート
＝３８／２５／３７モル比のランダム共重合物、分子量４万） ２７質量部
・プロピレングリコールモノメチルエーテルアセテート ７３質量部
＜ＤＰＨＡ液＞
・ジペンタエリスリトールヘキサアクリレート（重合禁止剤ＭＥＨＱ５００ｐｐｍ
含有、日本化薬（株）社製、商品名：ＫＡＹＡＲＡＤ ＤＰＨＡ） ７６質量部
・プロピレングリコールモノメチルエーテルアセテート ２４質量部
＜界面活性剤１＞
・下記化合物１ ３０質量部
・メチルエチルケトン ７０質量部

<Binder 1>
・ Polymer (benzyl methacrylate / methacrylic acid / methyl methacrylate = random copolymer of 38/25/37 molar ratio, 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 J for color filters were prepared in the same manner as described above except that the pigment dispersion compositions B to J 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. The results of measuring the R component contrast and light resistance of each of the obtained films in the same manner as in Test Example 2-1 are shown in Table 2-B below.
[Table 2-B]
Sample Contrast Light resistance (color difference) Remarks -------------------------------------
Colored photosensitive resin composition A 14500 2.2 The present invention Colored photosensitive resin composition B 14200 2.3 The present invention Colored photosensitive resin composition C 14000 2.1 The present invention Colored photosensitive resin composition D 12200 2.5 The present invention Colored photosensitive resin composition E 15900 2.0 The present invention Colored photosensitive resin composition F 15300 2.1 The present invention Colored photosensitive resin composition G 14400 2.0 The present invention Colored photosensitive resin composition H 15200 1 .8 Colored photosensitive resin composition I 6500 2.8 Comparative Example Colored photosensitive resin composition J 7100 4.5 Comparative example -------------------- -------------------

  As shown in Table 2-B, the colored photosensitive resin composition using organic particles dispersed and produced as nano-sized particles by the production method of the present invention has extremely excellent contrast as compared with the comparative example. It showed light resistance.

(Example 2-10)
[Preparation of color filter (preparation by application using slit 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., it is described in Table 2-2 below with 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 having the composition: 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]
Using the colored photosensitive resin composition R1 having the composition described in Table 2-3 below on the substrate on which the image K has been formed, a heat-treated pixel R is formed in the same process as the formation of the black (K) image. did.
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 application 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]
A heat-treated pixel is formed in the same process as the formation of the black (K) image using the colored photosensitive resin composition G1 having the composition described in Table 2-4 below on the substrate on which the image K and the pixel R are formed. G was 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 coating 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]
In the same process as the formation of the black (K) image, using the colored photosensitive resin composition B1 having the composition described in Table 2-5 below on the substrate on which the image K, the pixel R, and the pixel G are formed. A heat-treated pixel B was formed to obtain a target color filter A.
The film thickness of the photosensitive resin layer B1 and the coating amount 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 2-2 to 2-5 will be described in more detail.
The colored photosensitive resin composition K1 is first weighed in the amount of K pigment dispersion 1 and propylene glycol monomethyl ether acetate described in Table 2-2, mixed at a temperature of 24 ° C. (± 2 ° C.), and then at 150 rpm for 10 minutes. Stirring and then methyl ethyl ketone, binder 2, hydroquinone monomethyl ether, DPHA solution, 2,4-bis (trichloromethyl) -6- [4 '-(N, N-bisethoxycarbonyl) in the amounts shown in Table 2-2 Methyl) amino-3′-bromophenyl] -s-triazine and surfactant 1 are weighed out and added in this order at a temperature of 25 ° C. (± 2 ° C.) and 30 ° C. at a temperature of 40 ° C. (± 2 ° C.) at 150 rpm. Obtained by stirring for minutes.

In addition, the composition was shown below about the following component among the compositions of Table 2-2.
<K pigment dispersion 1>
・ Carbon black (trade name: Nipex 35, manufactured by Degussa Japan Co., Ltd.)
13.1 parts by mass-dispersing agent (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

  Colored photosensitive resin composition R1 is first weighed in amounts of R pigment dispersion A, R pigment dispersion 2 and propylene glycol monomethyl ether acetate described in Table 2-3 and mixed at a temperature of 24 ° C. (± 2 ° C.). And then stirred at 150 rpm for 10 minutes, and then the amounts of methyl ethyl ketone, binder 1, DPHA solution, 2-trichloromethyl-5- (p-styrylstyryl) -1,3,4-oxadi in the amounts shown in Table 2-3. The azole, 2,4-bis (trichloromethyl) -6- [4 ′-(N, N-bisethoxycarbonylmethyl) amino-3′-bromophenyl] -s-triazine, phenothiazine was weighed, and the temperature was 24 ° C. ± 2 ° C) in this order and stirred at 150 rpm for 30 minutes, and the surfactant 1 in the amount shown in Table 2-3 was weighed and added at a temperature of 24 ° C (± 2 ° C). And stirred for 5 minutes at 30rpm to give by filtration with a nylon mesh # 200.

Of the compositions listed in Table 2-3, the R pigment dispersion A was obtained in the same manner as the pigment dispersion composition A of Example 2-1, so that the composition would be the following parts by mass. It was prepared as follows.
<R pigment dispersion A>
-23 parts by mass of paste-like concentrated pigment liquid A (CIPR 254) of Example 2-1-0.8 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 2-4, and mixed at a temperature of 24 ° C. (± 2 ° C.). And stirred for 10 minutes at 150 rpm, and then the amounts of methyl ethyl ketone, cyclohexanone, binder 2, DPHA solution, 2-trichloromethyl-5- (p-styrylstyryl) -1,3,4 Weigh out oxadiazole, 2,4-bis (trichloromethyl) -6- [4 '-(N, N-bisethoxycarbonylmethyl) amino-3'-bromophenyl] -s-triazine, phenothiazine, temperature 24 Added in this order at 150 ° C. (± 2 ° C.), stirred at 150 rpm for 30 minutes, and further weighed out the surfactant 1 in the amount shown in Table 2-4 to give a temperature of 2 It was obtained by adding at 4 ° C. (± 2 ° C.), stirring at 30 rpm for 5 minutes, and filtering through nylon mesh # 200.

  In addition, among the compositions described in Table 2-4, “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.

  Colored photosensitive resin composition B1 is first weighed in amounts of B pigment dispersion 1, B pigment dispersion 2, and propylene glycol monomethyl ether acetate in the amounts shown in Table 2-5, and mixed at a temperature of 24 ° C. (± 2 ° C.). And then stirred at 150 rpm for 10 minutes, and then the amounts of methyl ethyl ketone, binder 3, DPHA solution, 2-trichloromethyl-5- (p-styrylstyryl) -1,3,4-oxadi in the amounts shown in Table 2-5 Azole and phenothiazine are weighed out and 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. Activator 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.

  Among the compositions described in Table 2-5, “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 for the R pigment dispersion A, R pigment dispersions B to H were prepared using concentrated pigment liquids B to H, respectively. Then, color filters B to H were prepared in the same manner as the method for manufacturing the color filter A except that R pigment dispersions B to H were used instead of the R pigment dispersion A, respectively.

(Comparative Example 2-3)
In contrast to the method for producing the color filter A, the paste-like concentrated pigment liquid A used for the R pigment dispersion A was changed to the pigment dispersion compositions I and J to produce color filters I and J.
(Test Example 2-2)
The results of measuring the contrast and light resistance of each color filter in the same manner as in Test Example 2-1 are shown in Table 2-C. Moreover, about the R pixel part of color filter A-F, the presence or absence of the deposit was observed at 500-times multiplication factor using the optical microscope (The Olympus Corporation make, MX-50). Any foreign matter or deposits that are not observed in the pixel or at the edge of the pixel are made uniform with no precipitate, and foreign matter or deposits that are observed in the pixel or at the edge of the pixel are found to be uniform. did. The results are shown in Table 3-C.

[Table 2-C]
Color filter Contrast Light resistance (color difference) Presence of precipitation -------------------------------------
A (Invention) 9800 2.2 Uniform without precipitation B (Invention) 9600 2.3 Uniform without precipitation C (Invention) 9500 2.1 Uniform without precipitation D (Invention) 7400 2.5 Uniform without precipitation E ( (Invention) 10900 2.0 Uniform without precipitation F (Invention) 10700 2.1 Uniform without precipitation G (Invention) 10000 2.0 Uniform without precipitation H (Invention) 10700 1.8 Uniform without precipitation I (Comparative Example) 3500 2.8 With precipitation J (Comparative example) 4000 4.5 With precipitation ------------------------------- --------

  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 and no precipitates. On the other hand, the color filter of the comparative example had a low contrast, a precipitate was observed, and the level did not satisfy practical requirements.

(Example 2-11)
[Production and Evaluation of Liquid Crystal Display]
A liquid crystal display device was produced using the color filters A to H, and 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 it on a substrate at 33 ° C. for 30 seconds in 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 alignment control projection on which the liquid crystal alignment control protrusion was formed was baked at 230 ° C. for 30 minutes to form a cured liquid crystal alignment control protrusion on the liquid crystal display substrate.
<Positive photosensitive resin layer coating solution formulation>
・ Positive resist solution (FUJIFILM Electronics
Materials Co., Ltd. FH-2413F): 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. .

(Comparative Example 2-4)
[Production and Evaluation of Liquid Crystal Display]
In the same manner as in Example 2-11, a liquid crystal display device was produced using the color filters I and J, and the display characteristics were evaluated.
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 2-12)
[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. Further, 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, and a dry layer are dried on the temporary support. 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 R101 and G101 having the compositions described in Tables 2-6 to 2-8 below are used as the colored photosensitive resin composition K1 used in the production of the photosensitive resin transfer material K1. Photoresin transfer materials R101, G101, and B101 were prepared in the same manner as described above except that they were changed to B101 and B101. 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 2-6, the additive 1 used was a phosphate ester special activator (manufactured by Enomoto 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)), rubber roller temperature 130 ° C., linear pressure Lamination was performed at 100 N / cm ² and a conveyance speed of 2.2 m / min.
After peeling the temporary support 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, 30 ° C. in 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 with a flat nozzle pressure of 0.04 MPa for 50 seconds.
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, defoaming agent, stabilizer, trade name "T-SD1 (Fuji Photo Film Co., Ltd.)" or sodium carbonate / phenoxyoxyethylene surfactant Containing the product name “T-SD2 (manufactured by Fuji Photo Film Co., Ltd.)”, removing the residue with a rotating brush having a shower and nylon bristles 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 from the resin layer side with an ultra-high pressure mercury lamp 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 application 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 substrate was sent to a substrate preheating device without using a silane coupling liquid.

[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 coating 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 amount of the pigment (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.

  R pigment dispersion A was changed to R pigment dispersions B to H, respectively, to the above method for producing color filter A1, and color filters B1 to H1 were produced.

(Comparative Example 2-5)
In contrast to the method for producing the color filter A1, the R pigment dispersion A was changed to the pigment dispersion compositions I and J, respectively, to produce color filters I1 and J1.

Table 2-D shows the results of measuring the contrast, color difference, and presence or absence of precipitates of the obtained color filters A1 to J1 in the same manner as in Test Example 2-2.
[Table 2-D]
Color filter Contrast Weather resistance (color difference) Presence or absence of precipitation -------------------------------------
A1 (Invention) 6000 2.1 Uniform without precipitation B1 (Invention) 5900 2.3 Uniform without precipitation C1 (Invention) 5800 2.2 Uniform without precipitation D1 (Invention) 5600 2.5 Uniform without precipitation E1 Invention) 6900 2.0 Uniform without precipitation F1 (Invention) 6300 2.0 Uniform without precipitation G1 (Invention) 6100 2.0 Uniform without precipitation H1 (Invention) 6300 1.9 Uniform without precipitation I1 (Comparative Example) 3000 2.7 Precipitation J1 (Comparative example) 3500 4.6 Precipitation ------------------------------- -------

  As shown in Table 2-D, the use of the production method of the present invention in which organic particles are dispersed and formed as nano-sized particles provides a very high contrast, excellent light resistance, and the generation of precipitates can be suppressed. It turns out that it can be set as a color filter without the nonuniformity of a part.

(Example 2-13)
[Production and Evaluation of Liquid Crystal Display]
A liquid crystal display device was produced using the color filters A1 to H1 in the same manner as in Example 2-11, and the display characteristics were evaluated.

(Comparative Example 2-6)
[Production and Evaluation of Liquid Crystal Display]
In the same manner as in Example 2-11, a liquid crystal display device was produced using the color filters I1 and J1, and display characteristics were evaluated.
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 has good display characteristics without display unevenness. It was confirmed.

(Example / Comparative Example 3)
(Example 3-1)
For the preparation of the pigment dispersion compositions of Examples 2-1 to 2-8, the pigments were prepared as C.I. I. Pigment Red 254 (Irgaphor Red BT-CF) I. Pigment dispersions VA to VH, pasty concentrated pigment solutions VA to VH, pigments in the same manner as in Examples 2-1 to 2-8, except that Pigment Violet 23 (Hostaperm Violet RL-NF manufactured by Clariant) was used. Liquid dispersion compositions VA to VH were respectively prepared.
For the preparation of the pigment dispersion compositions of Comparative Examples 2-1 and 2-2, the pigment was changed to C.I. I. Pigment Red 254 to C.I. I. Pigment dispersion compositions VI and VJ were prepared in the same manner as in Comparative Examples 2-1 and 2-2, respectively, except that Pigment Violet 23 was used.
The number average particle diameter and Mv / Mn of the pigment particles in each of the dispersion compositions were measured in the same manner as in Example 2-1, Comparative Examples 2-1 and 2-2. The results were as follows.
[Table 3-A]
Sample Number average particle diameter Mv / Mn
------------------------------
Pigment dispersion composition VA 34 nm 1.30
Pigment dispersion composition VB 36 nm 1.36
Pigment dispersion composition VC 35 nm 1.33
Pigment dispersion composition VD 33 nm 1.34
Pigment dispersion composition VE 32 nm 1.33
Pigment dispersion composition VF 33 nm 1.31
Pigment dispersion composition VG 33 nm 1.36
Pigment dispersion composition VH 34 nm 1.31
Pigment dispersion composition VI 86 nm 1.65
Pigment dispersion composition VJ 70 nm 1.72
-------------------------------

(Test Example 3-1)
For the pigment dispersion compositions VA to VJ, the contrast was measured in the same manner as in Test Example 2-1. The results are shown below.
[Table 3-B]
Sample Contrast Remarks -------------------------------
Pigment dispersion composition VA 10600 The present invention Pigment dispersion composition VB 10300 The present invention Pigment dispersion composition VC 11000 The present invention Pigment dispersion composition VD 12000 The present invention Pigment dispersion composition VE 12900 The present invention Pigment dispersion composition VF 12800 The present invention Pigment dispersion Composition VG 12000 Present invention Pigment dispersion composition VH 11800 Present invention Pigment dispersion composition VI 3600 Comparative example Pigment dispersion composition VJ 5000 Comparative example ------------------ ------------
As shown by the above results, the dispersion in which organic particles were dispersed and formed as nano-sized particles by the production method of the present invention exhibited extremely superior contrast and light resistance as compared with the comparative example.

(Example 3-2)
For the colored photosensitive composition A prepared in Example 2-9, except for using the pigment dispersion compositions VA to VJ in place of the pigment dispersion composition A, for the color filter, in the same manner as in Example 2-9 Colored photosensitive resin compositions VA to VJ were prepared, respectively. The contrast of the obtained colored photosensitive resin composition was measured in the same manner as in Test Example 3-1. The results are shown below.
[Table 3-C]
Sample Contrast Remarks -------------------------------
Colored photosensitive resin composition VA 11100 The present invention Colored photosensitive resin composition VB 12000 The present invention Colored photosensitive resin composition VC 11900 The present invention Colored photosensitive resin composition VD 12700 The present invention Colored photosensitive resin composition VE 13900 The present invention Colored photosensitive resin composition VF 13300 The present invention Colored photosensitive resin composition VG 12800 The present invention Colored photosensitive resin composition VH 12600 The present invention Colored photosensitive resin composition VI 4600 Comparative example Colored photosensitive resin composition VJ 6100 Comparative example -------------------------------
From the above results, the colored photosensitive resin composition using the nanoparticles obtained by the production method of the present invention is one prepared by a commonly used Eiger mill or one using a pigment refined by a salt milling method. It can be seen that the contrast is extremely excellent.

(Example 3-3)
[Preparation of color filter (preparation by application using slit nozzle)]
For the color filter A produced in Example 2-10, Example 2 except that the R pigment dispersion A was replaced with the following R pigment dispersion 1 and the B pigment dispersion 2 was replaced with the following B pigment dispersion VA. A color filter VA was produced in the same manner as −10.
<R pigment dispersion 1>
・ C. I. P. R. 254 (trade name: Irgaphor Red B-CF,
Ciba Specialty Chemicals Co., Ltd.) 8 parts by mass Dispersant (compound 1J) 0.8 parts by mass Polymer (benzyl methacrylate / methacrylic acid = 72/28
Random copolymer of molar ratio, weight average molecular weight 37,000) 8 parts by mass / propylene glycol monomethyl ether acetate 83.2 parts by mass <B pigment dispersion VA>
-Paste concentrated pigment liquid VA 22.9 parts by mass-Dispersant (compound 1J) 0.8 parts by mass-Polymer (benzyl methacrylate / methacrylic acid = 72/28 molar ratio)
Random copolymer, molecular weight 30,000) 8 parts by mass / propylene glycol monomethyl ether acetate 68.3 parts by mass

B pigment dispersions VB to VH were prepared using the concentrated pigment liquids VB to VH, respectively, instead of the concentrated pigment liquid VA used for the B pigment dispersion VA. Then, color filters VB to VH were produced in the same manner as in the above color filter VA except that B pigment dispersions VB to VH were used instead of B pigment dispersion VA, respectively.
The results of measuring the contrast of each color filter in the same manner as in Test Example 2-1 are shown in Table 3-D below.

[Table 3-D]
Sample Contrast Remarks -------------------------------
Color Filter VA 5300 Invention Color Filter VB 5000 Invention Invention Color Filter VC 5500 Invention Invention Color Filter VD 5900 Invention Invention Color Filter VE 6200 Invention Invention Color Filter VF 6000 Invention Invention Color Filter VG 6000 Invention Invention Color Filter VH 5700 Invention Invention Color Filter VI 4000 Comparative example Color filter VJ 4500 Comparative example ------------------------------

  From Table 3-D, the color filter using the nanoparticles obtained by the production method of the present invention is compared with a color filter using a pigment produced by a commonly used Eiger mill or a pigment refined by a salt milling method. It showed very good contrast.

(Example 3-4)
[Production and Evaluation of Liquid Crystal Display]
A liquid crystal display device was produced using the color filters VA to VJ, and display characteristics were evaluated in the same manner as in Example 2-11. As a result, in contrast 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 black color and blue descriptive power and exhibits good display characteristics. It was confirmed.

(Example 3-5)
[Production of color filter (production by lamination of photosensitive resin transfer material)]
For the color filter A1 produced in Example 2-12, Example 2-12 was performed except that the R pigment dispersion A was replaced with the R pigment dispersion 1, and the B pigment dispersion 2 was replaced with the B pigment dispersion VA. A color filter VA1 was produced in the same manner as described above.
Also. Color filters VB1 to VH1 were produced in the same manner as in the above color filter VA1, except that B pigment dispersions VB to VH were used instead of B pigment dispersion VA, respectively.
The results of measuring the contrast of each color filter in the same manner as in Test Example 2-1 are shown in Table 3-E below.

[Table 3-E]
Sample Contrast Remarks -------------------------------
Color filter VA1 5500 The present invention Color filter VB1 5100 The present invention Color filter VC1 5700 The present invention Color filter VD1 6000 The present invention Color filter VE1 6200 The present invention Color filter VF1 6100 The present invention Color filter VG1 6000 The present invention Color filter VH1 5800 The present invention Color filter VI1 4000 Comparative example Color filter J1 4500 Comparative example ------------------------------

  From Table 3-E, the color filter using the nanoparticles obtained by the production method of the present invention is a color filter of a comparative example using a pigment produced by a commonly used Eiger mill, a pigment refined by a salt milling method. It can be seen that the contrast is very excellent.

(Example 3-6)
[Production and Evaluation of Liquid Crystal Display]
A liquid crystal display device was formed using the color filters VA1 to VJ1 in the same manner as in Example 3-4, and display characteristics were evaluated. It was confirmed that the liquid crystal display device using the color filter of the present invention was superior to the liquid crystal display device using the color filter of the comparative example, and was excellent in blackness and blue descriptive power and exhibited good display characteristics.

Example 4
In the process of mixing the pigment solution with the poor solvent, the paste-like concentrated pigment was the same as the paste-like concentrated pigment liquid A of Example 2-1 except that the amount of the pigment and solvent used was 10 times and 100 times. Liquid A-10 and A-100 were produced. Furthermore, using these, color filters A1-10 and A1-100 were produced in the same manner as in Example 2-12.
Further, in the process of mixing the pigment solution with the poor solvent, the paste-like concentrated pigment solution H of Example 2-8 was used except that the amount of the pigment and solvent used was 10 times and 100 times. Concentrated pigment liquids H-10 and H-100 were prepared. Further, using these, color filters H1-10 and H1-100 were produced in the same manner as in Example 2-12.
The evaluation results of the contrast of the produced color filter are shown in Table 4-A.
[Table 4-A]
Sample Contrast Remarks -------------------------------
Color Filter A1 6000 Present Invention Color Filter A1-10 6400 Present Invention Color Filter A1-100 6700 Present Invention Color Filter H1 6300 Present Invention Color Filter H1-10 6500 Present Invention Color Filter H1-100 6900 Present Invention ------ -------------------------
From the results shown in Table 4-A, according to the organic nanoparticles obtained by the production method of the present invention, a high-contrast color filter can be obtained, and the excellent characteristics are maintained even when the nanoparticles are scaled up. In addition, it can be seen that further improvement is possible. Thereby, according to the manufacturing method of this invention, in manufacture of a color filter, it turns out that high quality and high productivity can be made compatible.

(Example 5-1)
Pigment Red 254 used in the production of the color filters A to J and color filters A1 to J, trade name Irgafore Red BT-CF manufactured by Ciba Specialty Chemicals was changed to Irgafore Red BT-C manufactured by Ciba Specialty Chemicals A color filter was produced in the same manner as the above-described color filter production procedures and material preparation procedures. When a liquid crystal display device was produced using the obtained color filter, the liquid crystal display device of the present invention showed good performance with respect to the comparative example.

(Example 5-2)
In color filters A to J and color filters A1 to J, Pigment Red 254 (Irgaphor Red BT-CF) used for the production is Irgaphor Red B-CF, Irgazin DPP Red BO, and Pigment Red 255 (Irgazin DPP Red 5G). Alternatively, a color filter was prepared in the same manner as the above-described color filter preparation procedures and material preparation procedures except that Pigment Red 264 (Irgazin DPP Rubin TR) was used (all manufactured by Ciba Specialty Chemicals). . When a liquid crystal display device was produced using the obtained color filter, the liquid crystal display device of the present invention showed good performance with respect to the comparative example.

(Example 5-3)
Pigment Violet 23 (Hostaperm Violet RL-NF) used for producing color filters VA to VJ and color filters VA1 to VJ1
Fastgen Super Violet BBL made by Dainippon Ink & Chemicals,
Violet RE 388-180NO The same as the above color filter preparation procedure and the material preparation procedure, except that it was replaced by Dainichi Seika Kogyo Co., Ltd. or Pigment Violet 37 (Chromophthal Violet B Ciba Geigy). A color filter was prepared. When a liquid crystal display device was produced using the obtained color filter, the liquid crystal display device of the present invention showed good performance with respect to the comparative example.

It is sectional drawing which shows schematically the preferable embodiment of the manufacturing apparatus used for the manufacturing method of this invention. It is sectional drawing which shows schematically another preferable embodiment of the manufacturing apparatus used for the manufacturing method of this invention. It is an expanded partial sectional view which shows a mixing chamber roughly with a partial cross section as one embodiment of the manufacturing apparatus of FIGS. It is an expanded partial sectional view which shows a mixing chamber roughly with a partial cross section as another embodiment of the manufacturing apparatus of FIGS. It is sectional drawing which shows schematically another preferable embodiment of the manufacturing apparatus used for the manufacturing method of this invention. It is sectional drawing which shows schematically another preferable embodiment of the manufacturing apparatus used for the manufacturing method of this invention. It is a front view which shows roughly an example of the dissolver stirring blade used for the manufacturing method of this invention. 4 is a drawing-substituting photograph of the dissolver stirring blade shown in FIG. 4-1. It is sectional drawing which shows roughly an example of the stirring part comprised from the turbine part which can be used for the manufacturing method of this invention, and the fixed stator part located in the circumference | surroundings with a slight gap. . It is explanatory drawing which shows one structural example of the ultrafiltration apparatus used for the manufacturing method 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 (30)

  A solution of an organic material dissolved in a good solvent and a solvent compatible with the good solvent and a poor solvent for the organic material are mixed to produce the organic material as nano-sized fine particles. A method for producing organic nanoparticles, comprising preparing a nanoparticle dispersion in a polymer compound having a weight average molecular weight of 1000 or more in the dispersion.   The method for producing organic nanoparticles according to claim 1, wherein the dispersion is concentrated.   The method for producing organic nanoparticles according to claim 1 or 2, wherein the solvent in the dispersion is removed.   The method for producing organic nanoparticles according to any one of claims 1 to 3, wherein the nanoparticles in the dispersion liquid are redispersible flocs. The method for producing organic nanoparticles according to any one of claims 1 to 4, wherein the polymer compound is 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 backbone. ] The said high molecular compound is represented by following General formula (2), The manufacturing method of the organic nanoparticle of any one of Claims 1-5 characterized by the above-mentioned.

[Wherein R ³ represents a (x + y) -valent linking group. R ⁴ and R ⁵ each independently represents a single bond or a divalent linking group. A ² 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, x A ² may be the same or different. y represents a number of 1 to 8, x represents a number of 2 to 9, and x + y satisfies 3 to 10. P ² represents a polymer skeleton. ] The A ¹ or the A ² is a monovalent organic group having a group selected from the group consisting of an acidic group, a group having a basic nitrogen atom, a urea group, and a hydrocarbon group having 4 or more carbon atoms. The method for producing organic nanoparticles according to claim 5 or 6, wherein: The polymer skeleton represented by P ¹ or P ² is a polymer or copolymer of a vinyl monomer, an ester compound polymer, an ether compound polymer, a urethane compound polymer, an amide compound polymer, an epoxy compound polymer, a silicone compound polymer, The method for producing organic nanoparticles according to any one of claims 5 to 7, wherein the organic nanoparticles are derived from at least one selected from the group consisting of these modified products and copolymers.   The method for producing organic nanoparticles according to any one of claims 1 to 8, wherein the polymer compound is a polymer compound having an acidic group.   The method for producing organic nanoparticles according to claim 9, wherein the acidic group of the polymer compound is a carboxyl group.   The method for producing organic nanoparticles according to any one of claims 1 to 10, wherein the polymer compound has a weight average molecular weight of 3000 to 100,000.   The organic nanoparticle according to any one of claims 1 to 11, wherein in preparing the dispersion liquid containing the organic nanoparticle, a pigment dispersant having an amino group is allowed to coexist in any step. Particle production method. In preparing the dispersion containing the organic nanoparticles, at least one compound represented by any one of the general formulas (D1), (D3), and (D4) is contained. The manufacturing method of the organic nanoparticle of any one of Claims 1-12.

(In general formula (D1), A represents a component capable of forming an azo dye together with XY. X represents a single bond or a structural formula represented by any of the following formulas (i) to (v). Represents a group selected from a valent linking group, Y represents a group represented by the following general formula (D2), or when n is 1, it may be —NH—X ₁ -Q.

(In General Formula (D2), Z represents a lower alkylene group. —NR ₂₁ represents a lower alkylamino group or a 5- to 6-membered saturated heterocyclic ring containing a nitrogen atom. A represents 1 or 2.)

(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 , An organic dye residue selected from a pyranthrone compound dye, a perinone compound dye, a perylene compound dye, and a thioindigo compound dye, wherein X ₁ is —CONH—Y ₂ —, —SO ₂ NH—Y ₂ —, or —CH _2. NH ₂ represents NHCOCH ₂ NH—Y ₂ —, Y ₂ represents an alkylene group or an arylene group which may have a substituent, and R ₁₁ and R ₁₂ are each independently a substituted or unsubstituted alkyl group or R ₁₁ and R heterocycle to form containing at least nitrogen atom at the ₁₂ Which may .Y ₁ represents -NH- or -O-, _{Z 1} represents a group represented by a hydroxyl group or formula (D3a), or n1 is good even if _-NH-X 1 -Q 1. m1 represents an integer of 1 to 6, and n1 represents an integer of 1 to 4.)

(In General Formula (D3a), Y ₃ represents —NH— or —O—, and m 1, R ₁₁ , and R ₁₂ are the same as in General Formula (D3).)

(In the formula (D4), Me represents a methyl group.)   The poor solvent for the organic material is an aqueous solvent, an alcohol compound solvent, a ketone compound solvent, an ether compound solvent, an ester compound solvent, or a mixture thereof. The manufacturing method of organic nanoparticles.   The good solvent of the organic material is an aqueous solvent, an alcohol compound solvent, a ketone compound solvent, an ether compound solvent, a sulfoxide compound solvent, an ester compound solvent, an amide compound solvent, or a mixture thereof. 14. The method for producing organic nanoparticles according to any one of 14 above.   In preparing the dispersion of the organic nanoparticles, the organic material solution and a poor solvent are mixed to produce organic nanoparticles, which are concentrated, and then the polymer compound is added. The manufacturing method of the organic nanoparticle of any one of Claims 1-15.   The method for producing organic nanoparticles according to claim 1, wherein the organic material is an organic pigment.   The method for producing organic nanoparticles according to claim 17, wherein the organic pigment is a pyrrolopyrrole compound pigment. The method for producing organic nanoparticles according to claim 18, wherein the pyrrolopyrrole compound pigment is a pigment represented by the following formula (V).

The method for producing organic nanoparticles according to claim 18, wherein the pyrrolopyrrole compound pigment is a pigment represented by the following formula (Z).

The method for producing organic nanoparticles according to claim 18, wherein the pyrrolopyrrole compound pigment is a pigment represented by the following formula (W).

  The method for producing organic nanoparticles according to claim 17, wherein the organic pigment is a dioxazine compound pigment.   The dioxazine compound pigment is C.I. I. 23. The method for producing organic nanoparticles according to claim 22, which is CI Pigment Violet 37.   The dioxazine compound pigment is C.I. I. 23. The method for producing organic nanoparticles according to claim 22, which is CI Pigment Violet 23.   25. When the organic material solution and the poor solvent are mixed to produce organic nanoparticles, the poor solvent produces nanoparticles on a scale of 10 L or more. The manufacturing method of the organic nanoparticle of description.   The organic nanoparticle manufactured by the method of any one of Claims 1-25.   A colored photosensitive resin composition comprising at least the organic nanoparticles according to claim 26, a binder, a monomer or an oligomer, and a photopolymerization initiator or a photopolymerization initiator system.   A photosensitive resin transfer material, wherein a photosensitive resin layer containing at least the colored photosensitive resin composition according to claim 27 is provided on a temporary support.   A color filter using the colored photosensitive resin composition according to claim 27 and / or the photosensitive resin transfer material according to claim 28. 30. A liquid crystal display device comprising the color filter according to claim 29.

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