JP2009215381A - Organic pigment dispersion - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an organic pigment dispersion which is capable of maintaining dispersion stability for a long term and excellent in temporal stability, and to provide ink-jet ink for a color filter using the organic pigment dispersion, a coloring photosensitive resin composition, a photosensitive resin transferring material, a color filter of high display quality having high contrast produced thereby and a liquid crystal display including it. <P>SOLUTION: The organic pigment dispersion is provided by: mixing a solution made by dissolving an organic pigment in a good solvent with a poor solvent of the organic pigment compatible with the good solvent to prepare a dispersion of organic pigment nanoparticles made by generating the organic pigment as nanosized fine particles; and then mixing two or more different pigment concentrates obtained by concentrating the dispersion in the state of higher pigment concentration than that at the time of generating the particles, followed by being diluted in desired pigment concentration. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

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

  In recent years, the quality of image-related precision equipment such as a color image sensor and a color liquid crystal display device has been rapidly improved and its application has been rapidly expanded. Reflecting this, there has been a strong demand for high-quality display performance for color filters. As for the color material of the color filter, organic pigments have been used instead of dyes, and recently, pigment fine particles having a nanometer size level and being monodispersed and stable have been demanded. And the manufacturing method of the novel color filter using an inkjet technique is examined. As a result, a significant improvement in design freedom and a significant reduction in cost are expected, but there is still no dispersion of pigment fine particles suitable for that and capable of exhibiting sufficient performance.

  Here, regarding the method for producing organic pigment particles, breakdown methods such as a bead mill method and a salt milling method are common. In the milling method, it takes a lot of time and energy to sufficiently refine the organic pigment and disperse it in the composition. Also, the types of pigment that can be used are limited. As the pigment becomes finer, the dispersion composition may exhibit high viscosity, and in some cases, the dispersion composition may gel during storage and become unusable.

On the other hand, recently, a method for producing a pigment dispersion composition by a liquid phase method has been developed, and it has been pointed out that the composition can be used as a high-contrast color filter (see, for example, Patent Document 1). However, the method described in Patent Document 1 has a problem in that when particles of differently prepared different pigment solvent dispersions are mixed, agglomeration of pigment particles occurs and the contrast is lowered. Therefore, further higher contrast has been desired.
International Publication No. WO2006 / 121016 Pamphlet

  An object of the present invention is to provide an organic pigment dispersion excellent in temporal stability that can maintain dispersion stability over a long period of time. In addition, an inkjet ink for a color filter using the organic pigment dispersion, a colored photosensitive resin composition, and a photosensitive resin transfer material, and a high-quality color filter having a high contrast produced by these, and the same are provided. An object is to provide a liquid crystal display device.

〔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。〕
［６］［１］〜［５］のいずれか１項に記載された顔料分散物と、バインダーと、モノマーもしくはオリゴマーと、光重合開始剤もしくは光重合開始剤系とを含むことを特徴とする着色感光性樹脂組成物。
［７］カラーフィルタ用インクジェットインクであることを特徴とする［６］項に記載の着色感光性樹脂組成物。
［８］仮支持体上に、少なくとも、［６］項に記載の着色感光性樹脂組成物を含む感光性樹脂層を設けたことを特徴とする感光性樹脂転写材料。
［９］［６］もしくは［７］項に記載の着色感光性樹脂組成物、及び／又は［８］項に記載の感光性樹脂転写材料を用いて作製したことを特徴とするカラーフィルタ。
［１０］［９］項に記載のカラーフィルタを備えたことを特徴とする液晶表示装置。
［１１］有機顔料を良溶媒に溶解した溶液と、該良溶媒と相溶する前記有機顔料の貧溶媒とを混合して、前記有機顔料をナノサイズの微粒子として生成させた有機顔料ナノ粒子の分散物を調製し、次いで該分散物を前記粒子生成時よりも顔料濃度が高い状態に濃縮することにより得られる異なる２種以上の顔料濃縮物を混合後、所望の顔料濃度に希釈することを特徴とする有機顔料ナノ粒子分散物の製造方法。 The above problems have been achieved by the following means.
[1] An organic pigment nanoparticle obtained by mixing a solution obtained by dissolving an organic pigment in a good solvent and a poor solvent of the organic pigment compatible with the good solvent to produce the organic pigment as nano-sized fine particles. By preparing a dispersion, and then mixing two or more different pigment concentrates obtained by concentrating the dispersion to a state in which the pigment concentration is higher than that at the time of particle formation, and then diluting to a desired pigment concentration Obtained organic pigment dispersion.
[2] The organic pigment dispersion as described in the item [1], wherein the pigment concentrate is prepared by precipitating the organic pigment fine particles and then removing the solvent from the mixed solution.
[3] A pigment concentrate was prepared by precipitating the organic pigment fine particles, substituting the solvent component of the mixed solution with a substitution solvent, and then removing the solvent component containing the substitution solvent. The organic pigment dispersion according to item [1], which is characterized.
[4] The organic pigment dispersion according to any one of [1] to [3], wherein a polymer compound having a mass average molecular weight of 1000 or more is contained.
[5] The organic pigment dispersion as described in the item [4], wherein the polymer compound is represented by the following general formula (1).

[Wherein, R ¹ represents a (m + n) -valent linking group, and R ² represents a single bond or a divalent linking group. A ¹ is an acidic group, a 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. ]
[6] A pigment dispersion described in any one of [1] to [5], a binder, a monomer or an oligomer, and a photopolymerization initiator or a photopolymerization initiator system. Colored photosensitive resin composition.
[7] The colored photosensitive resin composition as described in the item [6], which is an inkjet ink for a color filter.
[8] A photosensitive resin transfer material, wherein a photosensitive resin layer containing at least the colored photosensitive resin composition according to [6] is provided on a temporary support.
[9] A color filter produced using the colored photosensitive resin composition according to the item [6] or [7] and / or the photosensitive resin transfer material according to the item [8].
[10] A liquid crystal display device comprising the color filter according to the item [9].
[11] An organic pigment nanoparticle produced by mixing a solution obtained by dissolving an organic pigment in a good solvent and a poor solvent of the organic pigment compatible with the good solvent to produce the organic pigment as nano-sized fine particles. Preparing a dispersion, and then mixing two or more different pigment concentrates obtained by concentrating the dispersion to a state in which the pigment concentration is higher than that at the time of the particle formation, and then diluting to a desired pigment concentration. A method for producing an organic pigment nanoparticle dispersion.

The pigment dispersion composition of the present invention, the colored photosensitive composition containing the pigment dispersion composition, and the photosensitive resin transfer material can provide a color filter with high contrast and high display quality.
The liquid crystal display device using the color filter of the present invention has the excellent effect of blackening and good reproducibility.

Hereinafter, the present invention will be described in detail.
[Organic pigment dispersion]
The organic pigment dispersion of the present invention is prepared by mixing a solution in which an organic pigment is dissolved in a good solvent and a poor solvent for the organic pigment that is compatible with the good solvent to produce the organic pigment as nano-sized fine particles. A mixture of two or more different pigment concentrates obtained by preparing a dispersion of organic pigment nanoparticles, and then concentrating the dispersion to a state in which the pigment concentration is higher than that at the time of the particle formation. Obtained by diluting to a concentration.
In the present invention, the “organic pigment dispersion” refers to a dispersion of organic pigment particles in a medium, which may be a liquid composition or a solid composition, a pigment dispersion, an inkjet ink. , A pigment dispersion resist, a photosensitive transfer material having a pigment, and a pixel part of a color filter.

  The kind of the organic pigment used in the present invention is not limited in terms of hue. For example, perylene compound pigment, perinone compound pigment, quinacridone compound pigment, quinacridone quinone compound pigment, anthraquinone compound pigment, anthanthrone compound pigment, benz Imidazolone 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 pigment, Examples thereof include thioindigo compound pigments, isoindoline compound pigments, isoindolinone compound pigments, pyranthrone compound pigments, isoviolanthrone compound pigments, and mixtures thereof.

  Among them, a perylene compound pigment, a quinacridone compound pigment, an anthraquinone compound pigment, a diketopyrrolopyrrole compound pigment, an aminoanthraquinone compound pigment, a dioxazine compound pigment, a phthalocyanine compound pigment, or an azo compound pigment is preferable, and a diketopyrrolopyrrole compound More preferred are pigments, aminoanthraquinone compound pigments, phthalocyanine compound pigments, dioxazine compound pigments, or azo compound pigments.

  In the present invention, two or more different organic pigments are used. The combination of organic pigment species at this time is not particularly limited, but when two types of organic pigments are used, a combination of a diketopyrrolopyrrole compound pigment and an aminoanthraquinone compound pigment, a combination of a phthalocyanine compound pigment and an azo compound pigment, or A combination of a phthalocyanine compound pigment and a dioxazine compound pigment is preferred. Moreover, you may combine with organic pigment | dye (dye etc.), a polymeric organic material, etc.

The method for preparing the organic pigment dispersion of the present invention will be described below.
In the present invention, first, a solution in which an organic pigment is dissolved in a good solvent (first solvent) and a solvent (second solvent) that is compatible with the good solvent and becomes a poor solvent for the organic pigment. By mixing, a dispersion of organic pigment nanoparticles in which organic pigments are produced as nano-sized fine particles is prepared.
Here, the combination of the good solvent and the poor solvent needs to have a sufficient difference in the solubility of the organic pigment, and it is necessary to select a preferable one according to the organic pigment, but enables the process in the present invention. Any combination is possible.

The good solvent (first solvent) is not particularly limited as long as it can dissolve the organic pigment to be used and is compatible with or uniformly mixed with the poor solvent (second solvent). As for the solubility of the organic pigment in a good solvent, the solubility of the organic pigment is preferably 0.2% by mass or more, and more preferably 0.5% by mass or more. Although there is no particular upper limit to the solubility of the organic pigment in the good solvent, it is practical that it is 50% by mass or less in consideration of a commonly used organic pigment. This solubility may be the solubility when dissolved in the presence of an acid or alkali. In the present invention, two or more kinds of organic pigments different from each other are dissolved in a good solvent, but the two or more good solvents used at this time may be different from each other or the same.
The compatibility or uniform mixing property of the first solvent and the second solvent is preferably such that the amount of the first solvent dissolved in the second solvent is 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 good solvents include aqueous solvents, alcohol compound solvents, amide compound solvents, ketone compound solvents, ether compound solvents, aromatic compound solvents, carbon disulfide solvents, aliphatic compound solvents, nitrile compound solvents, sulfoxide compound solvents, halogens. Compound solvents, ester compound solvents, ionic liquids, mixed solvents thereof, and the like, aqueous solvents, alcohol compound solvents, ketone compound solvents, ether compound solvents, sulfoxide compound solvents, ester compound solvents, amide compound solvents, or these Mixtures are preferred, aqueous solvents, alcohol compound solvents, ester compound solvents, sulfoxide compound solvents or amide compound solvents are preferred, aqueous solvents, sulfoxide compound solvents or amide compound solvents are more preferred, sulfoxide compound solvents or Bromide compound solvents are particularly preferred.

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

  There are some common examples of those listed as specific examples of good solvents and those listed as poor solvents, but the same solvents are not combined as good solvents and poor solvents. It is sufficient that the solubility in is sufficiently higher than the solubility in a poor solvent. For example, the solubility difference 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 difference in solubility between the good solvent and the poor solvent, 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 a good solvent, a pigment dissolution accelerator such as acid or alkali may be added and dissolved. In general, in the case of a pigment having an alkaline and dissociable group in the molecule, addition of an alkali is performed. Is preferred. For example, quinacridone, diketopyrrolopyrrole and disazo condensation compound pigments are alkaline and dissolved. Phthalocyanine compound pigments are dissolved in an acidic manner, but some of them are dissolved in an alkaline manner, and the mechanism of dissolving in an alkaline manner is not clear.

  Examples of the alkali include inorganic bases such as lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, and barium hydroxide, or organic bases such as trialkylamine, diazabicycloundecene (DBU), and metal alkoxide. Of these, trialkylamines and metal alkoxides are preferable, and metal alkoxides are more preferable. The amount of alkali added 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, and 1.0 Particularly preferred is ˜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 include inorganic acids such as sulfuric acid, hydrochloric acid, and phosphoric acid, or organic acids such as acetic acid, trifluoroacetic acid, oxalic acid, methanesulfonic acid, and trifluoromethanesulfonic acid. Among them, inorganic acids are preferable. More preferably, it is sulfuric acid. The amount of acid to be added is not particularly limited, but it is often used in excess compared to the base. Regardless of the inorganic acid and organic acid, the organic pigment is preferably 3 to 500 molar equivalents, more preferably 10 to 500 molar equivalents, and particularly preferably 30 to 200 molar equivalents. .

  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.

  While dissolution of the organic pigment proceeds in a good solvent, decomposition of the organic pigment molecule may proceed. Although the decomposition of the pigment molecules will be described later, it is preferable to suppress the decomposition of the organic pigment when the organic pigment solution and the poor solvent are brought into contact with each other. In particular, when the organic pigment is dissolved by the action of the pigment dissolution accelerator and at the same time the decomposition of the organic pigment molecule proceeds, the pigment dissolution accelerator is added to the good solvent immediately before contacting the organic pigment solution with the poor solvent. Is preferably added. At this time, for example, an organic pigment is added to a good solvent (for example, dimethyl sulfoxide), prepared as a dispersion in which the organic pigment is not completely dissolved, and a pigment dissolution accelerator composed of the acid or alkali is added. An embodiment in which the pigment solution is mixed with the poor solvent immediately after the pigment solution is preferable.

  The viscosity of the organic pigment solution is preferably 0.5 to 80.0 mPa · s, and more preferably 1.0 to 50.0 mPa · s.

  Although a poor solvent (2nd solvent) is not specifically limited, It is preferable that the solubility of an organic pigment is 0.02 mass% or less, and it is more preferable that it is 0.01 mass% or less. Although there is no particular lower limit to the solubility of the organic pigment in the poor solvent, 0.000001% by mass or more is practical in consideration of a commonly used organic pigment. This solubility may be the solubility when dissolved in the presence of an acid or alkali. In addition, the compatibility or uniform mixing property of the good solvent and the poor solvent is preferably 30% by mass or more, more preferably 50% by mass or more, with respect to the poor solvent.

  Examples of the poor solvent include an aqueous solvent, an alcohol compound solvent, a ketone compound solvent, an ether compound solvent, an aromatic compound solvent, a carbon disulfide solvent, an aliphatic compound solvent, a nitrile compound solvent, a halogen compound solvent, an ester compound solvent, and an ion. An aqueous solvent, an alcohol compound solvent, a ketone compound solvent, an ether compound solvent, an ester compound solvent, or a mixture thereof, and an aqueous solvent, an alcohol compound solvent, or an ester compound solvent is more preferable. preferable.

Specific solvents that are preferably used as the first solvent or the second solvent will be described below.
Examples of the aqueous solvent include water, hydrochloric acid, sodium hydroxide aqueous solution, and the like.
Examples of the alcohol compound solvent include methanol, ethanol, isopropyl alcohol, n-propyl alcohol, 1-methoxy-2-propanol, 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.

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 sulfoxide compound solvent include dimethyl sulfoxide, diethyl sulfoxide, hexamethylene sulfoxide, sulfolane and the like.
Examples of the halogen compound solvent include dichloromethane and trichloroethylene.
Examples of the ester compound solvent include ethyl acetate, ethyl lactate, 2- (1-methoxy) propyl acetate and the like.
The ionic liquids, for example, 1-butyl-3-methylimidazolium and PF ₆ ^-, etc. and salts thereof.

  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 material 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 material 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 material that is usually used.

  There are no particular limitations on the conditions of the poor solvent when the pigment nanoparticles are precipitated and formed, and a range from normal pressure to subcritical and supercritical conditions can be selected. The temperature at normal pressure is preferably −30 to 100 ° C., more preferably −10 to 60 ° C., and particularly preferably 0 to 30 ° C.

  When mixing the organic pigment solution and the poor solvent, either of them may be added and mixed, but it is preferable to jet the organic pigment solution into the poor solvent and mix, and the poor solvent is stirred at that time. It is preferable that the The stirring speed is preferably 100 to 10,000 rpm, more preferably 150 to 8000 rpm, and particularly preferably 200 to 6000 rpm. A pump or the like may be used for the addition, or it may not be used. Moreover, although addition in a liquid or addition outside a liquid may be sufficient, addition in a liquid is more preferable. 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 poor solvent, the particle diameter of the pigment nanoparticles to be formed can be controlled. 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 and the second solvent meet. 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 equation (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 Formula (2)
It is preferable to form particles by injecting an organic pigment solution into a poor 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 poor 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 a stationary poor 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 in the range of materials preferably used in the present invention, it is actually 0.8 to 2.0 kg / m ³ , for example. Is. Also, the viscosity coefficient μ of the organic pigment solution is a value determined by the material used, the environmental 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 size of pigment nanoparticles (pigment particles having a particle size of nanometer size), preferably 100 or more, and more preferably 150 or more. More preferred. Although there is no particular upper limit to the number of lay nozzles, for example, favorable pigment nanoparticles can be controlled and obtained by adjusting 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 diameter by increasing the Reynolds number.

The mixing ratio of the organic pigment solution and the poor solvent is preferably 1/50 to 2/3 by volume, more preferably 1/40 to 1/2, and particularly preferably 1/20 to 3/8.
When pigment nanoparticles are deposited, the concentration of nanoparticles in the liquid is not particularly limited, but the pigment nanoparticles are preferably in the range of 10 to 40,000 mg, more preferably in the range of 20 to 30000 mg with respect to 1000 ml of the solvent. Especially 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 poor solvent is a 10-2000L preparation scale, and it is more preferable that it is a 50-1000L preparation scale.

  Regarding the particle diameter of pigment nanoparticles, there is a method of expressing the average size of the population by quantifying by a measurement method, but as a common method, the mode diameter indicating the maximum value of the distribution, the center of the integral distribution curve There are median diameters corresponding to the values, 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 a number. Mean diameter. The average particle diameter of the pigment nanoparticles (primary particles) is nanometer size, the average particle diameter is preferably 1 nm to 0.5 μm, more preferably 1 to 200 nm, and more preferably 2 to 100 nm. Further preferred is 5 to 80 nm. The particles formed in the present invention may be crystalline particles, amorphous particles, or a mixture thereof.

In the present invention, the ratio (Mv / Mn) of the volume average particle diameter (Mv) and the number average particle diameter (Mn) is used as an index representing the monodispersity of the particles unless otherwise specified. The monodispersity of the pigment nanoparticles (primary particles), that is, Mv / Mn, is preferably 1.0 to 2.0, more preferably 1.0 to 1.8, and 1.0 to 1 .5 is particularly preferred.
Examples of the method for measuring the particle size of pigment nanoparticles include a microscopy method, a mass method, a light scattering method, a light blocking method, an electrical resistance method, an acoustic method, and a dynamic light scattering method. Is particularly preferred. Examples of the microscope used for the microscopy include a scanning electron microscope and a transmission electron microscope. Examples of the particle measuring apparatus using the dynamic light scattering method include Nikkiso's Nanotrac UPA-EX150, Otsuka Electronics' dynamic light scattering photometer DLS-7000 series (all are trade names).

  In the present invention, in preparing a dispersion by precipitating pigment nanoparticles, it is preferable to include a dispersant in at least one of the pigment solution and the poor solvent, and it is preferable to include a dispersant in at least the pigment solution.

It is also preferable to use pigment nanoparticles that have been surface-treated with a dispersant in advance, and the pigment nanoparticles may be subjected to a surface treatment that can promote adsorption of the dispersant. The dispersant has the action of (1) quickly adsorbing on the deposited pigment surface 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, Japanese Patent Application Laid-Open No. 2000-239554, 2003-96329, 2001-31885, Japanese Patent Application Laid-Open No. 10-339949, Japanese Patent Publication No. 5-72943, and International Publication No. WO2006 / 121017. Examples include compounds described in paragraphs 0018 to 0033 of the pamphlet and Japanese Patent Application No. 2006-129714, 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 in the range of 1 to 500 parts by weight, more preferably in the range of 5 to 20 parts by weight. If the amount is less than 0.1 parts by mass, the dispersion stability of the 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, after preparing a dispersion of organic pigment nanoparticles, the dispersion is concentrated to a state where the pigment concentration is higher than that at the time of particle formation to obtain a pigment concentrate. At this time, after the pigment nanoparticles are precipitated, it is preferable to reduce or remove the solvent component (first solvent and second solvent) of the dispersion containing the precipitated particles (hereinafter, these steps are performed). Sometimes referred to as “concentration / removal step”). In addition, after the organic pigment fine particles are deposited, the solvent content of the mixed solution is replaced with a replacement solvent (third solvent) different from both the first solvent and the second solvent, and then the third solvent replacement solvent is included. The solvent component may be removed. In the solvent replacement here, it is not necessary to completely remove the first solvent and the second solvent, and the first solvent and the second solvent may remain within the range in which the third solvent acts. The amount by which the first solvent and the second solvent are reduced or removed will be described later as “concentration / removal amount”. By these operations, it is possible to obtain a nanoparticle concentrate or pigment nanoparticle powder suitable for a color filter coating liquid or ink jet ink.

  The concentration / removal step is not particularly limited. For example, an embodiment in which the solution is filtered through a filter to obtain a concentrated nanoparticle solution, an embodiment in which pigment nanoparticles are precipitated and concentrated by centrifugation, and an embodiment in which desalting and concentration is performed by ultrafiltration. Examples include a mode using spray drying, a mode in which the solvent is sublimated by vacuum freeze-drying, a mode in which the solvent is dried by heating or decompression, and a mode in which they are combined, and a combination of these. An embodiment using spray drying, an embodiment using spray drying, and an embodiment of drying and concentrating the solvent by heating to reduced pressure are preferred.

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

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

  In the aspect by filter filtration, for example, an apparatus such as pressure filtration can be used. Preferred filters include nanofilters and ultrafilters. At this time, it is preferable to filter-filter the organic nanoparticles concentrated and extracted as described below.

  The extraction solvent used for the concentration extraction is not particularly limited, but does not substantially mix with the dispersion solvent (for example, an aqueous solvent) of the organic nanoparticle dispersion (in the present invention, it is compatible with the mixture) The dissolution amount is preferably 50% by mass or less, more preferably 30% by mass or less, and there is no particular lower limit to the dissolution amount, but it is 1% by mass or more considering the solubility of ordinary solvents. It is practical.) A solvent that forms an interface when allowed to stand after mixing is preferable. In addition, this extraction solvent is a solvent that generates weak aggregation (floc that can be redispersed without applying high shearing force such as milling or high-speed stirring) in which organic nanoparticles can be redispersed in the extraction solvent. Is preferred. In such a state, it is possible to easily remove the dispersion solvent such as water by filter filtration or the like while wetting the target organic nanoparticles with the extraction solvent without causing strong aggregation that changes the particle size. This is preferable. The extraction solvent is preferably an ester compound solvent, an alcohol compound solvent, an aromatic compound solvent, or an aliphatic compound solvent, more preferably an ester compound solvent, an aromatic compound solvent, or an aliphatic compound solvent, and particularly preferably an ester compound solvent.

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

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

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

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

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

Any device may be used as the centrifuge as long as the organic nanoparticles can be precipitated. For example, in addition to a general-purpose device, a device having a skimming function (a function of sucking a supernatant layer during rotation and discharging it out of the system), a continuous centrifuge that continuously discharges solid matter, and the like can be given.
Centrifugation conditions are preferably 50 to 10000, more preferably 100 to 8000, and particularly preferably 150 to 6000 in terms of centrifugal force (a value representing how many times the gravitational acceleration is applied). Although the temperature at the time of centrifugation is based on the solvent seed | species of a dispersion liquid, -10-80 degreeC is preferable, -5-70 degreeC is more preferable, 0-60 degreeC is especially preferable.

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

Moreover, you may dry by the following aspects. For example, as dryers using hot air, shelf dryers, band dryers, stirring dryers, fluidized bed dryers, spray dryers, air dryers, etc., dryers using heat conduction are drum dryers, multiple dryers, etc. A tube dryer, a cylindrical dryer or the like is preferably used. Depending on the solvent composition, a freeze dryer or an infrared dryer can be used.
Among these means, from the viewpoint that it is suitable for obtaining pigment nanoparticle powder dried directly from the dispersion, a spray dryer (for example, COC-12 manufactured by Okawara Chemical Co., Ltd.), fluidized bed dryer ( For example, MSD-100 manufactured by Nara Machinery Co., Ltd. is particularly preferably used (both are trade names). Also, a plurality of drying means may be used in combination to obtain pigment nanoparticle 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. Processes such as obtaining pigment nanoparticle powders 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, it is possible to combine means such as depressurization, stirring and mixing and multi-stage depending on the type of dryer.

The amount to reduce or remove the solvent content (concentration / removal amount) is not particularly limited. However, in the aspect of reducing the solvent content, it is preferable to remove 50% by mass or more of the total solvent content, and to remove 75% by mass or more. Is more preferable. In the aspect of removing the solvent, it is preferable to remove 80% by mass or more of the total solvent, and more preferably 90% by mass or more.
When the solvent content is reduced by reducing or removing the solvent content, the water content in the remaining dispersion is not particularly limited, but is preferably 0.01 to 3% by mass, preferably 0.01 to 1%. It is more preferable to set it as the mass%. At this time, for example, it is preferable to remove the solvent component by the above-described drying method or the like to obtain a powder of pigment nanoparticles, for example, the solid content is preferably 50 to 100% by mass, and 70 to 100% by mass More preferably.
The concentration / removal step may be performed a plurality of times, for example, preferably before and / or after the addition of the third solvent described later.

In the present invention, it is preferable to redisperse the pigment nanoparticles in an aggregated state by concentration or powdering. The pigment nanoparticles contained in the concentrated liquid are usually sometimes aggregated due to the concentration. 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 pigment nanoparticles in such an agglomerated state, the pigment nanoparticles can be suitably redispersed, for example, by containing the following polymer compound.

  The organic pigment dispersion can be formed by controlling the soft aggregates of the organic pigment fine particles contained therein through a predetermined treatment / operation. Here, soft agglomeration means an agglomerated state that is weak enough to be redispersed as necessary as described above, and the soft agglomerates are sometimes called flocs. By doing in this way, for example, the organic nanoparticles precipitated in the aqueous dispersion can be flocated and quickly separated by filtration or the like. Then, the separated floc can be redispersed in an organic solvent suitable for production of a color filter, and an organic solvent-based dispersion can be efficiently obtained. That is, when the mixed solvent of the good solvent (first solvent) and the poor solvent (second solvent) is an aqueous solvent, this is efficiently replaced with a third solvent composed of an organic solvent, and the dispersion medium (continuous phase) Can be switched.

  In order to re-disperse the particles in the above-mentioned soft aggregation state, a normal dispersion method may be insufficient. The following polymer compound having a mass average molecular weight of 1000 or more acts on the formation and redispersion of such soft agglomerates (floc), and can be rapidly redispersed even if softly agglomerated once. Can be realized. Therefore, good fine dispersibility (characteristic that achieves uniform and fine particle size) and dispersion stability (uniform and fine particle size can be maintained for a long time) when deposited in a mixture of good and poor solvents. Characteristics) are maintained after the medium is switched to a final solvent suitable for the color filter and redispersed, and high performance in the color filter can be achieved. In addition, this polymer compound can achieve high performance in the color filter and the liquid crystal display device without interfering with the optical characteristics of the color filter.

In the present invention, a polymer compound having a mass average molecular weight of 1000 or more is preferably used, and a polymer compound represented by the following general formula (1) is more preferably used.

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 (where 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).
Examples of the “monovalent organic group having a urethane group” include —NHCOOR ¹⁶ , —OCONHR ¹⁷ (wherein R ¹⁶ and R ¹⁷ are each independently an alkyl group having 1 to 20 carbon atoms, 6 carbon atoms). 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 an acidic group, a basic group having a nitrogen atom, a urea group, or a monovalent organic group having a hydrocarbon group having 4 or more carbon atoms.

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

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

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.
Moreover, 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 preferable, and a polymer or copolymer of vinyl monomers is particularly preferable.
Furthermore, the polymer is preferably soluble in an organic solvent. If the affinity with the organic solvent is low, for example, when used as a pigment dispersant, the affinity with the dispersion medium is weakened, and it may not be possible to secure a sufficient adsorption layer for stabilizing the dispersion.
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, and the value of x and its preferred range are the same as n in the general 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. —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. O) —, —N (R ¹⁹ ) —, —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 (sb), wherein P ² is a polymer or copolymer of a vinyl monomer, an ester compound polymer, an ether compound polymer, a urethane polymer, or a modified product thereof, y Is a polymer compound in which x is 1 to 2 and x is 3 to 6. There. 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 present invention is preferably 1000 or more, more preferably 3000 to 100,000 in terms of mass average molecular weight, still more preferably 5000 to 80000, and more preferably 7000 to 60000. It is particularly preferred. 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) preferably used in the present invention 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 a terminal and a mercaptan having a plurality of functional groups (A ¹ or A ² in the general formula) are subjected to a Michael addition reaction.
3. A method in which a polymer in which a carbon-carbon double bond is introduced at a terminal 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 in which a plurality of mercaptans are introduced at the terminal and a functional group into which a carbon-carbon double bond is 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) can be obtained. 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 molecular weight measurement methods 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.

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.

The polymer compound may be water-soluble or oil-soluble, and may be water-soluble and oil-soluble.
The polymer compound may be added in a solution in an aqueous solvent or an organic solvent, in a solid state, or a combination thereof. Examples of the method of adding a solution dissolved in a solvent include a method of adding to an aggregated pigment nanoparticle solution in a state dissolved in the same solvent as the solvent, and a different solvent compatible with the solvent of the aggregated pigment nanoparticle solution. The method of adding in the state melt | dissolved in is mentioned. The concentration of the polymer compound when added in a solution dissolved in a solvent is not particularly limited, but is preferably 1 to 70% by mass, more preferably 2 to 65% by mass, and particularly preferably 3 to 60% by mass.
The polymer compound may be added at any time during or after the precipitation of pigment nanoparticles, during or after concentration, during or after the dispersion of aggregated pigment nanoparticles after concentration, or after the completion of these steps. Or may be added in multiple portions. In the present invention, a polymer compound having a mass average molecular weight of 1000 or more may be contained in the composition as a binder to be described later. For example, after the pigment nanoparticle deposit is concentrated, it may be added at the time of fine dispersion. preferable.

  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.

The amount of the polymer compound having a molecular weight of 1000 or more is preferably 0.1 to 1000 parts by weight, more preferably 5 to 500 parts by weight, and more preferably 10 to 300 parts by weight with respect to 100 parts by weight of the pigment. It is particularly preferable that
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, as described above, it is preferable to include a substitution solvent (third solvent) after pigment nanoparticle precipitation. The type of the third solvent is not particularly limited, but is preferably an organic solvent having an azeotropic property with the first solvent and / or the second solvent, for example, an ester compound solvent, an alcohol compound solvent, an aromatic compound solvent, Aliphatic compound solvents and ketone compound solvents are preferred, and ester compound solvents and ketone compound solvents are particularly preferred.

  Examples of the ester compound solvent include 2- (1-methoxy) propyl acetate, ethyl acetate, and ethyl lactate. Examples of the alcohol compound solvent include 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. Examples of the ketone compound solvent include methyl ethyl ketone, acetone, and cyclohexanone.

  Of these, ethyl lactate, ethyl acetate, acetone, 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 good solvent (first solvent) or the poor solvent (second solvent). Although the addition amount of a 3rd solvent is not specifically limited, It is preferable that it is 100-300000 mass parts with respect to 100 mass parts of organic nanoparticles, and it is more preferable that it is 500-10000 mass parts.

The timing of adding the substitution solvent is not particularly limited as long as it is after the precipitation of the pigment nanoparticles, but it is preferably added after the concentration / removal step described above. That is, it is preferable to replace the solvent component composed of the good solvent (first solvent) and the poor solvent (second solvent) in the mixed liquid in which the pigment nanoparticles are precipitated with the replacement solvent (third solvent).
When a pigment dispersion composition to be described later is used, after the first concentration / removal step (first concentration), the third solvent is added to replace the solvent, and the second concentration / removal step (second concentration). It is preferable to reduce the solvent content by concentration) to obtain a concentrated solution, or to remove the solvent content to obtain a powder. And a binder and / or a solvent can be added after that, and it can be set as a desired pigment dispersion composition.
Although the addition amount of the solvent for substitution is not specifically limited, It is preferable that it is 100-300000 mass parts with respect to 100 mass parts of pigment nanoparticles, and it is more preferable that it is 500-10000 mass parts.

  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 forming the pigment nanoparticles and the binder used for redispersion may be the same or different.

The pigment nanoparticle concentration of the pigment dispersion of the present invention is appropriately determined according to the purpose, but it is preferably 2 to 30% by mass of pigment nanoparticles, and preferably 4 to 20% by mass with respect to the total amount of the dispersion. More preferably, it is particularly preferably 5 to 15% by mass.
In the case of dispersing in the vehicle as described above, the amount of the binder and the dissolved dilution component is appropriately determined depending on the type of the organic pigment, etc. Preferably, it is 3-20 mass%, More preferably, it is 5-15 mass%. It is preferable that a dissolution dilution component is 5-80 mass%, and it is more preferable that it is 10-70 mass%.

In the concentrated pigment nanoparticle liquid with a reduced solvent content, as described above, the nanoparticles may aggregate. As a method of redispersing such aggregated pigment nanoparticles, for example, a dispersion method using ultrasonic waves or a method of applying physical energy can be used. The ultrasonic irradiation device used preferably has a function capable of applying an ultrasonic wave of 10 kHz or higher, and examples thereof include an ultrasonic homogenizer and an ultrasonic cleaner. When the liquid temperature rises during ultrasonic irradiation, thermal aggregation of the nanoparticles occurs (see Non-Patent Document 1). Therefore, the liquid temperature is preferably 1 to 100 ° C, more preferably 5 to 60 ° C. The temperature control method can be performed by controlling the dispersion temperature, controlling the temperature of the temperature adjusting layer that controls the temperature of the dispersion, or the like.
There are no particular limitations on the dispersing machine used to disperse the concentrated pigment nanoparticles by applying physical energy. Machine. In addition, a high-pressure dispersion method and a dispersion method using fine particle beads are also preferable.

  In the present invention, a pigment concentrate is prepared as described above for two or more different pigments. And after mixing 2 or more types of different pigment concentrates, the organic pigment dispersion of this invention is obtained by diluting to a desired pigment density | concentration. Thus, by mixing different pigments in the state of pigment concentrate, the organic pigment dispersion of the present invention prevents aggregation of pigment particles when mixing differently prepared different pigment solvent dispersions, A reduction in contrast can be prevented.

Examples of the machine used for mixing the pigment concentrate include a two-roll, a three-roll, a ball mill, a tron mill, a disper, a kneader, a kneader, a homogenizer, a blender, a single screw extruder and a twin screw extruder.
For details on kneading and dispersing, see T.W. C. It is also described in “Paint Flow and Pigment Dispersion” by Patton (published by John Wiley and Sons, 1964), and this method may be used.

[Colored photosensitive resin composition]
The colored photosensitive resin composition of the present invention includes a dispersion of the organic pigment nanoparticles, a binder, a monomer or an oligomer, and a photopolymerization initiator or a photopolymerization initiator system. Hereinafter, each component of the colored photosensitive resin composition will be described.

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

  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, neopentyl glycol di (meth) acrylate, pentaerythritol tetra (meth) acrylate, Pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipenta Rithritol penta (meth) acrylate, hexanediol di (meth) acrylate, trimethylolpropane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) isocyanurate, tri (acryloyloxyethyl) cyanurate, glycerin tri (meth) acrylate And polyfunctional acrylates and polyfunctional methacrylates such as those obtained by adding ethylene oxide or propylene oxide to 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 or the colored photosensitive resin composition, but it is added at the time of producing the pigment nanoparticle dispersion composition or forming the pigment nanoparticle. It is also preferable to do. A binder can also be added 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.

  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), US 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. The radiation that can be used for exposure is particularly preferably ultraviolet rays such as g-line and i-line. Irradiation dose is preferably 5~1500mJ / cm ^2, more preferably ^{10~1000mJ / cm 2, 10~500mJ / cm} 2 is particularly preferred.

  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 solvents, 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. The high-boiling organic solvent can be used as the fourth solvent. For example, a solvent having a boiling point of 180 ° C. to 250 ° C. can be used if necessary. As for content of a 4th solvent, 10-95 mass% is preferable with respect to the resin composition whole quantity.

  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.

[Inkjet ink]
In addition to the color filter, the inkjet ink of the present invention may be a normal inkjet ink for image formation or the like. In particular, the inkjet ink for a color filter is preferable. As an inkjet ink, although it does not specifically limit as an embodiment in this invention, For example, the method etc. which are described in Unexamined-Japanese-Patent No. 2002-201387 can be used preferably.
The inkjet ink of the present invention may be any ink using the organic pigment nanoparticles (a), and preferably further contains a binder (b) and a monomer or oligomer (c). Here, as a binder (b) monomer or oligomer (c), what was previously demonstrated in the colored photosensitive resin composition can be used. The inkjet ink of the present invention may further contain a photopolymerization initiator or a photopolymerization initiator system (d) and other additives. The content of each component ((a) to (d), other additives) may be the same as that described above for the colored photosensitive assembly. However, when the inkjet ink of the present invention is used as an ink for preparing a color filter, an embodiment that is not a photosensitive ink is preferable, and it is preferable not to use a photopolymerization initiator or a photopolymerization initiator system.

In the ink-jet ink of the present invention, it is preferable to control the ink temperature so that the fluctuation range of the viscosity is within ± 5%. The viscosity at the time of injection is preferably 5 to 25 mPa · s, more preferably 8 to 22 mPa · s, and particularly preferably 10 to 20 mPa · s (in the present invention, unless otherwise specified) It is a value at 25 ° C.). In addition to the setting of the injection temperature, the viscosity can be adjusted by adjusting the type and amount of components contained in the ink. The viscosity can be measured, for example, by a normal apparatus such as a conical plate type rotational viscometer or an E type viscometer.
The surface tension of the ink upon ejection is preferably 15 to 40 mN / m from the viewpoint of improving the flatness of the pixel (in the present invention, the surface tension is a value at 23 ° C. unless otherwise specified). ). More preferably, it is 20-35 mN / m, Most preferably, it is 25-30 mN / m. The surface tension can be adjusted by adding a surfactant or the type of solvent. For example, the surface tension is platinum by using a 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.). It can be measured by the plate method (both are trade names).

Ink jet ink for color filters can be sprayed by continuously ejecting charged ink and controlled by an electric field, intermittently ejecting ink using piezoelectric elements, or intermittently using ink by heating and foaming. Various methods such as a method of spraying 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 in advance and apply ink to a portion surrounded by the partition before forming pixels using the color filter inkjet ink. 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 this colored photosensitive resin composition, the above-mentioned monomer or oligomer is polymerized to form a colored photosensitive resin composition polymerized film, and a color filter having the same can be prepared (of the 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.

  Said colored photosensitive resin composition can be apply | coated by the normal apply | coating method, and a coating film can be formed by drying it. Examples of the coating method include coating with a slit nozzle, spin coating, and the like. The slit-like nozzle has a slit-like hole at a portion from which the liquid is discharged. Specifically, Japanese Patent Application Laid-Open No. 2004-89851, Japanese Patent Application Laid-Open No. 2004-17043, Japanese Patent Application Laid-Open No. 2003-170098, Slit nozzles and slit coaters described in JP-A Nos. 2003-164787, 2003-10767, 2002-79163, and 2001-310147 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.

[Photosensitive transfer material]
The photosensitive transfer material of the present invention has a photosensitive resin layer containing the above-described colored photosensitive resin composition, and the specific configuration is not particularly limited. For example, an integrated film is used. It is preferable that it is formed. As an example of the structure of the integral film, a structure in which a temporary support / thermoplastic resin layer / intermediate layer / photosensitive resin layer / protective film is laminated in this order can be given.

  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.

[Color filter]
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 when it is vertical (“1990 Seventh Color Optical Conference, 512-color display 10.4. "Refer to" Color TFT for size TFT-LCD, Ueki, Koseki, Fukunaga, Yamanaka "etc.).
The high contrast of the color filter means that the bright and dark discrimination when combined with the liquid crystal can be increased, and this is a very important performance in order to replace the liquid crystal display with a CRT.

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

xy 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 by a microspectrophotometer (manufactured by Olympus Optical Co., Ltd .; OSP100 or 200, both are trade names), calculated as a result of F10 light source field of view of 2 degrees, and expressed as xyY values in the xyz color system. To express. Further, the difference from the target chromaticity is represented by a color difference of the La ^* b ^* color system.

[Liquid Crystal Display]
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 further in detail based on an Example, this invention is not limited to these.

(Example 1 and Comparative Example 1)
<Production of Color Filter A1 (Production by Application Using Slit Nozzle)>
[Preparation of concentrated pigment liquid A]
To 800 ml of dimethyl sulfoxide (manufactured by Wako Pure Chemical Industries, Ltd.) I. Pigment Red 254 (Irgaphor Red BT-CF, trade name, manufactured by Ciba Specialty Chemicals Co., Ltd.) 38 g, and polyvinyl pyrrolidone (K-30, trade name, manufactured by Wako Pure Chemical Industries, Ltd.) 80 g added pigment solution Aa Was prepared. Apart from these, 1100 ml of water containing 30 ml of 1 mol / l hydrochloric acid aqueous solution (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 Aa was added to the NP-KX-500 type large solvent in a poor solvent stirred at 400 rpm by a GK-0222-10 type Lamond Stirrer (trade name, manufactured by Fujisawa Pharmaceutical Co., Ltd.). Organic pigment particles were formed by injecting 200 ml (2 minutes) at a flow rate of 100 ml / min using a capacity non-pulsating flow pump (trade name, manufactured by Nippon Seimitsu Chemical Co., Ltd.) to prepare a pigment dispersion Aa. When the particle size and monodispersity of this pigment dispersion were measured using Nanotrac UPA-EX150 (trade name, manufactured by Nikkiso Co., Ltd.), the number average particle size was 29 nm and Mv / Mn was 1.17.

  The pigment nanoparticle dispersion prepared by the above method is centrifuged at 3100 rpm (2000 G) for 1 hour using a high-speed centrifugal chiller HIMAC SCR20B (trade name, manufactured by Hitachi Koki Co., Ltd.), and the supernatant is discarded. The pigment nanoparticle concentrated paste Aa that settled down was recovered. When the pigment content of the paste was measured using an 8453 type spectrophotometer (trade name, manufactured by Agilent), Pigment Red 254 was 21.2% by mass.

On the other hand, 700 ml of methanesulfonic acid (manufactured by Wako Pure Chemical Industries, Ltd.) was mixed with pigment C.I. I. A pigment solution Ab to which 20 g of Pigment Red 177 (Chromofine Red 6605, trade name, manufactured by Dainichi Seika Co., Ltd.) and 30 g of polyvinylpyrrolidone (K-30, trade name, manufactured by Wako Pure Chemical Industries, Ltd.) was added was prepared. Apart from these, 1100 ml of water was prepared as a poor solvent.
Here, the temperature of the solution was controlled at 18 ° C., and the pigment solution Ab was added to the NP-KX-500 type large solvent in a poor solvent stirred at 400 rpm by a GK-0222-10 type Lamond Stirrer (trade name, manufactured by Fujisawa Pharmaceutical Co., Ltd.) Organic pigment particles were formed by injecting 100 ml (for 1 minute) at a flow rate of 100 ml / min using a capacity non-pulsating flow pump (trade name, manufactured by Nippon Seimitsu Chemical Co., Ltd.) to prepare a pigment dispersion Ab. When the particle diameter and monodispersity of this pigment dispersion were measured using Nanotrac UPA-EX150 (trade name, manufactured by Nikkiso Co., Ltd.), the number average particle diameter was 32 nm and Mv / Mn was 1.22.

  The pigment nanoparticle dispersion prepared by the above method is centrifuged at 3100 rpm (2000 G) for 1 hour using a high-speed centrifugal chiller HIMAC SCR20B (trade name, manufactured by Hitachi Koki Co., Ltd.), and the supernatant is discarded. The pigment nanoparticle concentrated paste Ab that settled down was recovered. When the pigment content of the paste was measured using an 8453 type spectrophotometer (trade name, manufactured by Agilent), Pigment Red 177 was 24.3% by mass.

  The pigment nanoparticle concentrated paste Aa (13.6 g) and the pigment nanoparticle concentrated paste Ab (1.4 g) were charged in a double-arm kneader and kneaded at 30 ° C. for 2 hours to prepare pigment nanoparticle concentrated paste A.

  The following pigment dispersant A (for pigment dispersant A was synthesized according to JP 2000-239554 A) was synthesized in 15.0 g of the above pigment nanoparticle concentrated paste A in 50.0 ml of ethyl lactate according to JP 2000-239554 A. ) Add a solution containing 0.6 g and 2.1 g of the exemplified compound (C-16) of the compound represented by the general formula (1), and after stirring at 3000 rpm for 60 minutes with a dissolver, an FP-010 filter (A trade name, manufactured by Sumitomo Electric Fine Polymer Co., Ltd.) is used to obtain a paste-like concentrated pigment liquid A (23.3 mass% for Pigment Red 254, 2.6 mass% for Pigment Red 177). It was.

[Preparation of R Pigment Dispersion A]
Using the paste, an R pigment dispersion A having the following composition was prepared.
13.5 g of the paste-like concentrated pigment liquid A
1-methoxy-2-propyl acetate (manufactured by Wako Pure Chemical Industries, Ltd.) 18.0 g

  The R pigment dispersion A having the above composition was dispersed with a motor mill M-50 (trade name, manufactured by Eiger Japan) for 1 hour at a peripheral speed of 7 m / s using zirconia beads having a diameter of 0.65 mm.

[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 1-1 below with a glass substrate coater (manufactured by FS Asia Co., Ltd., trade name: MH-1600) having a slit-like nozzle. A colored photosensitive resin composition K1 having the composition: Subsequently, a part of the solvent was dried by VCD (vacuum drying apparatus; manufactured by Tokyo Ohka Kogyo Co., Ltd.) for 30 seconds to eliminate the fluidity of the coating layer, and then pre-baked at 120 ° C. for 3 minutes to obtain a film thickness of A 4 μm photosensitive resin layer K1 was obtained.

[Table 1-1]
--------------------------------------
K pigment dispersion 1 (carbon black) 25 parts by mass Propylene glycol monomethyl ether acetate 8.0 parts by mass Methyl ethyl ketone 53 parts by mass Binder 2 9.1 parts by mass Hydroquinone monomethyl ether 0.002 parts by mass DPHA solution 4.2 parts by mass Polymerization start Agent 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, (Fujifilm Electronics Materials, Inc., 100-fold diluted solution) 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.

  For the colored photosensitive resin composition K1, first, K pigment dispersion 1 and propylene glycol monomethyl ether acetate are weighed, mixed at a temperature of 24 ° C. (± 2 ° C.), stirred at 150 rpm for 10 minutes, and then methyl ethyl ketone, binder 2 , Hydroquinone monomethyl ether, DPHA solution, polymerization initiator A (2,4-bis (trichloromethyl) -6- [4 '-(N, N-bisethoxycarbonylmethyl) amino-3'-bromophenyl] -s- Triazine) and surfactant 1 were weighed out, added in this order at a temperature of 25 ° C. (± 2 ° C.), and stirred at 150 rpm for 30 minutes at a temperature of 40 ° C. (± 2 ° C.).

<K pigment dispersion 1>
・ Carbon black (trade name: Nipex 35, manufactured by Degussa Japan Co., Ltd.)
13.1 parts by mass / dispersant (compound J1) 0.65 parts by mass / polymer (benzyl methacrylate / methacrylic acid = 72/28 molar ratio)
Random copolymer of, molecular weight 37,000) 6.72 parts by mass / propylene glycol monomethyl ether acetate 79.53 parts by mass

<Binder 2>
・ Polymer (benzyl methacrylate / methacrylic acid = 78/22 molar ratio
Random copolymer of, molecular weight 38,000) 27 parts by mass / propylene glycol monomethyl ether acetate 73 parts by mass <DPHA solution>
・ Dipentaerythritol hexaacrylate (containing polymerization inhibitor MEHQ 500 ppm, Nippon Kayaku Co., Ltd., trade name: KAYARAD DPHA) 76 parts by mass Propylene glycol monomethyl ether acetate 24 parts by mass <Surfactant 1>
MegaFuck F-780-F (manufactured by Dainippon Ink & Chemicals, Inc.): composition is as follows: C ₆ F ₁₃ CH ₂ CH ₂ OCOCH = 40 mass parts of CH ₂ 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 (molecular weight 30,000)
30 parts by mass, 70 parts by mass of methyl ethyl ketone

[Formation of red (R) pixels]
Using the colored photosensitive resin composition RA1 having the composition described in Table 1-2 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 RA1 and the coating amount of the pigment are shown below. In addition, the preparation procedure of the colored photosensitive resin composition was the same as that of the colored photosensitive resin composition K1.
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 ) 0.90
C. I. P. R. 177 coating amount (g / m ² ) 0.10

[Table 1-2]
--------------------------------------
R pigment dispersion A (CIPR254, CIPR177) 45 parts by mass Propylene glycol monomethyl ether acetate 7.6 parts by mass Methyl ethyl ketone 37 parts by mass Binder 1 0.7 parts by mass DPHA solution 3.8 parts by mass Polymerization initiator B 0.12 parts by mass Polymerization initiator A 0.05 mass part Phenothiazine 0.01 mass part Surfactant 1 0.06 mass part ------------------------- --------------

<Binder 1>
・ Polymer (benzyl methacrylate / methacrylic acid = 78/22 molar ratio
Random copolymer of, molecular weight 40,000) 27 parts by mass, 73 parts by mass of propylene glycol monomethyl ether acetate <polymerization initiator B>
2-Trichloromethyl- (p-styrylstyryl) 1,3,4-oxadiazole

[Formation of green (G) pixels]
In the same process as the formation of the black (K) image, the heat-treated pixel is formed using the colored photosensitive resin composition G1 having the composition described in Table 1-3 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. In addition, the preparation procedure of the colored photosensitive resin composition was the same as that of the colored photosensitive resin composition K1.
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 1-3]
--------------------------------------
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 2 2.5 parts by mass DPHA solution 3 0.5 part by weight Polymerization initiator B 0.12 part by weight Polymerization initiator A 0.05 part by weight Phenothiazine 0.01 part by weight Surfactant 1 0.07 part by weight ------------ --------------------------

<G pigment dispersion 1>
"Product name: GT-2" manufactured by FUJIFILM Electronics Materials Co., Ltd.

<Y pigment dispersion 1>
"Product name: CF Yellow-EX3393" manufactured by Gokoku Color Co., Ltd.

[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 1-4 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 A1. The film thickness of the photosensitive resin layer B1 and the coating amount of the pigment are shown below. In addition, the preparation procedure of the colored photosensitive resin composition was the same as that of the colored photosensitive resin composition K1.
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 1-4]
--------------------------------------
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 3 17 parts by mass DPHA solution 4.0 Parts by mass polymerization initiator B 0.17 parts by mass phenothiazine 0.02 parts by mass surfactant 1 0.06 parts by mass --------------------- ---------------

<B pigment dispersion 1>
"Product name: CF Bull-EX3357" manufactured by Gokoku Color Co., Ltd.
<B pigment dispersion 2>
"Product name: CF Bull-EX3383" manufactured by Gokoku Color Co., Ltd.
<Binder 3>
・ Polymer (benzyl methacrylate / methacrylic acid / methyl methacrylate = 36/22/42 molar ratio random copolymer, molecular weight 38,000) 27 parts by mass-propylene glycol monomethyl ether acetate 73 parts by mass

<Preparation of color filter B1>
Pigment nanoparticle concentrated paste Aa 15.2 g obtained in the preparation of color filter A1, 50.0 ml of ethyl lactate, 0.6 g of the pigment dispersant A and an exemplary compound (C-16) represented by the general formula (1) ) After adding a solution containing 2.1 g and stirring with a dissolver at 3000 rpm for 60 minutes, the mixture was filtered using an FP-010 filter (trade name, manufactured by Sumitomo Electric Fine Polymer Co., Ltd.) to obtain a paste-like Concentrated pigment liquid Ba (Pigment Red 254 was 23.0% by mass) was obtained.

  Pigment Nanoparticle Concentrated Paste Ab 13.3 g obtained in the production of Color Filter A1 was added to Pigment Dispersant A 0.6 g in ethyl lactate 50.0 ml and Compound (C-16) as an example compound represented by Formula (1). ) After adding a solution containing 2.1 g and stirring with a dissolver at 3000 rpm for 60 minutes, the mixture was filtered using an FP-010 filter (trade name, manufactured by Sumitomo Electric Fine Polymer Co., Ltd.) to obtain a paste-like Concentrated pigment liquid Bb (Pigment Red 177 was 21.2% by mass) was obtained.

  The above concentrated pigment solution Ba13.7g and concentrated pigment solution Bb1.7g were charged into a double-arm kneader and kneaded at 30 ° C. for 2 hours to obtain a paste-like concentrated pigment solution B (23.3% by weight of Pigment Red 254, Pigment Red). 177 was 2.6% by mass).

  Using the paste-like concentrated pigment liquid B, an R pigment dispersion B and a colored photosensitive resin composition RB1 were prepared in the same manner as in the production of the color filter A1, and a color filter B1 was produced.

<Preparation of color filter C1>
Pigment nanoparticle concentrated paste Aa 15.2 g obtained in the preparation of color filter A1, 50.0 ml of ethyl lactate, 0.6 g of the pigment dispersant A and an exemplary compound (C-16) represented by the general formula (1) ) After adding 2.1 g of the solution, stirring at 3000 rpm for 60 minutes with a dissolver, transferring to an eggplant-shaped flask and drying under reduced pressure at 70 ° C. for 1.5 hours with an evaporator, pigment dry powder Ca (pigment concentration) 50.0% by mass) was obtained.

  Pigment Nanoparticle Concentrated Paste Ab 13.3 g obtained in the production of Color Filter A1 was added to Pigment Dispersant A 0.6 g in ethyl lactate 50.0 ml and Compound (C-16) as an example compound represented by Formula (1). ) After adding 2.1 g of the solution, stirring with a dissolver at 3000 rpm for 60 minutes, transferring to an eggplant-shaped flask, and drying under reduced pressure at 70 ° C. for 1.5 hours with an evaporator, pigment dry powder Cb (pigment concentration) 45.3 mass%) was obtained.

  The pigment dry powder Ca 5.0 g and the pigment dry powder Cb 0.61 g were pulverized and mixed at room temperature for 10 minutes in a mortar, and the pigment dry powder C (pigment red 254 44.6 mass%, pigment red 177 4.9 mass%). ) Was prepared.

[Preparation of R Pigment Dispersion C]
Using the pigment dry powder C, an R pigment dispersion C having the following composition was prepared.
7.1 g of the pigment dry powder C
1-methoxy-2-propyl acetate (Wako Pure Chemical Industries, Ltd.) 24.6g

  The R pigment dispersion C having the above composition was dispersed with a motor mill M-50 (trade name, manufactured by Eiger Japan) for 1 hour at a peripheral speed of 7 m / s using zirconia beads having a diameter of 0.65 mm. An R pigment dispersion C and a colored photosensitive resin composition RC1 were prepared in the same manner as in the production of the color filter A1, and the color filter C1 was produced.

<Preparation of color filter D1>
[Preparation of R Pigment Dispersion Da]
Using the pigment dry powder Ca, an R pigment dispersion Da having the following composition was prepared.
7.0 g of dry pigment powder Ca
1-methoxy-2-propyl acetate (Wako Pure Chemical Industries, Ltd.) 24.5g

The R pigment dispersion Da having the above composition was dispersed with a motor mill M-50 (trade name, manufactured by Eiger Japan) for 1 hour at a peripheral speed of 7 m / s using zirconia beads having a diameter of 0.65 mm.

[Preparation of R Pigment Dispersion Db]
Using the pigment dry powder Cb, an R pigment dispersion Db having the following composition was prepared.
7.7 g of the pigment dry powder Cb
1-methoxy-2-propyl acetate (manufactured by Wako Pure Chemical Industries, Ltd.) 23.7 g

  The R pigment dispersion Db having the above composition was dispersed with a motor mill M-50 (trade name, manufactured by Eiger Japan) for 1 hour at a peripheral speed of 7 m / s using zirconia beads having a diameter of 0.65 mm.

  R pigment dispersion Db was prepared by adding 2.22 g of R pigment dispersion Db to 20 g of R pigment dispersion Da stirred with a stirrer. An R pigment dispersion D and a colored photosensitive resin composition RD1 were prepared in the same manner as in the production of the color filter A1, and a color filter D1 was produced.

<Preparation of color filter E1>
A pigment dispersion composition Ea having the following composition was prepared using a bead disperser as described below.
Pigment (Pigment Red 254) 5.2g
Pigment dispersant A 0.6g
Polyvinylpyrrolidone (manufactured by Wako Pure Chemical Industries, Ltd., K30) 1.3 g
Exemplary compound (C-16) of the compound represented by the general formula (1) 6.0 g
1-methoxy-2-propyl acetate 33.7 g

  In a 1-methoxy-2-propyl acetate solution, a powder of pigment (Pigment Red 254), polyvinylpyrrolidone, and the exemplified compound (C-16) of the compound represented by the general formula (1) are added and stirred, and the mixture is stirred. Obtained. Next, this mixed solution was dispersed with a motor mill M-50 (manufactured by Eiger Japan) for 10 hours at a peripheral speed of 9 m / s using zirconia beads having a diameter of 0.65 mm. When the particle size and monodispersity were measured in the same manner as in the measurement of the pigment dispersion Aa, the number average particle size was 53 nm and Mv / Mn was 1.50.

A pigment dispersion composition Eb having the following composition was prepared using a bead disperser as described below.
Pigment (Pigment Red 177) 4.4 g
Pigment dispersant A 0.8g
Polyvinylpyrrolidone (manufactured by Wako Pure Chemical Industries, Ltd., K30) 1.0 g
4.4 g of exemplary compound (C-16) of the compound represented by the general formula (1)
19.0 g of 1-methoxy-2-propyl acetate

  In a 1-methoxy-2-propyl acetate solution, a pigment (Pigment Red 177) powder, polyvinylpyrrolidone, and the exemplified compound (C-16) of the compound represented by the general formula (1) are charged and stirred. Obtained. Next, this mixed solution was dispersed with a motor mill M-50 (manufactured by Eiger Japan) for 10 hours at a peripheral speed of 9 m / s using zirconia beads having a diameter of 0.65 mm. When the particle size and monodispersity were measured in the same manner as in the measurement of the pigment dispersion Aa, the number average particle size was 48 nm and Mv / Mn was 1.44.

  R pigment dispersion Eb was prepared by adding 2.22 g of R pigment dispersion Eb to 20 g of R pigment dispersion Ea stirred with a stirrer. An R pigment dispersion E and a colored photosensitive resin composition RE1 were prepared in the same manner as in the production of the color filter A1, and the color filter E1 was produced.

[Measurement of contrast of color filters A1 to E1]
Using the produced color filter as a backlight unit, a three-wavelength cold cathode tube light source (FWL18EX-N, trade name, manufactured by Toshiba Lighting & Technology Co., Ltd.) with a diffusion plate installed, two polarizing plates (HLC2- 2518, trade name, manufactured by Sanritsu Co., Ltd.), measured the amount of transmitted light when the polarization axis was parallel and vertical, and made the ratio the contrast (Ueki, Koseki, Fukunaga, Yamanaka) , "512 color display 10.4" size TFT-LCD color filter ", 7th Color Optical Conference (1990), etc.).
The measurement results of the contrast of the color filters A1 to E1 are shown in Table 1-5.

[Evaluation of process stability]
The viscosity (initial viscosity) at 25 ° C. immediately after production of the produced colored photosensitive resin compositions RA1 to RE1 was measured. Moreover, the viscosity (viscosity with time) at 25 ° C. of the colored photosensitive resin compositions RA1 to RE1 stored for 4 months in an environment of 5 ° C. was measured. The results are shown in Table 1-5 together with the increased values when the initial viscosity and the viscosity with time are compared. At this time, the viscosity was measured using a vibration viscometer VM-100A-L.

[Table 1-5]
--------------------------------------
Color filter Contrast Initial viscosity Viscosity over time Viscosity increase --------------------------------
A1 9200 13cp 15cp 2cp
B1 8070 10cp 11cp 1cp
C1 9100 11cp 12cp 1cp
D1 7000 10cp 19cp 9cp
E1 4000 11cp 25cp 14cp
--------------------------------------

  As is apparent from the results of Table 1-5, it was found that the color filters A1 to C1 of the present invention example showed higher contrast and better display characteristics than the color filters D1 and E1 of the comparative example. In addition, the colored photosensitive resin compositions RA1 to RC1 of the present invention examples maintain high dispersion stability over a long period of time as compared with the colored photosensitive resin compositions RD1 and RE1 of the comparative examples, and have good stability over time. It was found to show sex.

(Example 2 and Comparative Example 2)
<Production of Color Filters A2 to E2 (Production by Laminating Photosensitive Resin Transfer Material)>
[Production of photosensitive resin transfer material]
On a 75 μm thick polyethylene terephthalate film temporary support, a coating solution for a thermoplastic resin layer having the following formulation H1 was applied and dried using a slit nozzle. Next, an intermediate layer coating solution having the following formulation P1 was applied and dried. Furthermore, the colored photosensitive resin composition K1 is applied and dried, and a thermoplastic resin layer having a dry film thickness of 14.6 μm, an intermediate layer having a dry film thickness of 1.6 μm, A photosensitive resin layer having a thickness of 2.4 μm was provided, and a protective film (polypropylene film having a thickness of 12 μm) was pressure-bonded.
Thus, a photosensitive resin transfer material K1 in which the temporary support, the thermoplastic resin layer, the intermediate layer (oxygen barrier film), and the black (K) photosensitive resin layer were integrated was produced.

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

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

  Next, the colored photosensitive resin composition RA2 and G101 having the compositions described in Tables 2-1 to 2-3 below are used as the colored photosensitive resin composition K1 used in the production of the photosensitive resin transfer material K1. Photoresin transfer materials RA2, 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 RA2, G101, and B101 is based on the preparation method of the said colored photosensitive resin composition RA1, G1, and B1, respectively.

[Table 2-1] RA2
--------------------------------------
R pigment dispersion A (CIPR254, CIPR177) 45 parts by mass Propylene glycol monomethyl ether acetate 7.1 parts by mass Methyl ethyl ketone 57 parts by mass Binder 1 0.8 parts by mass DPHA solution 4.4 parts by mass Polymerization initiator B 0.14 parts by mass Polymerization initiator A 0.06 parts by mass Phenothiazine 0.01 parts by mass Additive 1 0.52 parts by mass Surfactant 1 0.06 parts by mass ----------------- ---------------------

[Table 2-2] G101
--------------------------------------
G pigment dispersion 1 (CIPG 36) 28 parts by mass Y pigment dispersion 1 (CIPI 150) 13 parts by mass Propylene glycol monomethyl ether acetate 39 parts by mass Methyl ethyl ketone 16 parts by mass Cyclohexanone 1.3 parts by mass Binder 2 3.0 parts by mass DPHA solution 4 .3 parts by weight Polymerization initiator B 0.15 parts by weight Polymerization initiator A 0.06 parts by weight Phenothiazine 0.01 parts by weight Surfactant 1 0.07 parts by weight ------------ --------------------------

[Table 2-3] B101
--------------------------------------
B pigment dispersion 1 (CIPB 15: 6) 8.6 parts by mass B pigment dispersion 2 (CIPB 15: 6 + CIPV 23) 15 parts by mass Propylene glycol monomethyl ether acetate 28 parts by mass Methyl ethyl ketone 26 parts by mass Binder 3 18.5 parts by mass DPHA solution 4 .3 parts by mass Polymerization initiator B 0.17 parts by mass Phenothiazine 0.02 parts by mass Surfactant 1 0.06 parts by mass ------------------- -----------------

  In addition, among the compositions described in Table 2-1, as the additive 1, a phosphate ester special activator (manufactured by Enomoto Kasei Co., Ltd., trade name: HIPLAAD ED152) was used.

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

Next, a triethanolamine developer (containing 2.5% triethanolamine, trade name: T-PD2, Fuji Photo Film Co., Ltd., 12-fold diluted with pure water (1 part of T-PD2 The mixture was mixed at a ratio of 11 parts of water.))) At 30 ° C. for 50 seconds and a flat nozzle pressure of 0.04 MPa, and the thermoplastic resin layer and the intermediate layer were removed.
Subsequently, sodium carbonate developer (0.38 mol / liter sodium bicarbonate, 0.47 mol / liter sodium carbonate, 5% sodium dibutylnaphthalenesulfonate, anionic surfactant, antifoaming agent, stabilizer included , Trade name: T-CD1, manufactured by Fuji Photo Film Co., Ltd. diluted 5 times with pure water) and developed at 29 ° C. for 30 seconds at a cone type nozzle pressure of 0.15 MPa to develop the photosensitive resin layer. A patterning image was obtained.
Subsequently, using a solution obtained by diluting a cleaning agent (trade name “T-SD1 (manufactured by Fuji Photo Film Co., Ltd.) 10 times with pure water, a shower and nylon hair were removed at 33 ° C. for 20 seconds and a cone type nozzle pressure of 0.02 MPa. Residue removal was performed with a rotating brush, and a black (K) image was obtained, and then post-exposure was performed on the substrate from the resin layer side with a 500 mJ / cm ² light with an ultrahigh pressure mercury lamp. It heat-processed at 15 degreeC 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 RA2, heat-treated red (R) pixels R were obtained in the same process as the photosensitive resin transfer material K1. However, the exposure amount was 40 mJ / cm ² , and development with a sodium carbonate developer was 35 ° C. for 35 seconds. The film thickness of the photosensitive resin layer RA2 and the coating amounts of the 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 ) 0.90
C. I. P. R. 177 coating amount (g / m ² ) 0.10
The substrate on which the image K and the pixel R were formed was again cleaned with a brush as described above, and after pure water shower cleaning, the silane coupling liquid was not used and the substrate was sent to a substrate preheating device.

[Formation of green (G) pixels]
Using the photosensitive resin transfer material G101, a heat-treated green (G) pixel G was obtained in the same process as the photosensitive resin transfer material RA2. 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 amount of the pigment (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 RA2. 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, pixel G, pixel B, and image K were formed was baked at 240 ° C. for 50 minutes to obtain a color filter A2.

  R pigment dispersion A was changed to R pigment dispersions B to E, respectively, with respect to the production method of color filter A2, and colored photosensitive resin compositions RA2 to RE2 and color filters B2 to E2 were produced.

  In this specification, the color filters A2 to E2 produced by laminating the photosensitive resin transfer material as described above are collectively referred to as a color filter 2.

  The contrast of the obtained color filters A2 to E2 and the temporal stability of the colored photosensitive resin compositions RA2 to RE2 were evaluated in the same manner as in Example 1 and Comparative Example 1. The results are shown in Table 2-4.

[Table 2-4]
--------------------------------------
Color filter Contrast Initial viscosity Viscosity over time Viscosity increase --------------------------------
A2 12200 13cp 15cp 2cp
B2 11000 14cp 14cp 0cp
C2 10100 15cp 18cp 3cp
D2 8100 16cp 24cp 8cp
E2 7100 17cp 30cp 13cp
--------------------------------------

  As is clear from the results in Table 2-4, it was found that the color filters A2 to C2 of the present invention example showed higher contrast and better display characteristics than the color filters D2 and E2 of the comparative example. In addition, the colored photosensitive resin compositions RA2 to RC2 of the present invention examples maintain high dispersion stability over a long period of time as compared with the colored photosensitive resin compositions RD2 and RE2 of the comparative examples, and have good temporal stability. I found out.

(Example 3 and Comparative Example 3)
<Production of Color Filters A3 to E3 (Production by Inkjet)>
Regarding the production procedure of the photosensitive resin transfer material K1, the photosensitive resin transfer material K2 was similarly prepared except that the colored photosensitive resin composition K1 was replaced with the colored photosensitive resin composition K2 described in Table 3-1 below. Produced.

[Table 3-1] Colored photosensitive resin composition K2
--------------------------------------
K pigment dispersion 1 (carbon black) 30 parts by mass Propylene glycol monomethyl ether acetate 7.3 parts by mass Methyl ethyl ketone 34 parts by mass Cyclohexanone 8.6 parts by mass Binder 2 14 parts by mass DPHA solution 5.8 parts by mass Polymerization initiator A 0. 22 parts by mass Phenothiazine 0.006 parts by mass The above surfactant 1 0.058 parts by mass ----------------------------- ---------

  The resin composition K2 having light-shielding properties was first weighed in 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 described in Table 8-1. Of methyl ethyl ketone, cyclohexanone, binder 2, phenothiazine, DPHA solution, polymerization initiator A and surfactant 1 were added in this order at a temperature of 25 ° C. (± 2 ° C.), and a temperature of 40 ° C. (± 2 ° C. ) At 150 rpm for 30 minutes.

[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 K2, 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, a triethanolamine developer (containing 30% triethanolamine, trade name: T-PD2, manufactured by Fuji Photo Film Co., Ltd. 12 times with pure water (1 part of T-PD2 and 11 parts of pure water) The resulting mixture was diluted with a mixture) at 30 ° C. for 50 seconds at 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 (0.38 mol / liter sodium bicarbonate, 0.47 mol / liter sodium carbonate, 5% sodium dibutylnaphthalene sulfonate, anionic surfactant, antifoaming agent, stabilizer included , Trade name: T-CD1, manufactured by Fuji Photo Film Co., Ltd. diluted 5 times with pure water) and shower-developed at 29 ° C. for 30 seconds with a cone type nozzle pressure of 0.15 MPa to have a light shielding property Was developed to obtain a patterning separation wall (a partition wall pattern having a light shielding property).

Subsequently, using a cleaning agent (trade name “T-SD3 (manufactured by Fuji Photo Film Co., Ltd.)” diluted 10 times with pure water), a shower and nylon hair at 33 ° C. for 20 seconds and a cone type nozzle pressure of 0.02 MPa. Residue was removed with a rotating brush having a light shielding property to obtain a light-shielding partition. Thereafter, the substrate was further post-exposed with light of 500 mJ / cm ^{2 with} an ultrahigh pressure mercury lamp from the resin layer side, and then heat treated at 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 inkjet ink for a color filter was prepared according to the following formulation.
[Table 3-R]
--------------------------------------
Composition component Content (parts by mass) Ink RA3
--------------------------------------
R pigment dispersion A (CIPR254, CIPR177) 70
Polymer dispersant (Solsperse 20000 (trade name) manufactured by AVECIA) 1.0
Polymer 1 2.0 below
Dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd., trade name: KAYARAD DPHA) 6.0
Alkynoyl-modified dipentaerythritol triacrylate (Nippon Kayaku, KAYARAD D330) 4.0
Phenothiazine 0.005
1,3-butylene glycol diacetate 25
--------------------------------------

[Table 3-G]
--------------------------------------
Composition component Content (parts by mass) Ink G1
--------------------------------------
G pigment dispersion 1 (P.G.36) 35
Y pigment dispersion 1 (P.Y.150) 32
Polymer dispersant (Solsperse 20000 manufactured by AVECIA) 1.0
Polymer 1 2.0 below
Dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd., trade name: KAYARAD DPHA) 6.0
Alkynoyl-modified dipentaerythritol triacrylate (Nippon Kayaku, KAYARAD D330) 4.0
Phenothiazine 0.005
1,3-butylene glycol diacetate 25
--------------------------------------

[Table 3-B]
--------------------------------------
Composition component Content (parts by mass) Ink B1
--------------------------------------
B pigment dispersion 1 (P.B.15: 6 + P.V.23) 8
B pigment dispersion 2 (P.B.15: 6) 71
Polymer dispersant (Solsperse 20000 (trade name) manufactured by AVECIA) 1.0
Polymer 1 2.0 below
Dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd., trade name: KAYARAD DPHA) 6.0
Alkynoyl-modified dipentaerythritol triacrylate (Nippon Kayaku, KAYARAD D330) 4.0
Phenothiazine 0.005
1,3-butylene glycol diacetate 25
--------------------------------------
Polymer 1 Random copolymer of benzyl methacrylate / methacrylic acid = 72/28 molar ratio, molecular weight 37,000

  Regarding the mixing of each of the components in Tables 3-R, 3-G, and 3-B, first, the pigment and the polymer dispersant are charged into a part of the solvent, mixed, and stirred using a three roll and bead mill. Thus, a pigment dispersion was obtained. On the other hand, other compounding components were added to the remainder of the solvent, and were dissolved and dispersed by stirring to obtain a monomer solution. Then, while adding the pigment dispersion or the pigment dispersion composition little by little to the monomer solution, the mixture was sufficiently stirred with a dissolver to prepare an inkjet ink for a color filter.

[Pixel formation]
First, a color filter A3 was produced using the ink RA3, the ink G-1, and the ink B-1 described above as follows.
The inkjet head used was Dimatix SE-128, and the discharge controller used was Dimatix Apollo II. An inkjet head is mounted on an automatic two-dimensional moving stage (KS211-200 manufactured by Suruga Seiki), and the stage is moved from the head by the discharge control device while moving the stage so that a predetermined amount of ink is discharged into the gap of the partition wall produced above. The discharge was synchronized.
Here, the ink RA3, the ink G-1, and the ink B-1 described above are filled in different heads, each head is fixed on the XY stage, and each ink is in a predetermined position. The three heads were independently controlled by the discharge control device so as to land on.
For droplet ejection, the ink composition is discharged until the desired concentration is reached, heated and dried on a hot plate at 100 ° C. for 2 minutes, and then baked in an oven at 230 ° C. for 30 minutes to completely cure both the partition walls and pixels. A color filter A3 was produced.

  R pigment dispersion A was changed to R pigment dispersions B to E, respectively, and inks RB3 to RE3 and color filters B3 to E3 were prepared with respect to the method for producing color filter A3.

  In this specification, the color filters A3 to E3 produced by inkjet as described above are collectively referred to as the color filter 3.

  The contrast of the obtained color filters A3 to E3 and the temporal stability of the inks RA3 to RE3 were evaluated in the same manner as in Example 1 and Comparative Example 1. The results are shown in Table 3-2.

[Table 3-2]
--------------------------------------
Color filter Contrast Initial viscosity Viscosity over time Viscosity increase --------------------------------
A3 13100 10cp 13cp 3cp
B3 12500 9cp 9cp 0cp
C3 13700 12cp 14cp 2cp
D3 12900 11cp 11cp 10cp
E3 9500 10cp 22cp 12cp
--------------------------------------

  As is apparent from the results in Table 3-2, it can be seen that the color filters A3 to C3 of the example of the present invention show higher contrast and better display characteristics than the color filters D3, E3 and G3 of the comparative example. It was. In addition, it was found that the inks RA3 to RC3 of the present invention example maintained high dispersion stability over a long period of time as compared with the inks RD3 and RE3 of the comparative example, and exhibited good temporal stability.

(Example 4 and Comparative Example 4)
[Production of liquid crystal display elements]
A liquid crystal display device was produced according to the following method.
(1) A patterned 1 cm ² ITO film is formed on one surface of a glass substrate, and a commercially available liquid crystal aligning agent for active matrix is applied onto the ITO film using a spinner, and then 1 at 180 ° C. It was dried for a time to form a coating film having a thickness of 600 mm.
(2) After forming a patterned 1 cm ² ITO film on each of the color filters 1 to 3 produced in the above-mentioned examples and comparative examples, on the ITO film, in the same manner as (1), A liquid crystal aligning agent coating was formed.
(3) After forming an ITO film (continuous film) on one side of the glass substrate, a coating film of a liquid crystal aligning agent was formed on the ITO film in the same manner as (1).
(4) Next, the surface of the coating film on each substrate obtained in (1) to (3) is subjected to a rubbing process using a rubbing machine provided with a roll around which a cloth made of rayon is wound, and a liquid crystal alignment film Formed. The rubbing conditions at that time were a roll rotation speed of 400 rpm, a stage moving speed of 3 cm / second, and a push-in length of the hair foot of 0.4 mm.
(5) Among the substrates on which the liquid crystal alignment film is formed in this way, each substrate that has undergone the treatment of (1) or (2) is combined with the substrate that has undergone the treatment of (3) to form one set, For each set, an epoxy resin adhesive containing a silica gel columnar spacer with a diameter of 5.5 μm was applied to the outer edge of the two substrates by screen printing, and the rubbing direction of each liquid crystal alignment film crossed 90 degrees. As described above, the two substrates were placed facing each other with a gap between them, and the adhesive was cured by pressing so that the outer edge portions of each substrate were in contact with each other.
(6) Next, for each set, nematic liquid crystal “ZLI-5081” (trade name, made of fluorobiphenyl derivative) in a cell gap defined by the inner surface of the two substrates and the hardened layer of the adhesive. After injection and filling (Merck Japan Co., Ltd.), the injection hole was sealed to prepare a liquid crystal cell. Thereafter, a polarizing plate was bonded to the outer surface of the liquid crystal cell so that the polarization direction thereof coincided with the rubbing direction of the liquid crystal alignment film on each substrate, thereby producing a liquid crystal display element.

  The manufactured liquid crystal display device was visually evaluated for display characteristics (color unevenness, black margin). As a result, in the liquid crystal display element produced using each of the color filters A1 to C1, A2 to C2 and A3 to C3 of the example of the present invention, all of the color filters D1, E1, D2, E2, D3, Compared with the liquid crystal display element produced using E3, it turned out that a favorable display characteristic is shown.

  From the above results, by using the organic pigment dispersion of the present invention, a color filter with extremely high contrast can be obtained, and a liquid crystal display device using the color filter of the present invention exhibits good display characteristics. I understand.

Claims (11)

  A dispersion of organic pigment nanoparticles in which a solution obtained by dissolving an organic pigment in a good solvent and a poor solvent for the organic pigment compatible with the good solvent are mixed to produce the organic pigment as nano-sized fine particles. And then mixing the two or more different pigment concentrates obtained by concentrating the dispersion to a state in which the pigment concentration is higher than that at the time of the particle formation, and then diluting to the desired pigment concentration. Pigment dispersion.   2. The organic pigment dispersion according to claim 1, wherein the pigment concentrate is prepared by precipitating the organic pigment fine particles and then removing the solvent content of the mixed solution.   A pigment concentrate is prepared by precipitating the organic pigment fine particles, substituting the solvent component of the mixed solution with a substitution solvent, and then removing the solvent component containing the substitution solvent. The organic pigment dispersion according to claim 1.   The organic pigment dispersion according to any one of claims 1 to 3, further comprising a polymer compound having a mass average molecular weight of 1000 or more. The organic pigment dispersion according to claim 4, wherein the polymer compound is represented by the following general formula (1).

[Wherein, R ¹ represents a (m + n) -valent linking group, and R ² represents a single bond or a divalent linking group. A ¹ is an acidic group, a 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. ]   A colored photosensitive resin composition comprising the pigment dispersion according to any one of claims 1 to 5, a binder, a monomer or an oligomer, and a photopolymerization initiator or a photopolymerization initiator system. object.   The colored photosensitive resin composition according to claim 6, which is an inkjet ink for a color filter.   A photosensitive resin transfer material, wherein a photosensitive resin layer containing at least the colored photosensitive resin composition according to claim 6 is provided on a temporary support.   A color filter produced using the colored photosensitive resin composition according to claim 6 and / or the photosensitive resin transfer material according to claim 8.   A liquid crystal display device comprising the color filter according to claim 9.   A dispersion of organic pigment nanoparticles in which a solution obtained by dissolving an organic pigment in a good solvent and a poor solvent for the organic pigment compatible with the good solvent are mixed to produce the organic pigment as nano-sized fine particles. And then mixing the two or more different pigment concentrates obtained by concentrating the dispersion to a state in which the pigment concentration is higher than that at the time of the particle formation, and then diluting to a desired pigment concentration. Method for producing organic pigment nanoparticle dispersion.