JP5361142B2 - Method for producing organic pigment powder, method for producing organic pigment dispersion composition, method for producing pigment-dispersed photoresist, method for producing color filter for liquid crystal display device, and method for producing liquid crystal display device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an organic pigment powder which can be suitably used for manufacturing a dispersion having high stability with a passage of time and giving high contrast as a color filter, and its manufacturing method. <P>SOLUTION: This organic pigment powder comprises a fine powder of an organic pigment, and a polymeric compound having a mass average molecular weight of &ge;1,000. The organic pigment powder is prepared by mixing an organic pigment solution, which is produced by dissolving the organic pigment in a first solvent to be a good solvent containing no organic acid, with a second solvent to be a poor solvent for the organic pigment, thereafter precipitating a fine particle of a nanometer size of the organic pigment in the mixed solution, and removing the solvents thereafter. <P>COPYRIGHT: (C)2009,JPO&amp;INPIT

Description

The method of manufacturing the present invention is an organic pigment Powder containing fine particles of the organic pigment of nanometer size, a manufacturing method of organic pigment dispersion compositions, methods of preparation Pigment dispersion Photos registry, the color filter for a liquid crystal display device manufacturing methods, and a method for manufacturing a liquid crystal display equipment.

  Color filters used in cutting-edge image-related equipment such as liquid crystal color displays and video cameras are precision members with red (R), green (G), and blue (B) colored pixel portions formed on the substrate. is there. Each of these colored pixel portions has a fine structure in which a thin film of resin in which an organic pigment of each color is dispersed is provided on a substrate so that a predetermined color display is reproduced. A photocurable pigment composition may be used to form the colored pixel portion. This pigment composition is prepared by adjusting a chemical characteristic by adding a resin or the like to a pigment dispersion liquid and a photocurable compound in which an organic pigment is dispersed, if necessary.

  In order to satisfy the demand as a precision member used in the image-related equipment as described above, extremely high member characteristics are required. Color filters are also required to have high performance and high quality, and attempts have been made to improve organic pigments used in the production thereof. Specifically, in preparation of the pigment dispersion composition, those having excellent storage stability and those having excellent contrast of the coating film of the color filter colored pixel portion using the pigment dispersion composition are required.

  Here, the organic pigment dispersion method includes various milling methods such as a bead mill method and a salt milling method, and a liquid phase method. In the milling method, it is difficult to sufficiently refine the organic pigment and disperse it in the composition (see Patent Document 1). Although the liquid phase method is suitable for obtaining fine pigment particles, a dispersion composition containing the pigment often exhibits high viscosity. In some cases, it may gel during storage and become unusable. Patent Document 2 discloses a pigment dispersion composition obtained by a liquid phase method.

JP 2000-239554 A International Publication No. WO2006 / 121016 Pamphlet

The present invention, dispersions with high dispersion stability in a low viscosity, the ink-jet ink can be a pigment dispersion photoresist, and the production of powder organic pigment powder exhibiting high contrast and light fastness when a color filter The purpose is to provide a method. Further, the present invention is excellent in the organic process for producing a pigment dispersion composition, Pigments method of producing dispersed photo registry, color filter manufacturing method for a liquid crystal display device, as well as black depth, containing an organic pigment powder of the and an object thereof is to provide a method of manufacturing a liquid crystal display equipment capable of exhibiting a high image display performance.

〔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、窒素原子を有する塩基性基、ウレア基、ウレタン基、配位性酸素原子を有する基、炭素数４以上の炭化水素基、アルコキシシリル基、エポキシ基、イソシアネート基、および水酸基からなる群より選ばれる基を有する１価の有機基、または置換基を有してもよい有機色素構造もしくは複素環を含有する１価の有機基を表す。ただし、ｎ個のＡ^１は互いに同一であっても、異なっていてもよい。ｍは１〜８の数を表し、ｎは２〜９の数を表し、ｍ＋ｎは３〜１０を満たす。Ｐ^１は高分子化合物残基を表す。〕
〔第３溶媒：エステル化合物溶媒、アルコール化合物溶媒、芳香族化合物溶媒、および脂肪族化合物溶媒から選ばれる有機溶媒〕
〔２〕有機顔料溶液と第２溶媒とを、下記数式（１）で表されるレイノルズ数Ｒｅが５０以上となる条件下で混合したことを特徴とする〔１〕に記載の有機顔料粉末の製造方法。
Ｒｅ＝ρＵＬ／μ ・・・ 数式（１）
［数式（１）中、Ｒｅはレイノルズ数を表し、ρは有機顔料溶液の密度を表し、Ｕは有機顔料溶液と第２溶媒とが出会うときの相対速度を表し、Ｌは有機顔料溶液と第２溶媒とが出会う部分の流路もしくは供給口の等価直径を表し、μは有機顔料溶液の粘性係数を表す。］
〔３〕第１溶媒が、水性媒体、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〕または〔２〕に記載の有機顔料粉末の製造方法。
〔４〕第２溶媒が、水性媒体、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、またはこれらの混合物であることを特徴とする〔１〕〜〔３〕のいずれか１項に記載の有機顔料粉末の製造方法。
〔５〕第３溶媒が、水性媒体、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、有機酸化合物溶媒、またはこれらの混合物であることを特徴とする〔１〕〜〔４〕のいずれか１項に記載の有機顔料粉末の製造方法。
〔６〕第３溶媒の導入前もしくは後の溶媒の除去において、固−液もしくは気−液乾燥法により溶媒分を除去して微粒子を粉末化することを特徴とする〔１〕〜〔５〕のいずれか１項に記載の有機顔料粉末の製造方法。
〔７〕第３溶媒として乳酸エチル、酢酸エチル、またはエタノールを用いることを特徴とする〔１〕〜〔６〕のいずれか１項に記載の有機顔料粉末の製造方法。
〔８〕有機顔料微粒子の平均粒径が１ｎｍ〜１μｍである〔１〕〜〔７〕のいずれか１項に記載の有機顔料粉末の製造方法。
〔９〕第３溶媒の導入量を有機顔料微粒子１００質量部に対して、１００〜３０００００質量部とする〔１〕〜〔８〕のいずれか１項に記載の有機顔料粉末の製造方法。
〔１０〕〔１〕〜〔９〕のいずれか１項に記載の製造方法で得られた有機顔料粉末と第４溶媒とを含有させることを特徴とする有機顔料分散組成物の製造方法。
〔１１〕第４溶媒が、エステル化合物溶媒、アルコール化合物溶媒、芳香族化合物溶媒、または脂肪族化合物溶媒であることを特徴とする〔１０〕に記載の有機顔料分散組成物の製造方法。
〔１２〕〔１０〕または〔１１〕に記載の方法で得られた有機顔料分散組成物と硬化化合物とを含有させて得ることを特徴とする顔料分散フォトレジストの製造方法。
〔１３〕〔１０〕または〔１１〕に記載の方法で得られた有機顔料分散組成物を含有させて樹脂組成物とし、樹脂組成物を固形化することを特徴とする液晶表示装置用カラーフィルタの製造方法。
〔１４〕〔１３〕に記載の方法で液晶表示装置用カラーフィルタを作製し、さらにこれを組み込んで表示画面とすることを特徴とする液晶表示装置の製造方法。
[1] A method for producing an organic pigment powder comprising fine particles of an organic pigment and a polymer compound having a mass average molecular weight of 1000 or more,
An organic pigment solution in which an organic pigment is dissolved in a first solvent that is a good solvent that does not contain an organic acid, and a second solvent that is a poor solvent for the organic pigment are mixed, and the organic pigment is mixed in the mixture. Deposited as nanometer-sized fine particles,
After preparing the mixed liquid, the solvent was removed, and then the polymer compound represented by the following general formula (1) was introduced into 10 to 1000 parts by mass and a third solvent with respect to 100 parts by mass of the organic pigment. ,
A method for producing an organic pigment powder that further removes the solvent again to obtain an organic pigment powder having a solid content concentration of 60% by mass or more.

[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 basic group having a nitrogen atom, a urea group, a urethane group, a group having a coordinating oxygen atom, a hydrocarbon group having 4 or more carbon atoms, an alkoxysilyl group, an epoxy group, an isocyanate group, and A monovalent organic group having a group selected from the group consisting of a hydroxyl group, or a monovalent organic group containing an organic dye structure or a heterocyclic ring which may have a substituent. However, n pieces of A ¹ may be the same as or different from each other. m represents a number of 1 to 8, n represents a number of 2 to 9, and m + n satisfies 3 to 10. P ¹ represents a polymer compound residue. ]
[Third solvent: an organic solvent selected from an ester compound solvent, an alcohol compound solvent, an aromatic compound solvent, and an aliphatic compound solvent]
[2] The organic pigment solution and the second solvent, the organic pigment powder placing serial Reynolds number Re represented by the following equation (1), characterized in that the mixed under conditions of 50 or more [1] Manufacturing method .
Re = ρUL / μ Equation (1)
[In formula (1), Re represents the Reynolds number, ρ represents the density of the organic pigment solution, U represents the relative speed at which the organic pigment solution and the second solvent meet, and L represents the organic pigment solution and the second solvent. 2 represents the equivalent diameter of the flow path or supply port where the solvent meets, and μ represents the viscosity coefficient of the organic pigment solution. ]
[ 3 ] The first solvent is an aqueous medium, 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 [1] or [2] The method for producing an organic pigment powder according to [2].
[ 4 ] The second solvent is an aqueous medium, an alcohol compound solvent, a ketone compound solvent, an ether compound solvent, a sulfoxide compound solvent, an ester compound solvent, or a mixture thereof [1] to [3] The manufacturing method of the organic pigment powder of any one.
[ 5 ] The third solvent is an aqueous medium, an alcohol compound solvent, a ketone compound solvent, an ether compound solvent, a sulfoxide compound solvent, an ester compound solvent, an amide compound solvent, an organic acid compound solvent, or a mixture thereof. The method for producing an organic pigment powder according to any one of [ 1] to [4] .
[6] In the removal of the solvent before or after the introduction of the third solvent, the solvent is removed by a solid-liquid or gas-liquid drying method to pulverize the fine particles [1] to [5] The manufacturing method of the organic pigment powder of any one of these.
[7] The method for producing an organic pigment powder according to any one of [1] to [6], wherein ethyl lactate, ethyl acetate, or ethanol is used as the third solvent.
[8] The method for producing an organic pigment powder according to any one of [1] to [7], wherein the organic pigment fine particles have an average particle diameter of 1 nm to 1 μm.
[9] The method for producing an organic pigment powder according to any one of [1] to [8], wherein the amount of the third solvent introduced is 100 to 300,000 parts by mass with respect to 100 parts by mass of the organic pigment fine particles.
[10] [1] to the production method of any one organic pigment dispersion composition characterized in that the organic pigment powder and Ru are contained and a fourth solvent, which is produced by the method according to [9].
[11] The method for producing an organic pigment dispersion composition according to [10], wherein the fourth solvent is an ester compound solvent, an alcohol compound solvent, an aromatic compound solvent, or an aliphatic compound solvent.
[ 12 ] A method for producing a pigment-dispersed photoresist obtained by containing an organic pigment dispersion composition obtained by the method according to [10] or [11] and a curing compound.
[ 13 ] A color filter for a liquid crystal display device comprising the organic pigment dispersion composition obtained by the method according to [10] or [11] to obtain a resin composition, and solidifying the resin composition Manufacturing method.
[ 14 ] A method for producing a liquid crystal display device, comprising producing a color filter for a liquid crystal display device by the method according to [1 3 ] and further incorporating the color filter into a display screen.

According to the production method of the present invention, a dispersion having a low viscosity and high dispersion stability, an ink-jet ink, and a pigment-dispersed photoresist can be obtained, and when a color filter is formed, high contrast and light resistance are exhibited. Excellent operational effects. The above-mentioned pigment powder is suitably used for a color filter for liquid crystal display devices. When the color filter is incorporated in a liquid crystal display device to display an image, the black powder is excellent and excellent image display performance is exhibited. Play.

Hereinafter, the present invention will be described in detail.
The organic pigment used in the organic pigment powder of the present invention is not limited in hue. For example, perylene compound pigment, perinone compound pigment, quinacridone compound pigment, quinacridone quinone compound pigment, anthraquinone compound pigment, anthanthrone compound pigment Benzimidazolone compound pigment, disazo condensation compound pigment, disazo compound pigment, azo compound pigment, indanthrone compound pigment, phthalocyanine compound pigment, triarylcarbonium compound pigment, dioxazine compound pigment, aminoanthraquinone compound pigment, diketopyrrolopyrrole compound Pigments, thioindigo compound pigments, isoindoline compound pigments, isoindolinone compound pigments, pyranthrone compound pigments, isoviolanthrone compound pigments, and mixtures thereof.

  Among these, quinacridone compound pigments, diketopyrrolopyrrole compound pigments, dioxazine compound pigments, phthalocyanine compound pigments, or azo compound pigments are preferable, and diketopyrrolopyrrole compound pigments, phthalocyanine compound pigments, or dioxazine compound pigments are more preferable. .

  In the present invention, two or more kinds of organic pigments or solid solutions of organic pigments can be used in combination. Moreover, you may combine with an organic pigment | dye, a polymeric organic material, etc.

  In the present invention, the organic pigment fine particles are compatible with an organic pigment solution in which an organic pigment is dissolved in a good solvent (first solvent), the first solvent, and a poor solvent (second solvent) for the organic pigment. And nanometer-sized pigment fine particles (hereinafter, also referred to as pigment nanoparticles) precipitated by mixing.

The first solvent is not particularly limited as long as it does not contain an organic acid, can dissolve the organic pigment, and is compatible with or uniformly mixed with the second solvent. The solubility of the organic pigment in the first solvent 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, it is practical that the solubility is 50% by mass or less in consideration of a commonly used organic pigment. This solubility may be the solubility when dissolved in the presence of an acid or alkali.
As for the compatibility of the first solvent and the second solvent, the amount of the first solvent dissolved in the second solvent is preferably 30% by mass or more, and more preferably 50% by mass or more. There is no particular upper limit on the amount of the first solvent dissolved in the second solvent, but it is practical to mix them in an arbitrary ratio.

  Examples of the first 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, Examples include aliphatic compound solvents, nitrile compound solvents, sulfoxide compound solvents, halogen compound solvents, ester compound solvents, ionic liquids, mixed solvents thereof, aqueous solvents, alcohol compound solvents, ketone compound solvents, ether compound solvents, sulfoxides. A compound solvent, an ester compound solvent, an amide compound solvent, or a mixture thereof is preferable, and an aqueous solvent, an alcohol compound solvent, an ester compound solvent, a sulfoxide compound solvent or an amide compound solvent is preferable, and an aqueous solvent, a sulfoxide compound solvent or an amide compound is preferable. More preferably the solvent, a sulfoxide compound solvent or the amide compound solvent is particularly preferred.

  Examples of the sulfoxide compound solvent include dimethyl sulfoxide, diethyl sulfoxide, hexamethylene sulfoxide, sulfolane and the like. Examples of the amide compound solvent include N, N-dimethylformamide, 1-methyl-2-pyrrolidone, 2-pyrrolidinone, 1,3-dimethyl-2-imidazolidinone, 2-pyrrolidinone, ε-caprolactam, formamide, N -Methylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, N-methylpropanamide, hexamethylphosphoric triamide and the like.

In addition, the concentration of the organic pigment solution in which the organic pigment is dissolved in the first solvent is preferably in the range of the saturated concentration of the organic pigment to the first solvent in the dissolution condition or about 1/100 of this.
There are no particular limitations on the conditions for preparing the organic pigment solution, and a range from normal pressure to subcritical and supercritical conditions can be selected. The temperature at normal pressure is preferably −10 to 150 ° C., more preferably −5 to 130 ° C., and particularly preferably 0 to 100 ° C.

  Although there are some that are common between those listed as specific examples of the first solvent and those listed as the second solvent, the same thing as the first solvent and the second solvent is not combined, In view of this, the solubility in the first solvent should be sufficiently higher than the solubility in the second solvent. For example, the solubility difference is preferably 0.2% by mass or more, more preferably 0.5% by mass or more. There is no particular upper limit to the difference in solubility between the first solvent and the second solvent, but it is practical that the difference is 50% by mass or less in consideration of a commonly used organic pigment.

  When the organic pigment is uniformly dissolved in the first solvent, it may be dissolved acidic or alkaline. 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 when dissolving in an alkaline manner include inorganic bases such as lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, barium hydroxide, or trialkylamines, diazabicycloundecene (DBU), metals Examples include organic bases such as alkoxides, and inorganic bases are preferred.
The amount of the base to be used is not particularly limited, but in the case of an inorganic base, it is preferably 1.0 to 30 molar equivalents, more preferably 1.0 to 25 molar equivalents relative to the organic pigment. It is particularly preferably 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, and particularly preferably 20 to 100 molar equivalents with respect to the organic pigment.

Examples of the acid used when dissolving in an acidic manner include inorganic acids such as sulfuric acid, hydrochloric acid, and phosphoric acid. Among them, sulfuric acid is more preferable.
The amount of the acid to be used is not particularly limited, but it is often used in excess compared to the base, and is preferably 3 to 500 molar equivalents, more preferably 10 to 500 molar equivalents with respect to the organic pigment. 30 to 200 molar equivalents are particularly preferred.

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

  The viscosity of the organic pigment solution is preferably 0.5 to 100.0 mPa · s, and more preferably 1.0 to 50.0 mPa · s.

  The second solvent is not particularly limited, but the solubility of the organic pigment in the second solvent is preferably 0.02% by mass or less, and more preferably 0.01% by mass or less. Although there is no particular lower limit to the solubility of the organic pigment in the second solvent, 0.0001% by mass or more is practical in consideration of a commonly used organic pigment.

  Examples of the second solvent include alcohol compound solvents, ketone compound solvents, ether compound solvents, aromatic compound solvents, carbon disulfide solvents, aliphatic compound solvents, nitrile compound solvents, sulfoxide compound solvents, halogen compound solvents, and ester compound solvents. , An ionic liquid, an amide compound solvent, a mixed solvent thereof, and the like, and a ketone compound solvent, an alcohol compound solvent, a sulfoxide compound solvent, an ester compound solvent, an amide compound solvent, and a nitrile compound solvent are 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 sulfoxide compound solvent include dimethyl sulfoxide, diethyl sulfoxide, hexamethylene sulfoxide, sulfolane and the like.
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.

  Some are listed as specific examples of the first solvent and some are listed as the second solvent, but the same thing is not combined as the first solvent and the second solvent. It is sufficient that the solubility in the first solvent is sufficiently higher than the solubility in the second solvent in relation to each organic pigment employed. For example, the solubility difference is preferably 0.2% by mass or more, and more preferably 0.5% by mass or more. There is no particular upper limit to the difference between the solubility of the organic pigment in the first solvent and the solubility in the second solvent, but it is practical that it is 50% by mass or less in consideration of the organic pigment that is usually used.

  The state of the second solvent is not particularly limited, 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. The viscosity of the organic pigment solution is preferably 0.5 to 100.0 mPa · s, and more preferably 1.0 to 50.0 mPa · s.

  When mixing the organic pigment solution and the second solvent, either of them may be added and mixed. However, the organic pigment solution is preferably jetted into the second solvent and mixed, and in this case, the second solvent is mixed. Is preferably in a stirred 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. Further, it is preferable to continuously supply the liquid into the liquid through a supply pipe. The inner diameter of the supply pipe is preferably 0.1 to 200 mm, more preferably 0.2 to 100 mm. As a speed | rate supplied into a liquid from a supply pipe | tube, 1-1000 ml / min is preferable and 5-5000 ml / min is more preferable.

By adjusting the Reynolds number when mixing the organic pigment solution and the second solvent, it is possible to control the particle diameter of the pigment nanoparticles to be deposited. Here, the Reynolds number is a dimensionless number representing the state of fluid flow and is represented by the following equation.
Re = ρUL / μ Equation (1)
In Formula (1), Re represents the Reynolds number, ρ represents the density [kg / m ³ ] of the organic pigment solution, and U represents the relative speed [m / s] when the organic pigment solution meets the second solvent. L represents the equivalent diameter [m] of the flow path or supply port where the organic pigment solution and the second solvent meet, and μ represents the viscosity coefficient [Pa · s] of the organic pigment solution.

The equivalent diameter L refers to the diameter of the equivalent circular pipe when assuming an opening diameter of a pipe having an arbitrary cross-sectional shape or a circular pipe equivalent to the flow path. The equivalent diameter L is expressed by the following formula (2), where A is the cross-sectional area of the pipe, p is the wetted length (circumferential length) of the pipe, or p is the outer periphery of the flow path.
L = 4 A / p Equation (2)
It is preferable to form particles by injecting the organic pigment solution into the second solvent through a pipe. When a circular pipe is used for the pipe, the equivalent diameter matches the diameter of the circular pipe. For example, the equivalent diameter can be adjusted by changing the opening diameter of the liquid supply port. Although the value of the equivalent diameter L is not specifically limited, For example, it is synonymous with the preferable internal diameter of the supply port mentioned above.

  The relative speed U when the organic pigment solution and the second solvent meet is defined by the relative speed in the direction perpendicular to the surface of the portion where both meet. That is, for example, when the organic pigment solution is injected and mixed in the stationary second solvent, the injection speed from the supply port becomes equal to the relative speed U. Although the value of the relative speed U is not specifically limited, For example, it is preferable to set it as 0.5-100 m / s, and it is more preferable to set it as 1.0-50 m / s.

The density ρ of the organic pigment solution is a value determined by the type of material selected, but is practically 0.8 to 2.0 kg / m ³ , for example. The viscosity coefficient μ of the organic pigment solution is also a value determined by the material used, the ambient temperature, and the like, but its preferred range is synonymous with the preferred viscosity of the organic pigment solution described above.

  The smaller the Reynolds number (Re) value, the easier it is to form a laminar flow, and the larger the value, the easier it is to form a turbulent flow. For example, it can be obtained by adjusting the Reynolds number to 60 or more to control the particle diameter of the pigment nanoparticles, preferably 100 or more, and more preferably 150 or more. Although there is no particular upper limit to the number of lay nozzles, for example, favorable pigment nanoparticles can be obtained by controlling and controlling in the range of 100,000 or less, which is preferable. Or it is good also as conditions which raised Reynolds number so that the average particle diameter of the nanoparticle obtained may be 60 nm or less. At this time, within the above range, it is possible to control and obtain pigment nanoparticles having a smaller particle size by increasing the Reynolds number.

The mixing ratio of the organic pigment solution and the second solvent is preferably 1/50 to 2/3, more preferably 1/40 to 1/2, and particularly preferably 1/20 to 3/8.
When the organic fine particles are deposited, the concentration of nanoparticles in the liquid is not particularly limited, but the organic particles are preferably in the range of 10 to 40,000 mg, more preferably in the range of 20 to 30000 mg, especially with respect to 1000 ml of the solvent. Preferably it is the range of 50-25000 mg.
Moreover, the preparation scale at the time of producing | generating a pigment nanoparticle is although it does not specifically limit, It is preferable that the mixing amount of a 2nd solvent is a preparation scale of 10-2000L, and it is more preferable that it is a preparation scale of 50-1000L. .

Regarding the particle size of organic particles, there is a method of expressing the average size of the population by quantifying by a measurement method, but as a common use, the mode diameter indicating the maximum value of the distribution, the median value of the integral distribution curve Median diameter, various average diameters (number average, length average, area average, mass average, volume average, etc.), etc. In the present invention, unless otherwise specified, the average particle diameter is the number average. The diameter.
In the present invention, the average particle size of the pigment fine particles (primary particles) is nanometer size, the average particle size is preferably 1 nm to 1 μm, more preferably 1 to 200 nm, and more preferably 2 to 100 nm. Further preferred is 5 to 80 nm. The formed particles 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. In the present invention, the monodispersity of the pigment fine particles (primary particles), that is, Mv / Mn, is preferably 1.0 to 2.0, more preferably 1.0 to 1.8, -1.5 is particularly preferred.
Examples of the method for measuring the particle size of the organic particles include microscopy, mass 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.

  In preparing the dispersion liquid by precipitating the pigment fine particles, it is preferable to contain a dispersant in at least one of the pigment solution and the second solvent. At this time, it is preferable that at least the pigment solution contains a polymer compound.

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 the dispersant, for example, anionic, cationic, amphoteric, nonionic or pigment derivative polymer dispersants can be used.

The polymer dispersant preferably has a mass average molecular weight of 1,000 to 500,000, more preferably 10,000 to 500,000, and preferably 10,000 to 100,000. Particularly preferred.
Specifically, 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 butyralized product, vinylpyrrolidone- Vinyl acetate copolymer, polyethylene oxide / propylene oxide block copolymer, polyacrylate, polyvinyl sulfate, poly (4-vinylpyridine) salt, polyamide, polyallylamine salt, condensed naphthalenesulfonate, cellulose derivative, starch Derivatives and the like. 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 polymer compounds can be used singly or in combination of two or more, or a low molecular weight dispersant may be used 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.

  It is also preferable to use a pigment dispersant containing an amino group as the dispersant. 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 of these include, for example, JP-A Nos. 2000-239554, 2003-96329, 2001-31885, JP-A-10-339949, JP-B-5-72943, and JP-A-2006-129714. The compounds described in Paragraphs 0047 to 0113 of the document and Paragraphs 0018 to 0033 of the pamphlet of International Publication No. WO2006 / 121017 can be mentioned, but are not limited thereto.

  In order to further improve the uniform dispersibility and storage stability of the pigment nanoparticles, 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. Is the range of 1-500 mass parts, More preferably, it is the range of 5-200 mass parts. If the amount is less than 0.1 parts by mass, the dispersion stability of the pigment nanoparticles may not be improved. Moreover, a dispersing agent may be used independently or may be used in combination of multiple things.

  In the present invention, organic pigment nanoparticles are precipitated to form a dispersion containing a polymer compound having a mass average molecular weight of 1000 or more, which will be described later, and the solvent is removed to make a powder. Thereby, it is possible to obtain an organic pigment powder suitable for a color filter coating liquid for a liquid crystal display device or an inkjet ink.

For example, as a dryer using hot air as a dryer using a hot air, as a dryer utilizing heat conduction such as a shelf dryer, a band dryer, a stirring dryer, a fluidized bed dryer, a spray dryer, an air dryer, etc. A drum dryer, a multi-tube dryer, a cylindrical dryer or the like is preferably used. Depending on the solvent composition, a freeze dryer or an infrared dryer can also be used.
Among these means, a spray dryer (for example, COC-12 manufactured by Okawara Chemical Co., Ltd.), a fluidized bed dryer (for example, Okawara Kako Co., Ltd.) from the viewpoint that it is suitable for obtaining a dry powder directly from the dispersion. Nara Machinery Seisakusho MSD-100) is particularly preferably used. In addition, a plurality of drying means may be used in combination to produce a pigment powder with a small amount of residual solvent. For example, a pigment dispersion pre-concentrated with a cylindrical dryer is completely dried with a drum dryer. A process such as obtaining a powder can be used.
The drying conditions are not particularly limited as long as the solvent can be evaporated and materials such as pigments and dispersants are not denatured. Further, for the purpose of increasing the drying speed, means such as decompression, stirring and mixing, and multistage can be combined depending on the type of the dryer.

In the present invention, the amount for removing the solvent content is not particularly limited, but when removing the solvent content in the dispersion to form a powder, the solid content concentration of the powder is set to 60% by mass or more, and 70 to 100% by mass. More preferably, it is particularly preferably 80 to 100% by mass. In addition, it is preferable that the content rate of organic pigment fine particle is 10-99 mass% in the total solid of the organic pigment powder of this invention, and it is more preferable that it is 30-90 mass%.

  When removing and concentrating a part of the solvent before pulverization, the solid content in the obtained concentrate is preferably 5 to 70% by mass, more preferably 8 to 50% by mass. preferable. The removal or partial removal of the solvent may be performed a plurality of times. For example, partial removal (concentration) of the solvent is performed before addition of the third solvent described later, and removal (powdering) is performed after the addition of the third solvent ) Is preferable.

In the present invention, it is preferable to redisperse the pigment fine particles in an aggregated state by removing the solvent. Organic particles from which the solvent has been removed may be agglomerated. As a result, rapid filter filtration is possible, but in order to obtain a good dispersion state again, it is preferable to obtain flocs aggregated to such an extent that they can be redispersed.
Further, in order to disperse the above-mentioned aggregated particles, a normal dispersion method may be insufficient. Even in the organic particles in such an agglomerated state, the organic particles can be suitably redispersed, for example, by containing the following polymer compound.

In the present invention, Ru using the polymer compounds represented by weight-average molecular weight of 1,000 or more lower following general formula (1).

In the general formula (1), A ¹ is an acidic group, a basic group having a 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 basic group having a 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 ) having a monovalent organic group (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 a carbon number) 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 carbon; It represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or 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 or an aralkyl group having 7 to 30 carbon atoms is represented. And the like.

As the “monovalent organic group having a urea group”, for example, —NHCONHR ¹⁵ (wherein R ¹⁵ is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, Or an aralkyl group having 7 to 30 carbon atoms).
As the “monovalent organic group having a urethane group”, for example, —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). Or an aryl group having 20 or less or an aralkyl group having 7 to 30 carbon atoms).
Examples of the “monovalent organic 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 “monovalent organic 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, a naphthyl group, etc.), an aralkyl group having 7 or more carbon atoms (for example, a benzyl group) and the like. At this time, there is no upper limit to the number of carbon atoms, but it is preferably 30 or less. Examples of the “monovalent organic group having an alkoxysilyl group” include groups having a trimethoxysilyl group, a triethoxysilyl group, and the like.
Examples of the “monovalent organic group having an epoxy group” include a group having a glycidyl group.
Examples of the “monovalent organic group having an isocyanate group” include a 3-isocyanatopropyl group.
Examples of the “monovalent organic group having a hydroxyl group” include a 3-hydroxypropyl group.

A ¹ is preferably a monovalent organic group having an acidic group, a basic group having a nitrogen atom, a urea group, or a hydrocarbon group having 4 or more carbon atoms.

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

  The organic dye structure or the heterocyclic ring may have a substituent T. Examples of the substituent T include alkyl groups having 1 to 20 carbon atoms such as a methyl group and an ethyl group, a phenyl group, and a naphthyl group. Aryl groups having 6 to 16 carbon atoms such as groups, acyloxy groups having 1 to 6 carbon atoms such as acetoxy groups, alkoxy groups having 1 to 6 carbon atoms such as methoxy groups and ethoxy groups, halogen atoms such as chlorine and bromine, C2-C7 alkoxycarbonyl groups such as methoxycarbonyl group, ethoxycarbonyl group and cyclohexyloxycarbonyl group, carbonate groups such as cyano group and t-butyl carbonate, hydroxyl group, amino group, carboxyl group, sulfonamide group, N -A sulfonylamide group etc. are mentioned.

Also, the A ¹ can be represented by the following general formula (4).

In the general formula (4), B ¹ is an acidic group, a basic group having a 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. Preferred embodiments of the group represented by the general formula (4) has the same meaning as the A ^1.

R ¹⁸ represents a single bond or an a1 + 1 valent linking group, and a1 represents 1 to 5. The linking group R ¹⁸ is a group consisting of 1 to 100 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to 200 hydrogen atoms, and 0 to 20 sulfur atoms. And may be unsubstituted or may further have a substituent. 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. The linking group R ¹⁸ may have the substituent T.

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, 1 to 200 hydrogen atoms, and A group consisting of 0 to 20 sulfur atoms is included, which may be unsubstituted or may further have a substituent. R ¹ is preferably an organic linking group.

Specific examples of R ¹ include the groups (which may form a ring structure) configured by combining the groups (t-1) to (t-34) or a plurality thereof. . When the linking group R ¹ has a substituent, examples of the substituent include the substituent T described above.

R ² represents a single bond or a divalent linking group. R ² includes a group consisting of 1 to 100 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to 200 hydrogen atoms, and 0 to 20 sulfur atoms. It may be unsubstituted or may further have a substituent.
Specific examples of R ² include groups formed by combining the groups of t-3 to 5, 7 to 18, 22 to 26, 32, and 34, or a plurality thereof. R ² preferably has a sulfur atom at the position of connection with R ¹ . When R ² has a substituent, examples of the substituent include the substituent T.

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. n is preferably 2 to 8, more preferably 2 to 7, and particularly preferably 3 to 6.

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

  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), the same applies its specific preferred embodiment. A ² may have a substituent, and examples thereof include the substituent T.

In the general formula (2), R ³ represents a (x + y) -valent linking group. R ³ has the same meaning as R ¹ , and the preferred range is also the same. At this time, R ³ is an x + y-valent linking group, but the value of x and its preferred range are the same as n in formula (1), the value of y and its preferred range are the same as m, and x + y The value of and the preferred range thereof are the same as m + n.

The linking group represented by R ³ is preferably an organic linking group, and preferred specific examples of the organic linking group are shown below. However, the present invention is not limited to these.

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

Further, when the above R ³ has a substituent, the substituent T can be cited as the substituent.

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 is a linear, branched, or cyclic alkylene group, arylene group, or aralkylene group, which may have a substituent, — O -, - S -, - C (= O) -, - N (R 19) -, - SO -, - SO 2 -, - CO 2 -, or _{^{-N (R 20) SO 2 -}} , or they A divalent group in which two or more groups are combined is preferable (the R ¹⁹ and R ²⁰ each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms). Of these, an organic linking group is preferred.

As R ⁴ , a linear or branched alkylene group or aralkylene group, —O—, —C (═O) —, —N (R ¹⁹ ) —, —SO ₂ —, —CO ₂ —, or — N (R ²⁰ ) SO ₂ — or a divalent group in which two or more of these groups are combined is more preferable, and a linear or branched alkylene group or aralkylene group, —O—, —C (═O) —, —N (R ¹⁹ ) —, —CO ₂ —, or a divalent group in which two or more of these groups are combined is particularly preferable.

R ⁵ is a single bond, straight chain or branched alkylene group, aralkylene group, —O—, —C (═O) —, —N (R ¹⁹ ) —, —SO ₂ —, —CO _2. —, Or —N (R ²⁰ ) SO ₂ —, or a divalent group in which two or more of these groups are combined is more preferable. A linear or branched alkylene group, an aralkylene group, —O—, —C (= O) —, —N (R ¹⁹ ) —, or —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, the said substituent T is mentioned as this substituent.

P ² in the general formula (2) represents a polymer skeleton and can be appropriately selected from ordinary polymers 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, linear or branched, alkylene group or aralkylene group, —O—, —C (═O) —, —N (R ¹⁹ ) -, or -CO 2 _-, or a divalent organic group formed by combining two or more of these groups, R ⁵ is a single bond, an ethylene group, a propylene group, or the following general formula (s-a) or A linking group represented by (s-b), wherein P ² is a polymer or copolymer of a vinyl monomer, an ester compound polymer, an ether compound polymer, a urethane compound polymer, or a modified product thereof, y Is a polymer compound in which x is 1-2 and x is 3-6 Masui. In the following groups, R ²¹ represents a hydrogen atom or a methyl group, and l represents 1 or 2.

  The mass average molecular weight of the polymer compound used in the production of the organic pigment powder of the present invention is preferably 1000 or more, more preferably 3000 to 100,000, and even more preferably 5000 to 80000 in terms of mass average molecular weight. 7000 to 60000 is particularly preferable. When the mass average molecular weight is within the above range, the effects of the multiple functional groups introduced at the polymer ends are sufficiently exhibited, and the performance of adsorbing to a solid surface, micelle forming ability, and surface activity is excellent. Good dispersibility and dispersion stability can be achieved.

  Specific examples of the compound represented by the general formula (1) are shown below. However, the present invention is not limited to these specific examples.

The polymer compound represented by the general formula (1) or (2) can be synthesized, for example, by the following methods.
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.
Of these, 2, 3, 4, 5 are preferable, 3, 4, 5 are more preferable, and 5 is particularly preferable because of ease of synthesis. As for these synthesis methods, the contents described in paragraphs 0184 to 0216 of Japanese Patent Application No. 2006-129714 can be referred to.

In addition, as a polymer compound having a molecular weight of 1000 or more, a polymer compound having the following acidic group (hereinafter, this compound may be referred to as “acidic group-containing polymer compound”) may be used. It is preferably a polymer compound having a group, and (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. More preferred are copolymer compounds containing seeds.
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.

In the formula, R ₁ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. 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 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 each represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. i represents the number of 1-5. 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 represents an alkyl group having 2 to 5 carbon atoms or an aryl group having 6 to 20 carbon atoms. R ₁₀ and R ₁₁ represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. j represents a number from 1 to 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) The quantity ratio% to the number of repeating units is preferably 3 to 40, more preferably 5 to 35.
In the present invention, the molecular weight means a mass average molecular weight unless otherwise specified. Examples of the molecular weight measuring method include chromatography, viscosity, light scattering, sedimentation rate, etc. In the present invention, unless otherwise specified, polystyrene measured by gel permeation chromatography (carrier: tetrahydrofuran). The converted mass average molecular weight is used.

The polymer compound may be either water-soluble or oil-soluble, and may be water-soluble and oil-soluble. Specifically, the compound represented by the general formula (1) is basically oil-soluble, but usually has some water solubility.
The mode of addition of the polymer compound is not particularly limited, and the polymer compound may be added as a solution dissolved in an aqueous solvent or an organic solvent, may be added in a solid state, or may be added in combination. When adding by dissolving in a solvent, for example, (i) a mode in which a solution in which a predetermined polymer compound is dissolved in the same or the same kind of solvent as the dispersion or the like is added to a dispersion or concentrated liquid of pigment fine particles (Ii) A mode in which a solution in which a predetermined polymer compound is dissolved in a solvent that is different from the solvent such as the dispersion but has compatibility is added. In an embodiment in which a solution in which a predetermined polymer compound is dissolved in a solvent is added, the concentration of the polymer compound in the solution is not particularly limited, but is preferably 1 to 70% by mass, and preferably 2 to 65% by mass. Is more preferable, and it is especially preferable to set it as 3-60 mass%.
The addition of the polymer compound is performed by (a) at the time of precipitation formation of pigment nanoparticles or before and after that, (b) when removing or reducing the solvent content, or (c) after removing or reducing the solvent content, May be added at any time after re-dispersing, before or after that, and (d) after the completion of those steps, or may be added in a plurality of times. In particular, in the present invention, when the solvent content of the dispersion containing the pigment fine particles is removed or reduced and concentrated or powdered, when the concentrate or powder is redispersed, a predetermined polymer compound is added to the organic solvent. An embodiment in which a solution in which is dissolved is added is preferable.

The addition amount of the polymer compound with respect to 100 parts by weight of the pigment, 1 and 0 to 1000 parts by weight, it is good Mashiku to 5 to 500 parts by weight, particularly preferably 10 to 300 parts by weight.
In the organic pigment powder of the present invention, the content of the polymer compound having a mass average molecular weight of 1000 or more varies depending on the amount contained in the dispersion and the concentration / substitution mode of the solvent, but the total mass of the organic pigment powder. The content is preferably 2.5 to 90.0% by mass, and more preferably 5.0 to 75.0% by mass.

  In addition to the above compounds, the polymer compound having a molecular weight of 1000 or more, for example, polyvinylpyrrolidone, polyvinyl alcohol, polyvinyl methyl ether, polyethylene oxide, polyethylene glycol, polypropylene glycol, polyacrylamide, vinyl alcohol-vinyl acetate copolymer, polyvinyl alcohol -Partially formalized product, polyvinyl alcohol-partially butyralized product, vinylpyrrolidone-vinyl acetate copolymer, polyethylene oxide / propylene oxide block copolymer, polyamide, cellulose derivative, starch derivative and the like. In addition, natural polymer compounds such as alginate, gelatin, albumin, casein, gum arabic, tonganto gum and lignin sulfonate can also be used. Examples of the polymer compound having an acidic group include polyvinyl sulfate and condensed naphthalene sulfonic acid.

Examples of the polymer compound having a carboxyl group include polyacrylic acid, polymethacrylic acid, and cellulose derivatives having a carboxyl group in the side chain. A copolymer compound containing (A) at least one repeating unit derived from a compound having a carboxyl group and (B) at least one repeating unit derived from a compound having a carboxylic ester group is disclosed in 59-44615, JP-B 54-34327, JP-B 58-12577, JP-B 54-25957, JP-A 59-53836, and JP-A 59-71048. Examples thereof include methacrylic acid copolymers, acrylic acid copolymers, itaconic acid copolymers, crotonic acid copolymers, maleic acid copolymers, and partially esterified maleic acid copolymers. Further, as particularly preferred examples, acrylic acid-acrylic acid ester copolymers, methacrylic acid-acrylic acid ester copolymers, acrylic acid-methacrylic acid ester copolymers, methacrylic acid-described in US Pat. No. 4,139,391 are described. Examples include methacrylic acid ester copolymers, and multi-component copolymers of acrylic acid or methacrylic acid, acrylic acid ester or methacrylic acid ester, 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.
Only one type of polymer compound having a molecular weight of 1000 or more may be used, or two or more types may be used in combination, or a compound having a molecular weight of less than 1000 may be used in combination.

In the present invention, Ru is contained third solvent to the mixed liquid after the pigment nanoparticle precipitation. Third Solvent Ri organic solvent der, an ester compound solvent, selected alcohol compound solvent, an aromatic compound solvent, and an aliphatic compound solvent. An ester compound solvent, an aromatic compound solvent or an aliphatic compound solvent is more preferred, and an ester compound solvent is particularly preferred. The third solvent may be a pure solvent based on the above solvent or a mixed solvent composed of a plurality of solvents. At this time, it is preferable to incorporate the polymer compound having a mass average molecular weight of 1000 or more into the third solvent and introduce it together to redisperse the pigment fine particle concentrate or its powder.

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

  Of these, ethyl lactate, ethyl acetate, and ethanol are preferable, and ethyl lactate is more preferable. These may be used alone or in combination of two or more. The third solvent is not the same as the first solvent or the second solvent.

The timing of the addition of the third solvent is not particularly limited as long as it is after the precipitation of the pigment nanoparticles, but a part of the solvent in the mixed liquid in which the pigment nanoparticles are precipitated is removed (concentrated) in advance (first removal). It is preferable to add after that. That is, it is preferable that the third solvent is used as a substitution solvent, and the solvent component composed of the first solvent and the second solvent in the dispersion liquid in which the pigment nanoparticles are precipitated is substituted with the third solvent.
In addition, when a pigment dispersion composition to be described later is used, after the first solvent removal step (first removal), the third solvent is added to replace the solvent, and the second solvent removal step ( It is preferable to remove the solvent by the second removal) and pulverize. And a binder and / or a solvent can be added after that, and it can be set as a desired pigment dispersion composition.
The addition amount of the third solvent is not particularly limited, but is preferably 100 to 300,000 parts by mass, and more preferably 500 to 10,000 parts by mass with respect to 100 parts by mass of the pigment nanoparticles.

  The pigment nanoparticles 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 for nanoparticle formation and the binder used for redispersion may be the same or different.

  The pigment nanoparticle concentration of the pigment nanoparticle dispersion composition after redispersion is appropriately determined according to the purpose, but preferably the pigment nanoparticle content is 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 dispersing in the vehicle as described above, the amount of the binder and dissolved dilution component is appropriately determined depending on the type of the organic pigment 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 nanoparticle powder from which the solvent is removed, the nanoparticles may aggregate as described above. As a method of redispersing 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, so 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 limitations on the disperser used when dispersing the pigment nanoparticles by applying physical energy, for example, dispersers such as kneaders, roll mills, atriders, super mills, dissolvers, homomixers, and sand mills. Can be mentioned. Further, a high-pressure dispersion method and a dispersion method using fine particle beads are also preferable.

  The colored photosensitive resin composition (pigment-dispersed photoresist) of the present invention contains a dispersion of the organic pigment nanoparticles and a monomer or oligomer (curing compound), preferably further a binder, and a photopolymerization initiator or photopolymerization start. Including drug systems. Hereinafter, each component of the colored photosensitive resin composition will be described.

  The organic pigment fine particles and the method for producing the powder have already been described in detail. The content of the pigment nanoparticles in the colored photosensitive resin composition is 3 to 90% by mass with respect to the total solid content (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 pigment nanoparticles functioning as a colorant (pigment particles) 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.

  The monomer or oligomer is preferably a polyfunctional monomer that has two or more ethylenically unsaturated double bonds and undergoes addition polymerization upon irradiation with light. Examples of such monomers and oligomers include compounds having at least one addition-polymerizable ethylenically unsaturated group in the molecule and having a boiling point of 100 ° C. or higher at normal pressure. Examples include monofunctional acrylates and monofunctional methacrylates such as dipentaerythritol hexa (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate and phenoxyethyl (meth) acrylate; polyethylene glycol di ( (Meth) acrylate, polypropylene glycol di (meth) acrylate, trimethylolethane triacrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane diacrylate, neopentylglycol di (meth) acrylate, pentaerythritol tetra (meth) acrylate, Pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipenta Rithritol penta (meth) acrylate, hexanediol di (meth) acrylate, trimethylolpropane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) isocyanurate, tri (acryloyloxyethyl) cyanurate, glycerin tri (meth) acrylate And polyfunctional acrylates and polyfunctional methacrylates such as those obtained by adding ethylene oxide or propylene oxide to a polyfunctional alcohol such as trimethylolpropane or glycerin and then (meth) acrylated. Further, 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.

  Monomers or oligomers may be used alone or in admixture of two or more. The content of the colored photosensitive resin composition with respect to the total solid content is generally 5 to 50% by mass, and 10 to 40% by mass. Is preferred. 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.

  As the binder, a binder having an acidic group is preferable, and it can be added at the time of preparing the inkjet ink for color filter or the colored photosensitive resin composition, but when producing the pigment nanoparticle dispersion composition, or pigment nanoparticle It is also preferable to add at the time of formation. It is also possible to add a binder to both or one of the poor solvent for adding the organic pigment solution and the organic pigment solution to form pigment nanoparticles. Alternatively, it is also preferable to add the binder solution in a separate system when forming the pigment nanoparticles.

  The binder is preferably an alkali-soluble polymer having a polar group such as a carboxylic acid group or a carboxylic acid group in the side chain. Examples thereof include JP-A-59-44615, JP-B-54-34327, JP-B-58-12577, JP-B-54-25957, JP-A-59-53836, and JP-A-57-36. A methacrylic acid copolymer, an acrylic acid copolymer, an itaconic acid copolymer, a crotonic acid copolymer, a maleic acid copolymer, a partially esterified maleic acid copolymer as described in JP-A-59-71048 Etc. Moreover, the cellulose derivative which has a carboxylic acid group, carboxylate, etc. in a side chain can also be mentioned, In addition to this, what added the cyclic acid anhydride to the polymer which has a hydroxyl group can also be used preferably. As particularly preferred examples, copolymers of benzyl (meth) acrylate and (meth) acrylic acid described in US Pat. No. 4,139,391, benzyl (meth) acrylate and (meth) acrylic acid are used. And multi-component copolymers with other monomers.

  The binder may be used singly or may be used in the state of a composition used in combination with a normal film-forming polymer, and the addition amount relative to 100 parts by mass of pigment nanoparticles is generally 10 to 200 parts by mass. And 25-100 mass parts is preferable.

  In addition, in order to improve the crosslinking efficiency, a polymerizable group may be included in the side chain, and a UV curable resin, a thermosetting resin, or the like is also useful. Furthermore, as the binder resin, an organic high molecular polymer having a water-soluble atomic group in a part of the side chain can be used.

  As a photopolymerization initiator or a photopolymerization initiator system (in the present invention, a photopolymerization initiator system refers to a mixture that exhibits a photopolymerization initiation function by a combination of a plurality of compounds), U.S. Pat. No. 2,367,660 Vicinal polyketaldonyl compounds disclosed in US Pat. No. 2,448,828, acyloin ether compounds described in US Pat. No. 2,448,828, α-hydrocarbon-substituted fragrances described in US Pat. No. 2,722,512 Group acyloin compounds, polynuclear quinone compounds described in US Pat. Nos. 3,046,127 and 2,951,758, combinations of triarylimidazole dimers described in US Pat. No. 3,549,367 and p-amino ketones, Benzothiazole compounds and trihalomethyl-s-triazines described in Japanese Patent No. 51-48516 Compound, trihalomethyl are described in U.S. Patent No. 4239850 - triazine compounds include U.S. Patent trihalomethyl oxadiazole compounds described in No. 4,212,976 specification or the like. 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.

The photopolymerization initiator or the photopolymerization initiator system may be used alone or in combination of two or more, but it is particularly preferable to use two or more. When at least two kinds of photopolymerization initiators are used, display characteristics, particularly display unevenness, can be reduced.
The content of the photopolymerization initiator or the photopolymerization initiator system with respect to the total solid content of the colored photosensitive resin composition is generally 0.5 to 20% by mass, and preferably 1 to 15% by mass. If this amount is too large, the sensitivity becomes too high and control becomes difficult. If the amount is too small, the exposure sensitivity becomes too low.

  In the colored photosensitive resin composition, in addition to the above components, an organic solvent for preparing a resin composition (fourth solvent) may be further used. Examples of the fourth solvent include, but are not limited to, esters, ethers, and ketones. Among these, 1,3-butylene glycol diacetate, 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. 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. As for content of a 4th solvent, 10-95 mass% is preferable with respect to the resin composition whole quantity.

  Moreover, it is preferable to contain an appropriate surfactant in the colored photosensitive resin composition. Suitable surfactants include those 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.

  The colored photosensitive resin composition 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.

In addition to the colorant (pigment), a colorant (dye or pigment) can be added to the colored photosensitive resin composition 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.

The colored photosensitive resin composition 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.
As for content of a ultraviolet absorber, 5 mass% or less is preferable with respect to the resin composition whole quantity.

  Further, in the colored photosensitive resin composition, in addition to the above additives, “adhesion aid” described in JP-A-11-133600, other additives, and the like can be contained.

The colored photosensitive resin composition of the present invention can be made into an inkjet ink by appropriately adjusting the composition. In addition to the color filter, the inkjet ink may be a normal inkjet ink such as for printing. Among them, the inkjet ink for the color filter is preferable.
The ink-jet ink of the present invention only needs to contain the organic pigment powder, and is preferably a medium containing a polymerizable monomer and / or a polymerizable oligomer containing the organic pigment powder. Here, as the polymerizable monomer and / or polymerizable oligomer, those described above for the colored photosensitive resin composition can be used.
At this time, it is preferable to control the ink temperature so that the fluctuation range of the viscosity is within ± 5%. The viscosity at the time of injection is preferably 5 to 25 mPa · s, more preferably 8 to 22 mPa · s, and particularly preferably 10 to 20 mPa · s (in the present invention, unless otherwise specified) It is a value at 25 ° C.). In addition to the setting of the injection temperature, the viscosity can be adjusted by adjusting the type and amount of components contained in the ink. The viscosity can be measured, for example, by a normal apparatus such as a conical plate type rotational viscometer or an E type viscometer.
The surface tension of the ink upon ejection is preferably 15 to 40 mN / m from the viewpoint of improving the flatness of the pixel (in the present invention, the surface tension is a value at 23 ° C. unless otherwise specified). ). More preferably, it is 20-35 mN / m, Most preferably, it is 25-30 mN / m. The surface tension can be adjusted by adding a surfactant or the type of solvent. The surface tension is measured using a known measuring instrument such as a surface tension measuring device (CBVP-Z, manufactured by Kyowa Interface Science Co., Ltd.) or a fully automatic balanced electro surface tension meter ESB-V (manufactured by Kyowa Scientific Co., Ltd.). And can be measured by a platinum plate method.

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

  As the ink jet head (hereinafter also simply referred to as a head), a normal one can be applied, and a continuous type and a dot on demand type can be used. Among the dot-on-demand types, the thermal head is preferably a type having an operation valve as described in JP-A-9-323420 for discharging. As the piezo head, for example, the heads described in European Patent A277,703, European Patent A278,590 and the like can be used. The head preferably has a temperature control function so that the temperature of the ink can be controlled. It is preferable to set the injection temperature so that the viscosity at the time of ejection is 5 to 25 mPa · s, and to control the ink temperature so that the fluctuation range of the viscosity is within ± 5%. Moreover, as a drive frequency, it is preferable to operate | move at 1-500 kHz.

In addition, after each pixel is formed, a heating step of performing heat treatment (so-called baking treatment) can be provided. That is, a substrate having a layer photopolymerized by light irradiation is heated in an electric furnace, a dryer or the like, or an infrared lamp is irradiated. The temperature and time of heating depend on the composition of the photosensitive dark color composition and the thickness of the formed layer, but generally from about 120 ° C. to the point of obtaining sufficient solvent resistance, alkali resistance, and ultraviolet absorbance. Heating at about 250 ° C. for about 10 minutes to about 120 minutes is preferred.
The pattern shape of the color filter thus formed is not particularly limited, and may be a general black matrix shape such as a stripe shape, a lattice shape, or a delta arrangement. May be.

  In the present invention, it is preferable to prepare a partition wall in advance before the pixel forming step using the color filter inkjet ink described above, and to apply the ink to a portion surrounded by the partition wall. Any partition may be used, but in the case of manufacturing a color filter, it is preferably a light-blocking partition having a black matrix function (hereinafter also simply referred to as “partition”). The partition wall can be produced by the same material and method as those of a normal color filter black matrix. For example, paragraph numbers [0021] to [0074] of JP 2005-3861 A, black matrices described in paragraph numbers [0012] to [0021] of JP 2004-240039 A, and JP 2006-17980 A. And the inkjet black matrix described in paragraphs [0009] to [0044] of JP-A-2006-10875.

  The components contained in the coating film using the colored photosensitive resin composition are the same as those already described. Moreover, although the thickness of the coating film using a colored photosensitive resin composition can be suitably determined according to the use, it is preferable that it is 0.5-5.0 micrometers, and is 1.0-3.0 micrometers. It is more preferable. In the coating film using the colored photosensitive resin composition, the above-described monomer or oligomer is polymerized to form a colored photosensitive resin composition polymerized film, and a color filter having the polymerized film can be produced (color filter). The production will be described later.) Polymerization of the polymerizable monomer or polymerizable oligomer can be carried out by allowing a photopolymerization initiator or a photopolymerization initiator system to act upon irradiation with light.

  In addition, although the said coating film can be formed by apply | coating and drying a colored photosensitive resin composition with a normal application method, in this invention, it has a slit-shaped hole in the part which discharges a liquid. It is preferable to apply by a slit 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 having excellent solubility in a 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.

  The photosensitive transfer material is preferably formed using a 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, and the photosensitive transfer material is colored as described above. A photosensitive resin is provided by using a photosensitive resin composition.

  In the photosensitive transfer material, it is necessary that the temporary support has flexibility and does not cause significant deformation, contraction or elongation even under pressure, or under pressure and heat. 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.

  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.

In the photosensitive transfer material, 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.

  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 it must be easily separated from the photosensitive resin layer. For example, silicone paper, polyolefin or polytetrafluoroethylene sheet is suitable as the protective film material.

The photosensitive transfer material is provided with a thermoplastic resin layer by applying a coating solution (thermoplastic resin coating solution) in which a thermoplastic resin layer additive is dissolved on a temporary support, followed by drying. An intermediate layer material solution composed of a solvent that does not dissolve the thermoplastic resin layer is applied and dried on the resin layer, and then the photosensitive resin layer is prepared by applying and drying with a solvent that does not dissolve the intermediate layer. Can do.
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 transfer material, 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. 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, it is preferable to perform with the coating apparatus (slit coater) using the slit-shaped nozzle already demonstrated. Preferred specific examples of the slit coater are the same as described above.

The color filter of the present invention is excellent in contrast. In the present invention, the contrast represents the ratio of the amount of transmitted light between two polarizing plates when the polarization axis is parallel and 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, which is a very important performance in order to replace the liquid crystal display with a CRT.

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

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

In the present invention, 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.

  The liquid crystal display device provided with the color filter of the present invention has a high contrast and excellent descriptive power such as black spots, and is particularly preferably a VA system. 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 color filter of the present invention can be used for a CCD device and exhibits excellent performance.

EXAMPLES Hereinafter, although this invention is demonstrated in more detail based on an Example, this invention is limited to this and is not interpreted.
(Example 1 and Comparative Example 1)
<Preparation of organic pigment powder A and pigment dispersion composition A>
1000 ml of dimethyl sulfoxide (manufactured by Wako Pure Chemical Industries, Ltd.), 33.3 ml of 28% sodium methoxide methanol solution, pigment C.I. I. Pigment Red 254 (Irgaphor Red BT-CF, trade name, manufactured by Ciba Specialty Chemicals Co., Ltd.) 50 g, and polyvinylpyrrolidone (K-25, mass average molecular weight 30000, trade name, manufactured by Wako Pure Chemical Industries, Ltd.) 0 g was added to prepare Pigment Solution A. As a result of measuring the viscosity of this pigment solution A using Viscomate VM-10A-L (trade name, manufactured by CBC Materials), the viscosity when the liquid temperature of the pigment solution A is 24.5 ° C. is 16. It was 8 mPa · s. Separately, 1000 ml of water containing 16 ml of 1 mol / l hydrochloric acid (manufactured by Wako Pure Chemical Industries, Ltd.) was prepared as a poor solvent.

Here, the temperature of the solution was controlled at 18 ° C., and the pigment solution A was added to 1000 ml of poor solvent water stirred at 500 rpm with a GK-0222-10 type Lamond Stirrer (trade name, manufactured by Fujisawa Pharmaceutical Co., Ltd.). NP-KX-500 Organic pigment particles are formed by injecting 100 ml at a flow rate of 100 ml / min from a liquid feed pipe having a channel diameter of 0.8 mm using a large-capacity non-pulsating flow pump (trade name, manufactured by Nippon Seimitsu Chemical Co., Ltd.) A nanoparticle dispersion A was prepared.
The pigment nanoparticle dispersion liquid A prepared by the above procedure was concentrated at 5000 rpm for 90 minutes using an H-112 type centrifugal filter manufactured by Kokusan Co., Ltd. and a P89C type cloth manufactured by Shikishima Canvas Co., Ltd. The obtained pigment nanoparticle concentrated paste was recovered.

  It was 16.4 mass% when the pigment content of the pigment nanoparticle concentration paste was measured using an Agilent 8453 type spectrophotometer. 0.1 g of the following pigment dispersant A synthesized according to JP 2000-239554 A and 2.6 g of the exemplified compound C-1 of the polymer compound represented by the general formula (1) were added to 50.0 cc of ethyl lactate. The solution is added to 14.5 g of the pigment nanoparticle concentrated paste, and after stirring at 1500 rpm for 60 minutes with a dissolver, 25.0 cc of ethyl acetate is added, and further stirred at 500 rpm for 10 minutes with a dissolver, and pigment nanoparticle ethyl lactate dispersion A was obtained.

The organic pigment powder A (solid content concentration: 93% by mass) of the present invention was obtained by removing the solvent of the pigment nanoparticle ethyl lactate dispersion A with an evaporator.
Using the organic pigment powder A, a pigment dispersion composition A having the following composition was prepared.
14.0 g of the organic pigment powder A
1,3 Butylene glycol diacetate 46.3g
The pigment dispersion composition A having the above composition was dispersed with a motor mill M-50 (manufactured by Eiger Japan) for 1 hour at a peripheral speed of 9 m / s using zirconia beads having a diameter of 0.65 mm.

<Preparation of organic pigment powder B and pigment dispersion composition B>
In the preparation of the pigment dispersion composition A, the organic pigment powder B and the pigment dispersion composition B of the present invention were prepared in the same manner except that the solid content concentration was changed to 81% by mass.

<Preparation of organic pigment powder C and pigment dispersion composition C>
In preparing the pigment dispersion composition A, the organic pigment powder C and the pigment dispersion composition C of the present invention were prepared in the same manner except that the solid content concentration was changed to 73% by mass.

<Preparation of organic pigment powder D and pigment dispersion composition D>
Except that the polymer dispersant C-1 was changed to a random copolymer (molecular weight 37,000) of benzyl methacrylate / methacrylic acid = 72/28 molar ratio, the same procedure as in the preparation of the pigment dispersion composition A was performed. The organic pigment powder D and the pigment dispersion composition D of the present invention were prepared.

<Preparation of organic pigment powder E and pigment dispersion composition E>
In the procedure for preparing the pigment dispersion composition A, the pigment nanoparticle concentrated paste was solvent-removed on a hot plate at 100 ° C. to obtain an organic pigment powder E (solid content concentration 89% by mass).
Using the organic pigment powder B, a pigment dispersion composition E having the following composition was prepared.
14.0 g of the organic pigment powder E
1,3 Butylene glycol diacetate 46.3g
The pigment dispersion composition E having the above composition was dispersed with a motor mill M-50 (manufactured by Eiger Japan) for 1 hour at a peripheral speed of 9 m / s using zirconia beads having a diameter of 0.65 mm.

<Preparation of pigment dispersion composition F>
Pigment dispersion composition F was prepared in the same manner except that the solid content concentration was changed to 56% by mass in the procedure for preparing pigment dispersion composition A.

<Preparation of pigment dispersion composition G>
The pigment nanoparticle ethyl lactate dispersion liquid A was filtered using an FP-010 filter manufactured by Sumitomo Electric Fine Polymer Co. to obtain a paste-like concentrated pigment liquid A (solid content concentration 31 mass%).
Using the pasty concentrated pigment liquid A, a pigment dispersion composition G having the following composition was prepared.
The paste-like concentrated pigment liquid A 18.0 g
1,3 Butylene glycol diacetate 46.3g
The pigment dispersion composition G having the above composition was dispersed with a motor mill M-50 (manufactured by Eiger Japan) for 1 hour at a peripheral speed of 9 m / s using zirconia beads having a diameter of 0.65 mm.

<Preparation of pigment dispersion composition H>
A pigment dispersion composition H having the following composition was prepared as follows.
Pigment (Pigment Red 254) 6.43g
Sodium chloride 64.0g
Polymer dispersing agent C-1 14.9g
40% 1-methoxy-2-propyl acetate solution Sodium powder, pigment (Pigment Red 254) powder and polymer dispersant C-1 were charged into a 1,3 butylene glycol diacetate solution in a double-arm kneader, and 80 ° C. And kneading for 10 hours. After kneading, it was taken out into 500 parts by mass of 1% aqueous hydrochloric acid solution at 80 ° C., stirred for 1 hour, filtered, washed with hot water, dried and pulverized, and then 2.4 g of 1,3 butylene glycol diacetate was added to 1 g of the pulverized product and mixed. . The pigment composition was dispersed with a motor mill M-50 (manufactured by Eiger Japan) for 1 hour at a peripheral speed of 9 m / s using zirconia beads having a diameter of 0.65 mm. A pigment dispersion composition H was obtained.

<Preparation of organic pigment powder I and pigment dispersion composition I>
In preparing the pigment dispersion composition A, an organic pigment powder I and a pigment dispersion composition I were prepared in the same manner except that the polymer dispersant C-1 was not used.

[Contrast measurement]
The obtained pigment dispersion compositions A to I were each coated on a glass substrate so as to have a thickness of 2.0 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 Sanlitz 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.).

[Measurement of number average particle diameter and viscosity]
The pigment dispersion composition was measured for number average particle diameter Mn using Nanotrac UPA-EX150 (trade name, manufactured by Nikkiso Co., Ltd.), and Viscomate VM-10A-L (trade name, manufactured by CBC Materials). Was used to measure the viscosity. In the following examples and comparative examples, the number average particle diameter and the viscosity were measured by the above measurement methods unless otherwise specified.

  The measurement results of contrast, number average particle diameter, and viscosity in each pigment dispersion composition are shown in Table 1 below.

[Table 1]
------------------------------------
Pigment dispersion composition Contrast Viscosity [cp] Number average particle diameter [nm]
------------------------------------
A 23000 8 26
B 22000 15 32
C 21000 27 25
D 18000 9 39
E 24000 8 26
F 21000 38 35
G 22000 49 29
H 9000 13 67
I 13000 10 55
------------------------------------

As shown in the above table, the pigment dispersion compositions A to E and I in which nanometer-sized organic particles were dispersed with the organic pigment powder of the present invention exhibited both sufficient contrast and low viscosity. If the contrast of the dispersion composition is 10,000 or more (preferably 15000 or more) and the viscosity is 30 cp or less, the level required for the production of a high-quality color filter is satisfied.
From the above results, although the organic pigment powder of the present invention strongly aggregated particles by drying, it can be dispersed again in a solvent and finely dispersed to form a low-viscosity dispersion, and a color filter It can be seen that high contrast is exhibited.

(Example 2 and Comparative Example 2)
<Production of liquid crystal display device>
[Production of photosensitive transfer material]
On a 75 μm thick polyethylene terephthalate film temporary support, a coating solution for a thermoplastic resin layer having the following formulation H1 was applied and dried using a slit nozzle. Next, an intermediate layer coating solution having the following formulation P1 was applied and dried. Furthermore, a light-shielding resin composition K1 having the composition described in Table 2-A below is applied and dried, and a thermoplastic resin layer having a dry film thickness of 15 μm on the temporary support and a dry film thickness is formed. A 1.6 μm intermediate layer and a light-shielding resin layer having a dry film thickness of 2.4 μm were provided, and a protective film (12 μm thick polypropylene film) was pressure-bonded.
Thus, a photosensitive resin transfer material in which the temporary support, the thermoplastic resin layer, the intermediate layer (oxygen barrier film), and the light-shielding resin layer were integrated was prepared, and the sample name was designated as photosensitive resin transfer material K1. .

* Coating solution for thermoplastic resin layer: Formulation H1
Methanol 11.1 parts by mass Propylene glycol monomethyl ether acetate 6.4 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 = 100,000, Tg≈70 ° C.)
5.83 parts by mass / styrene / acrylic acid copolymer (copolymerization composition ratio (molar ratio))
= 63/37, molecular weight = 10,000, Tg≈100 ° C.) 3.6 parts by mass. 2,2-bis [4- (methacryloxypolyethoxy) phenyl]
Propane (made by Shin-Nakamura Chemical Co., Ltd.) 9.1 parts by mass / surfactant 1 0.54 parts by mass

<Surfactant 1> (Megafac F-780-F (produced by Dainippon Ink & Chemicals Co., _{Ltd.)) · C 6 F 13 CH} 2 CH 2 OCOCH = CH 2: 40 parts by weight and H (OCH (CH ₃ ) CH ₂ ) ₇ OCOCH═CH ₂ : 55 parts by mass and H (OCH ₂ CH ₂ ) ₇ OCOCH═CH ₂ : 5 parts by mass
Copolymer (molecular weight 30,000) 30 parts by mass / methyl ethyl ketone 70 parts by mass

<Intermediate layer (oxygen barrier layer) coating formulation: P1>
-Polyvinyl alcohol ... 32.2 parts by mass (PVA205 (saponification rate = 88%); manufactured by Kuraray Co., Ltd.)
・ Polyvinylpyrrolidone ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 14.9 parts by mass (PVP, K-30; manufactured by ISP Japan Co., Ltd.)
・ Methanol ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 429 parts by mass ・ Distilled water ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・.... 524 parts by mass

[Table 2-A]
--------------------------------------
K pigment dispersion 1 25 parts by weight Propylene glycol monomethyl ether acetate 8.0 parts by weight Methyl ethyl ketone 53 parts by weight Binder 1 9.1 parts by weight Hydroquinone monomethyl ether 0.002 parts by weight DPHA solution 4.2 parts by weight Polymerization initiator A 0. 16 parts by mass Surfactant 1 0.044 parts by mass ----------------------------------- −

  The resin composition K1 having a light-shielding property is first weighed K pigment dispersion 1 and propylene glycol monomethyl ether acetate, mixed at a temperature of 24 ° C. (± 2 ° C.) and stirred at 150 rpm for 10 minutes, and then binder 1 and hydroquinone monomethyl. Ether, DPHA liquid, polymerization initiator A (2,4-bis (trichloromethyl) -6- [4 ′-(N, N-bisethoxycarbonylmethyl) amino-3′-bromophenyl] -s-triazine), Surfactant 1 was weighed out, added in this order at a temperature of 25 ° C. (± 2 ° C.), and stirred at a temperature of 40 ° C. (± 2 ° C.) at 150 rpm for 30 minutes.

<K pigment dispersion 1>
Carbon black (Degussa, trade name Special Black 250) 13.1 parts by mass Pigment dispersant A 0.65 parts by mass Polymer (benzyl methacrylate / methacrylic acid = 72/28 molar ratio random copolymer, molecular weight 37,000) 6.72 parts by mass / propylene glycol monomethyl ether acetate 79.53 parts by mass

<Binder 1>
・ Polymer (benzyl methacrylate / methacrylic acid = 78/22 molar ratio
Random copolymer of, molecular weight 40,000) 27 parts by mass, propylene glycol monomethyl ether acetate 73 parts by mass

<DPHA solution>
Dipentaerythritol hexaacrylate (containing 500 ppm of polymerization inhibitor MEHQ,
Nippon Kayaku Co., Ltd., trade name: KAYARAD DPHA) 76 parts by mass / propylene glycol monomethyl ether acetate 24 parts by mass

[Formation of light-blocking partition walls]
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 by a substrate preheating apparatus.

After peeling off the protective film of the photosensitive resin transfer material K1, a substrate heated at 100 ° C. for 2 minutes using a laminator (manufactured by Hitachi Industries, Ltd. (Lamic II type)), a rubber roller temperature of 130 ° C., a wire Lamination was performed at a pressure of 100 N / cm and a conveyance speed of 2.2 m / min.
After peeling off the temporary support, exposure is performed with 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 with image pattern) standing vertically. The distance between the mask surface and the thermoplastic resin layer was set to 200 μm, and pattern exposure was performed with an exposure amount of 100 mJ / cm ² . The mask shape is a lattice shape, and the radius of curvature of the corner protruding toward the light-shielding partition wall in the portion corresponding to the boundary line between the pixel and the light-shielding partition wall is 0.6 μm.

Next, with a triethanolamine developer (2.5% triethanolamine-containing, nonionic surfactant-containing, polypropylene-based antifoamer-containing, trade name: T-PD1, manufactured by Fuji Photo Film Co., Ltd.) Shower development was performed at 30 ° C. for 50 seconds and a flat nozzle pressure of 0.04 MPa to remove the thermoplastic resin layer and the intermediate layer (oxygen barrier layer).
Subsequently, sodium carbonate developer (0.06 mol / liter sodium bicarbonate, sodium carbonate of the same concentration, 1% sodium dibutylnaphthalenesulfonate, anionic surfactant, antifoaming agent, stabilizer, trade name: Using T-CD1, Fuji Photo Film Co., Ltd., shower developing at 29 ° C. for 30 seconds and cone-type nozzle pressure of 0.15 MPa, developing a light-shielding resin layer, and patterning separation wall (a partition wall pattern having a light-shielding property) )

Subsequently, a detergent (containing phosphate, silicate, nonionic surfactant, antifoaming agent and stabilizer, trade name “T-SD1 (manufactured by Fuji Photo Film Co., Ltd.)”), 33 ° C., 20 seconds, cone type Residue removal was performed with a rotary brush having a shower and nylon hair at a nozzle pressure of 0.02 MPa to obtain a light-shielding partition. Thereafter, the substrate was further post-exposed with light of 500 mJ / cm ^{2 with} an ultra-high pressure mercury lamp from the resin layer side, and then heat treated at 240 ° C. for 50 minutes.

[Plasma water repellency treatment]
Thereafter, plasma water repellency treatment was performed by the following method.
Plasma water repellency treatment was performed on the substrate on which the light-shielding partition walls were formed using a cathode coupling parallel plate type plasma processing apparatus under the following conditions.
Gas used: CF ₄
Gas flow rate: 80sccm
Pressure: 40Pa
RF power: 50W
Processing time: 30 sec

[Preparation of inkjet ink for color filter]
An ink-jet ink for a color filter was prepared according to the following formulation with reference to Example 1 of JP-A-2002-201387.

  Regarding the mixing of each component in Table 2-B, first, the pigment and the polymer dispersant were added to a part of the solvent, mixed, and stirred using a three roll and bead mill to obtain a pigment dispersion. On the other hand, other blending components were added to the remainder of the solvent, and dissolved and dispersed by stirring to obtain a binder solution. Then, while adding the pigment dispersion or the pigment dispersion composition little by little to the binder solution, the mixture was sufficiently stirred with a dissolver to prepare an inkjet ink for a color filter.

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

Each of R, G, and B is desired by controlling the conveying speed and the driving frequency so that the coating amount of the pigment is 1.1 g / m ² , 1.8 g / m ² , and 0.75 g / m ^2. R, G, and B inks were ejected into the recesses corresponding to R, G, and B.
The ejected ink is conveyed to an exposure unit and exposed by an ultraviolet light emitting diode (UV-LED). NCCU033 (trade name) manufactured by Nichia Corporation was used as the UV-LED. This LED outputs ultraviolet light having a wavelength of 365 nm from one chip. When a current of about 500 mA is applied, light of about 100 mW is emitted from the chip. A plurality of these are arranged at intervals of 7 mm, and a power of 0.3 W / cm ² can be obtained on the surface. The exposure time after the droplet ejection and the exposure time can be changed according to the transport speed of the medium and the distance between the head and the LED in the transport direction. After landing, the film was dried at 100 degrees for 10 minutes and then exposed.
Depending on the setting of the distance and the conveyance speed, the exposure energy on the medium can be adjusted between 0.01 and 15 J / cm ² . The exposure energy was adjusted according to the conveyance speed.
A spectroradiometer URS-40D (trade name) manufactured by USHIO ELECTRIC CO., LTD. Was used for measurement of these exposure power and exposure energy, and a value obtained by integrating the wavelength between 220 nm and 400 nm was used.
The glass substrate after droplet ejection was baked in an oven at 230 ° C. for 30 minutes, so that both the light-shielding partition and each pixel were completely cured.

[Production of liquid crystal display devices]
A liquid crystal display device was produced using the produced color filter (referred to as color filter A), 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 prepared 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 (Dainippon Ink Chemical Co., Ltd.): 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. Polarizing plates HLC2-2518 manufactured by Sanlitz Co., Ltd. were 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.) is configured and arranged on the back side of the liquid crystal cell provided with the polarizing plate. did.

  The color filters B to I and the liquid crystals are the same as the color filter A and the liquid crystal display device A, except that the R ink 1 used when the liquid crystal display device A is manufactured from the color filter A is changed to R inks 2 to 9, respectively. Display devices B to I were produced.

<Evaluation of ink and liquid crystal display device>
[Measurement of contrast]
The contrast and viscosity of the inkjet inks A to I were measured in the same manner as in Example 1 and Comparative Example 1. The results are shown in Table 2-C below.

[Table 2-C]
------------------------------------
Pigment dispersion composition Liquid crystal display device Inkjet ink Viscosity (inkjet ink) contrast [cp]
------------------------------------
A (R ink 1) A 21000 5
B (R ink 2) B 19000 13
C (R ink 3) C 22000 24
D (R ink 4) D 16000 7
E (R ink 5) E 21000 7
F (R ink 6) F 20000 34
G (R ink 7) G 21000 50
H (R ink 8) H 7000 12
I (R ink 9) I 11000 10
------------------------------------

  From this result, the inkjet ink for color filter of the present invention achieves both high contrast and low viscosity (R inks 1 to 5, 9), and in particular, the polymer compound represented by the general formula (1) The R inks 1 to 3 and 5 using A showed higher contrast. The level of contrast and viscosity required for the color filter ink-jet ink is the same as that of the dispersion composition described above.

(Example 3 and Comparative Example 3)
The pigment dispersion composition A was mixed with other components so as to have the composition shown in Table 3-1 below to prepare a colored photosensitive resin composition A for color filters.

[Table 3-1]
--------------------------------------
Pigment dispersion composition A 44.5 parts by mass Propylene glycol monomethyl ether acetate 7.6 parts by mass Methyl ethyl ketone 37 parts by mass Binder 2 0.7 parts by mass DPHA solution 3.8 parts by mass 2-Trichloromethyl- (p-styrylstyryl)
1,3,4-oxadiazole 0.12 parts by mass Polymerization initiator A 0.05 parts by mass Phenothiazine 0.01 parts by mass Surfactant 2 0.06 parts by mass ----------- --------------------------

<Binder 2>
-Polymer (benzyl methacrylate / methacrylic acid / methyl methacrylate = 38/25/37 molar ratio random copolymer, molecular weight 40,000) 27 parts by mass-propylene glycol monomethyl ether acetate 73 parts by mass <Surfactant 2>
・ The following structure 1 30 mass parts ・ Methyl ethyl ketone 70 mass parts

Colored photosensitive resin compositions B to I for color filters were prepared in the same manner as described above except that the pigment dispersion compositions B to I 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 of each film obtained in the same manner as in Example 1 are shown in Table 3-B below.

[Table 3-B]
-------------------------
Sample Contrast Viscosity [cp]
-------------------------
Colored photosensitive resin A 21000 9
Colored photosensitive resin B 20000 17
Colored photosensitive resin C 21000 29
Colored photosensitive resin D 17000 10
Colored photosensitive resin E 22000 9
Colored photosensitive resin F 19000 38
Colored photosensitive resin G 21000 55
Colored photosensitive resin H 8000 17
Colored photosensitive resin I 11000 15
-------------------------

  As shown in Table 3-B, colored photosensitive resin compositions A to E and I using organic particles dispersed and formed as nanometer-sized particles with the organic pigment powder of the present invention have sufficiently high contrast. In addition, the colored photosensitive resin compositions A to C and E using the polymer compound represented by the general formula (1) exhibited a particularly high contrast. The level of contrast and viscosity required in the colored photosensitive resin composition is the same as that of the above-described dispersion composition.

(Example 4 and Comparative Example 4)
[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 3-2 below on a glass substrate coater (manufactured by FS Asia Co., Ltd., trade name: MH-1600) having a slit-like nozzle. A colored photosensitive resin composition K2 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 K2 was obtained. In addition, the preparation procedure of the colored photosensitive resin composition K2 is the same as the procedure of the previous resin composition K1.

[Table 3-2]
--------------------------------------
K pigment dispersion 2 25 parts by mass Propylene glycol monomethyl ether acetate 8.0 parts by mass Methyl ethyl ketone 53 parts by mass Binder 3 9.1 parts by mass Hydroquinone monomethyl ether 0.002 parts by mass DPHA liquid 4.2 parts by mass Polymerization initiator A 0. 16 parts by mass Surfactant 1 0.044 parts by mass ----------------------------------- −

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, (Fuji Film 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.

<K pigment dispersion 2>
・ 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 3>
・ 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

[Formation of red (R) pixels]
Using the colored photosensitive resin composition R1 having the composition described in Table 3-3 below on the substrate on which the image K is formed, the 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 the pigment are shown below. The procedure for preparing the colored photosensitive resin composition is the same as that for the colored photosensitive resin composition K2.
Photosensitive resin film thickness (μm) 1.60
Pigment coating amount (g / m ² ) 1.00
C. I. P. R. 254 coating amount (g / m ² ) 0.80
C. I. P. R. 177 coating amount (g / m ² ) 0.20

[Table 3-3]
--------------------------------------
R pigment dispersion A 40 parts by mass R pigment dispersion 2 (CIPR177) 4.5 parts by mass Propylene glycol monomethyl ether acetate 7.6 parts by mass Methyl ethyl ketone 37 parts by mass Binder 2 0.7 parts by mass DPHA solution 3.8 parts by mass 2 -Trichloromethyl- (p-styrylstyryl)
1,3,4-oxadiazole 0.12 parts by mass Polymerization initiator A 0.05 parts by mass Phenothiazine 0.01 parts by mass Surfactant 2 0.06 parts by mass ----------- --------------------------

<R pigment dispersion A>
Pigment dispersion composition A (CIPR 254) 11 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

[Formation of green (G) pixels]
A pixel on which heat treatment has been performed 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 3-4 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 amount of the pigment are shown below. The procedure for preparing the colored photosensitive resin composition is the same as that for the colored photosensitive resin composition K2.
Photosensitive resin film thickness (μm) 1.60
Pigment application amount (g / m ² ) 1.92
C. I. P. G. 36 coating amount (g / m ² ) 1.34
C. I. P. Y. 150 coating amount (g / m ² ) 0.58

[Table 3-4]
--------------------------------------
G pigment dispersion 1 (CIPG 36) 28 parts by mass Y pigment dispersion 1 (CIPI 150) 15 parts by mass Propylene glycol monomethyl ether acetate 29 parts by mass Methyl ethyl ketone 26 parts by mass Cyclohexanone 1.3 parts by mass Binder 3 2.5 parts by mass DPHA solution 3 0.5 part by mass 2-trichloromethyl- (p-styrylstyryl)
1,3,4-oxadiazole 0.12 parts by mass Polymerization initiator A 0.05 parts by mass Phenothiazine 0.01 parts by mass Surfactant 2 0.07 parts by mass ----------- --------------------------

  As the G pigment dispersion 1, “trade name: GT-2” manufactured by Fuji Film Electronics Materials Co., Ltd. was used. As the Y pigment dispersion 1, “trade name: CF Yellow EX3393” manufactured by Mikuni Color Co., Ltd. was used.

[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 3-5 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 the pigment are shown below. The film thickness of the photosensitive resin layer R1 and the coating amount of the pigment are shown below. The procedure for preparing the colored photosensitive resin composition is the same as that for the colored photosensitive resin composition K2.
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

[Table 3-5]
--------------------------------------
B pigment dispersion 1 (CIPB15: 6) 8.6 parts by mass B pigment dispersion 2 (CIPB15: 6 + CIPV23) 15 parts by mass Propylene glycol monomethyl ether acetate 28 parts by mass Methyl ethyl ketone 26 parts by mass Binder 4 17 parts by mass DPHA solution 4.0 Parts by mass 2-trichloromethyl- (p-styrylstyryl)
1,3,4-oxadiazole 0.17 parts by mass Phenothiazine 0.02 parts by mass Surfactant 2 0.06 parts by mass ------------------- ------------------

  As the B pigment dispersion 1, “trade name: CF Bull-EX3357” manufactured by Mikuni Dye Co., Ltd. was used. As the B pigment dispersion 2, “trade name: CF Bull-EX3383” manufactured by Mikuni Color Co., Ltd. was used.

<Binder 4>
・ 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 pigment dispersion composition A used for the R pigment dispersion A, R pigment dispersions B to I were prepared using the pigment dispersion compositions B to I, respectively. Then, color filters B to I were prepared in the same manner as the color filter A, except that R pigment dispersions B to I were used instead of the R pigment dispersion A, respectively.

The contrast of each color filter was measured in the same manner as in Example 1 and Comparative Example 1, and the light resistance was measured as described below. The results are shown in Table 3-C.
[Measurement of light resistance]
The sample used for the measurement of the contrast 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 and used as an indicator of light resistance. 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. A smaller color difference means higher light resistance.

[Table 3-C]
---------------------------
Color filter Contrast Light resistance (color difference Δ)
---------------------------
A 21000 1.4
B 19000 1.6
C 20000 1.6
D 15000 1.5
E 22000 3.9
F 18000 2.6
G 21000 3.2
H 7000 3.8
I 9000 4.1
---------------------------

From the above results, it can be seen that the color filters A to E and I of the present invention exhibit sufficiently high contrast and light resistance. Note that the contrast required when a high-quality color filter is used is 10,000 or more, and the color difference can be distinguished by a viewer if the color difference is two or more. This difference is further enlarged by long-term use (for example, one year or more), and becomes a significant difference on the display screen.
Furthermore, the color filters A to E using the polymer compound represented by the general formula (1) exhibited much higher contrast among the examples.

(Example 5 and Comparative Example 5)
[Production and Evaluation of Liquid Crystal Display]
A liquid crystal display device was prepared using the color filters A to I, 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 prepared 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
FH-2413F manufactured by Materials Co., Ltd.): 53.3 parts by mass / methyl ethyl ketone: 46.7 parts by mass / Megafac F-780F (manufactured by Dainippon Ink & Chemicals, Inc.): 0.04 parts by mass ( Creation of liquid crystal display device)
An alignment film made of polyimide was further provided on the liquid crystal display substrate obtained above.
After that, an epoxy resin sealant is printed at a position corresponding to a black matrix outer frame provided around the pixel group of the color filter, and MVA mode liquid crystal is dropped and bonded to the counter substrate. The bonded substrate was heat treated to cure the sealant. Polarizing plates HLC2-2518 manufactured by Sanlitz Co., Ltd. were 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. .

[Production and Evaluation of Liquid Crystal Display]
In the same manner as the color filter A, a liquid crystal display device was manufactured using the color filters B to I, and the display characteristics were evaluated.

  Compared with the liquid crystal display device using the color filters F to H of the comparative example, the liquid crystal display device using the color filters A to E and I of the present invention is excellent in blackness and red descriptive power, and has no display unevenness. It was confirmed that good display characteristics were exhibited.

(Example 6 and Comparative Example 6)
[Production of color filter (production by lamination of photosensitive resin transfer material)]
[Production of photosensitive resin transfer material]
On a polyethylene terephthalate film temporary support having a thickness of 75 μm, a coating solution for a thermoplastic resin layer having the following formulation H2 was applied and dried using a slit nozzle. Next, an intermediate layer coating solution having the following formulation P2 was applied and dried. Furthermore, the colored photosensitive resin composition K2 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.
In this way, a photosensitive resin transfer material K3 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 H2>
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 2 0.54 parts by mass

<Intermediate layer coating solution: prescription P2>
・ 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 compositions K101 and G101 having the compositions described in Tables 3-6 to 3-8 below are used as the colored photosensitive resin composition K2 used in the production of the photosensitive resin transfer material K3. 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.

[Table 3-6] R101
--------------------------------------
R pigment dispersion A 40 parts by mass R pigment dispersion 2 (CIPR177) 4.5 parts by mass Propylene glycol monomethyl ether acetate 7.6 parts by mass Methyl ethyl ketone 37 parts by mass Binder 2 0.8 parts by mass DPHA solution 4.4 parts by mass 2 -Trichloromethyl- (p-styrylstyryl)
1,3,4-oxadiazole 0.14 parts by weight Polymerization initiator A 0.06 parts by weight Phenothiazine 0.01 parts by weight Additive 1 0.52 parts by weight Surfactant 2 0.06 parts by weight ---- ----------------------------------

[Table 3-7] G101
--------------------------------------
G pigment dispersion 1 (CIPG36) 28 parts by mass Y pigment dispersion 1 (CIPI150) 15 parts by mass Propylene glycol monomethyl ether acetate 29 parts by mass Methyl ethyl ketone 26 parts by mass Cyclohexanone 1.3 parts by mass Binder 3 3.0 parts by mass DPHA solution 4 .3 parts by mass 2-trichloromethyl- (p-styrylstyryl)
1,3,4-oxadiazole 0.15 parts by mass Polymerization initiator A 0.06 parts by mass Phenothiazine 0.01 parts by mass Surfactant 2 0.07 parts by mass ----------- --------------------------

[Table 3-8] B101
--------------------------------------
B pigment dispersion 1 (CIPB15: 6) 8.6 parts by mass B pigment dispersion 2 (CIPB15: 6 + CIPV23) 15 parts by mass Propylene glycol monomethyl ether acetate 28 parts by mass Methyl ethyl ketone 26 parts by mass Binder 4 18.5 parts by mass DPHA solution 4 .3 parts by mass 2-trichloromethyl- (p-styrylstyryl)
1,3,4-oxadiazole 0.17 parts by mass Phenothiazine 0.02 parts by mass Surfactant 2 0.06 parts by mass ------------------- ------------------

  In addition, among the compositions described in Table 3-6, the additive 1 used was a phosphate ester special activator (Takamoto Kasei Co., Ltd., trade name: HIPLAAD ED152).

[Formation of black (K) image]
The alkali-free glass substrate was washed with a rotating brush having nylon hair while spraying a glass detergent solution adjusted to 25 ° C. for 20 seconds by showering, and after washing with pure water shower, silane coupling solution (N-β (aminoethyl)) A 0.3% by mass aqueous solution of γ-aminopropyltrimethoxysilane, trade name: KBM603, manufactured by Shin-Etsu Chemical Co., Ltd.) was sprayed for 20 seconds with a shower and washed with pure water. This substrate was heated at 100 ° C. for 2 minutes with a substrate preheating device and sent to the next laminator.
After peeling off the protective film of the photosensitive resin transfer material K2, 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 K2. However, the exposure amount was 40 mJ / cm ² , and development with a sodium carbonate developer was 35 ° C. for 35 seconds. The film thickness of the photosensitive resin layer R101 and the coating amount of pigments (CIPR 254 and CIPR 177) are shown below.
Photosensitive resin film thickness (μm) 2.00
Pigment coating amount (g / m ² ) 1.00
C. I. P. R. 254 coating amount (g / m ² ) 0.80
C. I. P. R. 177 coating amount (g / m ² ) 0.20
The substrate on which the image K and the pixel R were formed was again cleaned with a brush as described above, and after pure water shower cleaning, the 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 application amount (g / m ² ) 1.92
C. I. P. G. 36 coating amount (g / m ² ) 1.34
C. I. P. Y. 150 coating amount (g / m ² ) 0.58
The substrate on which the image K, the pixel R, and the pixel G were formed was again cleaned with a brush as described above, and after pure water shower cleaning, the silane coupling liquid was not used and the substrate was sent to a substrate preheating device.

[Formation of blue (B) pixels]
Using the photosensitive resin transfer material B101, heat-treated blue (B) pixels B were obtained in the same process as the photosensitive resin transfer material R101. However, the exposure amount was 30 mJ / cm ² , and development with a sodium carbonate developer was 36 ° C. for 40 seconds. The film thickness of the photosensitive resin layer B101 and the coating 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.

  The R pigment dispersion A was changed to the R pigment dispersions B to I, respectively, to the color filter A1, and the color filters B1 to I1 were produced. At this time, the color filter was produced immediately after the dispersion was prepared (within 24 hours).

The contrast of the obtained color filters A1 to I1 and the contrast of the color filter produced after preparing each R pigment dispersion and leaving it still for 7 days are shown.
[Table 3-D]
--------------------------------------
Color filter Prepared immediately after dispersion preparation Prepared 7 days after dispersion preparation
Color filter contrast Color filter contrast -------------------------------------
A1 18000 18000
B1 17000 16000
C1 17000 14000
D1 14000 13000
E1 18000 18000
F1 17000 11000
G1 17000 9000
H1 6000 2000
I1 9000 8000
--------------------------------------

As shown in Table 3-D above, the color filter produced using the organic pigment powder of the present invention showed sufficient contrast (color filters A1 to E1 and I1), and the one that was allowed to stand after preparation of the dispersion. Even when used, there was almost no decrease in contrast (the level of contrast required for a high-quality color filter is as described above).
Among them, the one using the compound represented by the general formula (1) shows a higher contrast (color filters A1 to C1 and E1), and even if it has such a high contrast, the preparation of the dispersion It was hardly affected by the later standing.
From these results, the organic pigment powder of the present invention exhibits high dispersion stability when made into a dispersion, and also realizes high contrast as a color filter, and can realize stable and high product quality and manufacturing quality. It can be seen that it is.

(Example 7 and Comparative Example 7)
[Production and Evaluation of Liquid Crystal Display]
A liquid crystal display device was produced using the color filters A1 to I1 in the same manner as in Example 5 and Comparative Example 5, and the display characteristics were evaluated.
Compared to the liquid crystal display device using the color filters F1 to H1 of the comparative example, the liquid crystal display device using the color filters A1 to E1 and I1 of the present invention is excellent in blackness and red descriptive power and has a good display. It was confirmed to show characteristics.

Example 8 and Comparative Example 8
Pigment dispersion compositions K and L were prepared by using Pigment Green 36 and Pigment Blue 15: 6 in place of Pigment Red 254 in the preparation of Pigment Dispersion Composition A, respectively.
Pigment dispersion compositions K and L were used in place of the pigments PG36 and PB15: 6 in the preparation of the G ink 1 and the preparation of the B ink 1, respectively, and the pigment concentration was not changed except for the benzyl methacrylate-methacrylic acid copolymer. Thus, G ink 2 and B ink 2 were prepared by reducing the amount of diethylene glycol monobutyl ether acetate. G ink 2 was used instead of G ink 1 and B ink 2 was used instead of B ink 1 as an inkjet ink for color filters. As a result, both G ink 2 and B ink 2 exhibited low viscosity and high contrast, and exhibited excellent image display performance when incorporated into a liquid crystal display device as a color filter.

Claims (14)

A method for producing an organic pigment powder comprising fine particles of an organic pigment and a polymer compound having a mass average molecular weight of 1000 or more,
An organic pigment solution in which the organic pigment is dissolved in a first solvent that is a good solvent that does not contain an organic acid, and a second solvent that is a poor solvent for the organic pigment are mixed, Precipitating the organic pigment as nanometer-sized fine particles,
After preparing the mixed solution, the solvent is removed, and then the polymer compound represented by the following general formula (1) is introduced into 10 to 1000 parts by mass and a third solvent with respect to 100 parts by mass of the organic pigment. And
A method for producing an organic pigment powder that further removes the solvent again to obtain an organic pigment powder having a solid content concentration of 60% by mass or more.

[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 basic group having a nitrogen atom, a urea group, a urethane group, a group having a coordinating oxygen atom, a hydrocarbon group having 4 or more carbon atoms, an alkoxysilyl group, an epoxy group, an isocyanate group, and A monovalent organic group having a group selected from the group consisting of a hydroxyl group, or a monovalent organic group containing an organic dye structure or a heterocyclic ring which may have a substituent. However, n pieces of A ¹ may be the same as or different from each other. m represents a number of 1 to 8, n represents a number of 2 to 9, and m + n satisfies 3 to 10. P ¹ represents a polymer compound residue. ]
[Third solvent: an organic solvent selected from an ester compound solvent, an alcohol compound solvent, an aromatic compound solvent, and an aliphatic compound solvent] 2. The method of producing an organic pigment powder according to claim 1, wherein the organic pigment solution and the second solvent are mixed under a condition that the Reynolds number Re represented by the following formula (1) is 50 or more. .
Re = ρUL / μ Equation (1)
[In formula (1), Re represents the Reynolds number, ρ represents the density of the organic pigment solution, U represents the relative speed at which the organic pigment solution and the second solvent meet, and L represents the organic pigment solution and the second solvent. 2 represents the equivalent diameter of the flow path or supply port where the solvent meets, and μ represents the viscosity coefficient of the organic pigment solution. ] Wherein the first solvent is an aqueous medium, an alcohol compound solvent, a ketone compound solvent, an ether compound solvent, a sulfoxide compound solvent, an ester compound solvent, the amide compound solvent or in claim 1 or 2, characterized in that a mixture of these, The manufacturing method of the organic pigment powder of description. The second solvent is an aqueous medium, an alcohol compound solvent, a ketone compound solvent, an ether compound solvent, a sulfoxide compound solvent, an ester compound solvent, or any one of claims 1 to 3, characterized in that a mixture of these, The manufacturing method of the organic pigment powder as described in 2. above. The third solvent is an aqueous medium, an alcohol compound solvent, a ketone compound solvent, an ether compound solvent, a sulfoxide compound solvent, an ester compound solvent, an amide compound solvent, an organic acid compound solvent, or a mixture thereof. Item 5. The method for producing an organic pigment powder according to any one of Items 1 to 4 .   6. The removal of the solvent before or after the introduction of the third solvent, the solvent is removed by a solid-liquid or gas-liquid drying method to pulverize the fine particles. 2. A method for producing an organic pigment powder according to item 1.   The method for producing an organic pigment powder according to any one of claims 1 to 6, wherein ethyl lactate, ethyl acetate, or ethanol is used as the third solvent.   The method for producing an organic pigment powder according to any one of claims 1 to 7, wherein an average particle diameter of the organic pigment fine particles is 1 nm to 1 µm.   The method for producing an organic pigment powder according to any one of claims 1 to 8, wherein the amount of the third solvent introduced is 100 to 300,000 parts by mass with respect to 100 parts by mass of the organic pigment fine particles. The method of producing an organic pigment dispersion composition characterized in that the organic pigment powder obtained by the production method according Ru are contained and a fourth solvent to any one of claims 1-9. The method for producing an organic pigment dispersion composition according to claim 10, wherein the fourth solvent is an ester compound solvent, an alcohol compound solvent, an aromatic compound solvent, or an aliphatic compound solvent. A method for producing a pigment-dispersed photoresist, comprising: an organic pigment-dispersed composition obtained by the method according to claim 10 or 11; and a cured compound. The manufacturing method of the color filter for liquid crystal display devices characterized by making the resin composition contain the organic pigment dispersion composition obtained by the method of Claim 10 or 11, and solidifying this resin composition. Method of manufacturing a liquid crystal display device to produce a liquid crystal display device for color filters by the method of claim 1 3, further characterized in that the display screen incorporating the same.