JP2008231167A - Manufacturing method of organic pigment nanoparticle, organic pigment fine particle powder obtained by the same, pigment dispersion, colored photosensitive resin composition, photosensitive resin transfer material, and color filter and liquid crystal display obtained using these - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a manufacturing method of an organic pigment nanoparticle that realizes high contrast when a color filter is made therefrom and realizes high display quality with suppressed generation of color unevenness in a liquid crystal display, an organic pigment fine particle powder obtained by the same, a pigment dispersion, a colored photosensitive resin composition, a photosensitive resin transfer material, and a color filter and a liquid crystal display obtained using these. <P>SOLUTION: The manufacturing method of an organic pigment nanoparticle comprises mixing an organic pigment solution containing the organic pigment dissolved in a good solvent with a poor solvent for the organic pigment before the decomposition ratio of the pigment in the organic pigment solution reaches at least 20% thereby to make the organic pigment to deposit as a fine particle of a nanometer size in the mixed solution. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a method for producing organic pigment nanoparticles, organic pigment fine particle powder, pigment dispersion, colored photosensitive resin composition and photosensitive resin transfer material obtained thereby, a color filter using them, 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 is refined, the dispersion composition may have a 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 Patent Document 1). However, higher contrast is desired. Moreover, it is not known whether high performance can be exhibited when mounted on a liquid crystal display device.

International Publication No. WO2006 / 121016 Pamphlet

  The present invention relates to a method for producing organic pigment nanoparticles that exhibit high contrast when used as a color filter and that can achieve high display quality with reduced color unevenness in a liquid crystal display device, and organic pigment fine particle powder obtained thereby Another object is to provide a pigment dispersion, a colored photosensitive resin composition, a photosensitive resin transfer material, a color filter using them, and 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。〕
（８）（５）〜（７）のいずれか１項に記載された顔料分散物と、重合性モノマーおよび／または重合性オリゴマーとを含むことを特徴とするカラーフィルタ用インクジェットインク。
（９）（５）〜（７）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。
（１０）仮支持体上に、少なくとも、（９）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。
（１１）（８）に記載のインクジェットインク、（９）に記載の着色感光性樹脂組成物、及び／又は（１０）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。
（１２）（１１）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。 The above problems have been achieved by the following means.
(1) An organic pigment solution in which an organic pigment is dissolved in a good solvent and a solvent that is a poor solvent for the organic pigment are mixed before the decomposition rate of the pigment in the organic pigment solution reaches 20% or more. Then, the organic pigment is precipitated as nanometer-sized fine particles in the mixed liquid, and the method for producing organic pigment nanoparticles is characterized in that
(2) The method for producing organic pigment nanoparticles according to (1), wherein a decomposition rate index of the pigment in the organic pigment solution is 0.02 or more.
(3) Organic pigment fine particles characterized in that after the organic pigment fine particles have been deposited by the production method according to (1) or (2), the solvent is removed from the mixed solution to powder the fine particles. Powder.
(4) After depositing the organic pigment fine particles by the production method according to (1) or (2), the solvent content of the mixed solution is replaced with a replacement solvent, and then the solvent content containing the replacement solvent Organic pigment fine particle powder characterized by being removed and powdered.
(5) A mixed liquid having organic pigment fine particles precipitated by the production method according to (1) or (2) or an organic pigment fine particle powder according to (3) or (4) Pigment dispersion.
(6) The pigment dispersion as described in (5), wherein a polymer compound having a mass average molecular weight of 1000 or more is contained.
(7) The pigment dispersion as described in (6), 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. ]
(8) A color filter inkjet ink comprising the pigment dispersion described in any one of (5) to (7) and a polymerizable monomer and / or a polymerizable oligomer.
(9) A pigment dispersion described in any one of (5) to (7), a binder, a monomer or an oligomer, and a photopolymerization initiator or a photopolymerization initiator system. Colored photosensitive resin composition.
(10) A photosensitive resin transfer material, wherein a photosensitive resin layer containing at least the colored photosensitive resin composition according to (9) is provided on a temporary support.
(11) A color produced by using the inkjet ink according to (8), the colored photosensitive resin composition according to (9), and / or the photosensitive resin transfer material according to (10). filter.
(12) A liquid crystal display device comprising the color filter according to (11).

The organic pigment nanoparticles produced by the production method of the present invention exhibit high contrast when used in a color filter, and suppress color unevenness when realizing image display by incorporating it in a liquid crystal display device, thereby realizing high display quality. There is an excellent effect.
Moreover, according to the manufacturing method of this invention, the organic pigment nanoparticle which has said outstanding characteristic can be produced efficiently on an industrial scale.

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

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

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

  In the production method of the present invention, an organic pigment 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). The pigment nanoparticles are precipitated by mixing with the solvent. 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 the combination that enables the process in the present invention Any choice is possible.

  The good solvent is not particularly limited as long as it can dissolve the organic pigment to be used and is compatible with or uniformly mixed with the poor solvent. As for the solubility of the organic pigment in a good solvent, the solubility of the organic pigment is preferably 0.2% by mass or more, and more preferably 0.5% by mass or more. Although there is no particular upper limit to the solubility of the organic pigment in the good solvent, it is practical that it is 50% by mass or less in consideration of a commonly used organic pigment. This solubility may be the solubility when dissolved in the presence of an acid or alkali.

  Examples of the good solvent include an aqueous solvent (for example, water or hydrochloric acid, an aqueous sodium hydroxide solution), an alcohol compound solvent, an amide compound solvent, a ketone compound solvent, an ether compound solvent, an aromatic compound solvent, a carbon disulfide solvent, and a fat. Group compound solvents, nitrile compound solvents, sulfoxide compound solvents, halogen compound solvents, ester compound solvents, ionic liquids, mixed solvents thereof, and the like, aqueous solvents, alcohol compound solvents, ketone compound solvents, ether compound solvents, sulfoxide compounds Solvents, ester compound solvents, amide compound solvents, or mixtures thereof are preferred, aqueous solvents, alcohol compound solvents, ester compound solvents, sulfoxide compound solvents or amide compound solvents are preferred, aqueous solvents, sulfoxide compound solvents or amide compounds. More preferably medium, sulfoxide compound solvent or the amide compound solvent is particularly preferred.

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

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

  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. Generally, in the case of a pigment having an alkaline dissociable group in the molecule, the addition of an alkali is performed. When there is no alkaline dissociable group and there are many nitrogen atoms or the like in the molecule that are prone to add protons, an acid is added. 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 the decomposition of the organic pigment molecules proceeds at the same time, the pigment dissolution accelerator in 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 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 (for example, water or hydrochloric acid, an aqueous sodium hydroxide solution), an alcohol compound solvent, a ketone compound solvent, an ether compound solvent, an aromatic compound solvent, a carbon disulfide solvent, an aliphatic compound solvent, Examples thereof include nitrile compound solvents, halogen compound solvents, ester compound solvents, ionic liquids, and mixed solvents thereof, and aqueous solvents, alcohol compound solvents, ketone compound solvents, ether compound solvents, ester compound solvents, or mixtures thereof are preferable. An aqueous solvent, an alcohol compound solvent or an ester compound solvent is more preferable.

Examples of the alcohol compound solvent include methanol, ethanol, isopropyl alcohol, n-propyl alcohol, 1-methoxy-2-propanol and the like. Examples of the ketone compound solvent include acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone. Examples of the ether compound solvent include dimethyl ether, diethyl ether, tetrahydrofuran, and the like. Examples of the aromatic compound solvent include benzene and toluene. Examples of the aliphatic compound solvent include hexane. Examples of the nitrile compound solvent include acetonitrile. Examples of the halogen compound solvent include dichloromethane and trichloroethylene. Examples of the ester compound solvent include ethyl acetate, ethyl lactate, 2- (1-methoxy) propyl acetate and the like. The ionic liquids, for example, 1-butyl-3-methylimidazolium and PF ₆ ^-, etc. and salts thereof.

  There are no particular limitations on the conditions of the poor solvent for precipitation of the organic particles, 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 size of the organic nanoparticles to be deposited 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 formula (2), where A is the cross-sectional area of the pipe, p is the wetted length (circumferential length) of the pipe, or p is the outer periphery of the flow path.
L = 4 A / p Equation (2)
It is preferable to form particles by injecting 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 is, for example, 0.8 to 2.0 kg / m ³ in the range of materials preferably used in the production method of the present invention. That is practical. The viscosity coefficient μ of the organic pigment solution is also a value determined by the material used, the ambient temperature, and the like, but its preferred range is synonymous with the preferred viscosity of the organic pigment solution described above.

  The smaller the Reynolds number (Re) value, the easier it is to form a laminar flow, and the larger the value, the easier it is to form a turbulent flow. For example, the particle size of the organic nanoparticles can be controlled by adjusting the Reynolds number to 60 or more, preferably 100 or more, and more preferably 150 or more. There is no particular upper limit to the number of lay nozzles, but it is preferable because, for example, good organic nanoparticles can be controlled and obtained by adjusting and controlling in the range of 100,000 or less. 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 organic 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 the organic fine particles are deposited, the concentration of nanoparticles in the liquid is not particularly limited, but the organic particles are preferably in the range of 10 to 40,000 mg, more preferably in the range of 20 to 30000 mg, especially with respect to 1000 ml of the solvent. Preferably it is the range of 50-25000 mg.
Moreover, the preparation scale at the time of producing | generating a pigment nanoparticle is although it does not specifically limit, It is preferable that the mixing amount of a poor solvent is a 10-2000L preparation scale, and it is more preferable that it is a 50-1000L preparation scale.

[Measurement calculation method of decomposition rate]
In the present invention, the decomposition rate Φ is defined as the ratio of pigment molecules that have been decomposed immediately before the organic pigment solution and the poor solvent are brought into contact with each other among all pigment molecules added to the pigment solution. However, since it is not practical to directly measure and identify this, the decomposition rate Φ is determined as follows based on the fact that the absorbance at a predetermined absorption wavelength of the pigment decreases as the pigment molecules decompose.
The process of adding organic pigment powder (aggregation of pigment molecules) in a good solvent and dissolving the pigment in a monomolecular state, and the process of decomposition of the pigment molecules, that is, the change of the chemical structure of the pigment molecules The absorption spectrum of the pigment solution is measured by the following method, the following values A and B are calculated, and the decomposition rate Φ is obtained by the following equation (Equation 1).
φ = (1-B / A) × 100 Formula 1
The calculation of the value A will be described. The organic pigment powder Xmg was weighed in advance and placed in a beaker kept at 20 ° C., and 100 cc of a good solvent used at 20 ° C. was added to the beaker over 5 seconds. And an attached stirring blade propeller R, and stirring at 800 rpm. The amount (Xmg) of the organic pigment powder at this time is set to an amount such that the absorbance ODm of a predetermined absorption wavelength λ derived from pigment molecules to be measured later is 0.3 to 0.5.
After the start of stirring, the absorption spectrum of the pigment solution is measured every 30 seconds in a 1 mm thick cell using an 8453 type spectrophotometer (trade name, manufactured by Agilent). At this time, a sample is taken from the pigment solution 10 seconds before each measurement time.
From the maximum value (ODm) of the absorbance at a predetermined absorption wavelength λ derived from the pigment molecule obtained by this measurement, the value of A is obtained by the following formula 2.
A = ODm / X Expression 2

Next, calculation of the value B will be described. When mixing an organic pigment solution and a poor solvent over time, the organic pigment solution immediately before mixing the two at an arbitrary time, specifically, one second before and after the organic pigment solution and the poor solvent contact each other Was collected at room temperature (25 ° C.), held at that temperature, and based on the time of collection, 1 minute later (measurement time 1), 2 minutes later (measurement time 2), 3 minutes later (measurement time 3) The absorbance at a predetermined absorption wavelength λ derived from the pigment molecules is measured using the spectrophotometer and the cell. At this time, the collected organic pigment solution is diluted 30 seconds before each measurement time so that the maximum value of the absorbance is 0.5, and the absorbance is measured at each measurement time. The dilution rate is the same at any time point. The dilution factor at this time is K times. However, dilution is not necessary when the maximum absorbance is 0.5 or less.
The absorbances measured at the above four measurement times are plotted, and three of them are fitted with an exponential function, and the absorbance ODn corresponding to 0 minute later, that is, immediately before the organic pigment solution and the poor solvent come into contact with each other, is obtained. The minimum absorbance at ODn at an arbitrary time is defined as ODna. When the amount of pigment powder contained in 100 cc of the organic pigment solution is Ymg, the value of B is obtained by the following formula 3 using the values of ODna and K.
B = ODna × K / Y Equation 3

  In the present invention, the decomposition rate Φ is preferably 20% or less, more preferably 10% or less, and particularly preferably 5% or less. For example, after the organic pigment is dissolved in a good solvent, the decomposition rate Φ increases when the organic pigment is allowed to stand for a longer period of time, while it decreases when the standing time is shorter.

[Measurement calculation method of decomposition rate index]
In the present invention, the pigment decomposition rate index V is defined as an index of the number of pigment molecules that decompose per unit time after the organic pigment is dissolved in a good solvent. However, since it is difficult to directly measure and identify this, it is determined as follows based on the fact that the absorbance at a predetermined absorption wavelength of the pigment decreases as the pigment molecules decompose. The process of adding organic pigment powder (aggregation of pigment molecules) in a good solvent and dissolving the pigment in a monomolecular state, and the process of decomposition of the pigment molecules, that is, the change of the chemical structure of the pigment molecules Then, the absorption spectrum of the pigment solution is measured by the following method, and the decomposition rate V is obtained by the following mathematical formula 4.
Pigment powder Xmg was weighed in advance and placed in a beaker kept at 20 ° C., and 100 cc of a good solvent used at 20 ° C. was added over 5 seconds. Upon completion of the addition, Three One Motor BL1200 (trade name, manufactured by HEIDON) ) And an attached stirring blade propeller R. The amount (Xmg) of the organic pigment powder at this time is set to an amount such that the absorbance at a predetermined absorption wavelength λ derived from pigment molecules to be measured later becomes 0.3 to 0.5.
After the start of stirring, the absorption spectrum of the pigment solution is measured every 30 seconds in a 1 mm cell using an 8453 type spectrophotometer (trade name, manufactured by Agilent). At this time, a sample is taken from the pigment solution 10 seconds before each measurement time.
The maximum value (ODm) of the absorbance at a predetermined absorption wavelength λ of the pigment molecule obtained by this measurement, and the absorbance (ODp) after 30 minutes from the time showing the maximum value (ODm), the pigment decomposition rate index V is obtained by the following mathematical formula 4.
V = 1−ODp / ODm Expression 4
There is no unit of this value, and it is a dimensionless number. The closer to “1”, the faster the decomposition rate of the pigment molecule, and when “0”, the decomposition of the pigment molecule does not occur.
The decomposition rate index V increases, for example, by increasing the pigment concentration in the good solvent, and decreases by decreasing the pigment concentration in the good solvent.

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

  In the production method of the present invention, in preparing the dispersion liquid by precipitating the pigment fine particles, 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 at least the dispersant in the pigment solution. .

It is also preferable to use pigment particles that have been surface-treated with a dispersant in advance, and the pigment particles may be subjected to a surface treatment that can promote adsorption of the dispersant. The dispersant (1) has a function of quickly adsorbing on the surface of the deposited pigment to form fine nanoparticles and (2) preventing these particles from aggregating again.
As the dispersant, for example, anionic, cationic, amphoteric, nonionic or pigment derivative polymer dispersants can be used.

The polymer dispersant preferably has a mass average molecular weight of 1,000 to 500,000, more preferably 10,000 to 500,000, and preferably 10,000 to 100,000. Particularly preferred.
Specifically, polyvinyl pyrrolidone, polyvinyl alcohol, polyvinyl methyl ether, polyethylene glycol, polypropylene glycol, polyacrylamide, vinyl alcohol-vinyl acetate copolymer, polyvinyl alcohol-partial formalized product, polyvinyl alcohol-partial butyralized product, vinylpyrrolidone- Vinyl acetate copolymer, polyethylene oxide / propylene oxide block copolymer, polyacrylate, polyvinyl sulfate, poly (4-vinylpyridine) salt, polyamide, polyallylamine salt, condensed naphthalenesulfonate, cellulose derivative, starch Derivatives and the like. In addition, natural polymers such as alginate, gelatin, albumin, casein, gum arabic, tonganto gum and lignin sulfonate can also be used. Of these, polyvinylpyrrolidone is preferable. These polymer compounds can be used singly or in combination of two or more, or a low molecular weight dispersant may be used in combination. The dispersant used for dispersing the pigment is described in detail on pages 29 to 46 of “Pigment dispersion stabilization and surface treatment technology / evaluation” (Chemical Information Association, issued in December 2001).

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

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

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

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

  It is also preferable to use a pigment dispersant containing an amino group as the dispersant. Here, the amino group includes a primary amino group, a secondary amino group, and a tertiary amino group, and the number of amino groups may be one or more. A pigment derivative compound in which a substituent having an amino group is introduced into the pigment skeleton, or a polymer compound having a monomer having an amino group as a polymerization component may be used. Examples of these include, for example, JP 2000-239554 A, 2003-96329 JP, 2001-31885 JP, JP 10-339949 A, JP 5-72943 A, and International Publication No. WO 2006/121017. 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 production method of the present invention, after the organic pigment fine particles are precipitated, it is preferable to reduce or remove the solvent content of the dispersion containing the precipitated particles (hereinafter, this operation may be simply referred to as concentration). is there.). Thereby, it can be set as the nanoparticle concentrated liquid and organic pigment fine particle powder suitable for a color filter coating liquid and an inkjet ink.

In the present invention, a normal apparatus can be used alone or in combination for the concentration of the solvent. 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, a spray dryer (for example, COC-12 manufactured by Okawara Chemical Co., Ltd.), fluidized bed dryer ( For example, Nara Machinery Co., Ltd. MSD-100) is particularly preferably used. In addition, a plurality of drying means may be used in combination in order to obtain organic pigment fine particle powder with a small amount of residual solvent. For example, a pigment dispersion pre-concentrated with a cylindrical dryer is completely dried with a drum dryer. A process such as obtaining a fine powder can be used.
The drying conditions are not particularly limited as long as the solvent can be evaporated and materials such as pigments and dispersants are not denatured. Of course, when other dispersants are denatured at a lower temperature, it is necessary to lower the temperature. However, depending on the type of solvent used, the drying speed may be reduced within the allowable temperature range. In this case, for the purpose of increasing the drying speed, depending on the type of dryer, means such as decompression, stirring and mixing, multiple stages, etc. Can be combined.

The amount to reduce or remove the solvent content is not particularly limited, but in an embodiment in which the solvent content is reduced, it is preferable to remove 50% by mass or more of the total solvent content, and more preferably 75% by mass or more. In an embodiment in which the solvent content is removed to obtain organic pigment fine particle powder, it is preferable to remove 80% by mass or more, and more preferably 90% by mass or more of the total solvent content.
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 mass%. At this time, it is preferable to remove the solvent by, for example, the above-described drying method to obtain organic pigment fine particle powder. At this time, the solid content is preferably 50 to 100% by mass, and 70 to 100% by mass. More preferably.
The concentration 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 production method of the present invention, it is preferable to re-disperse the organic particles that are in an aggregated state by the above concentration or pulverization. The organic particles contained in the organic particle liquid concentrated by the extraction solvent, centrifugation, drying, etc. described above may usually be agglomerated by concentration or powdering. As a result, rapid filter filtration is possible, but in order to obtain a good dispersion state again, it is preferable to obtain flocs aggregated to such an extent that they can be redispersed.
Further, in order to disperse the above-mentioned aggregated particles, a normal dispersion method may be insufficient. Even in the organic particles in such an agglomerated state, the organic particles can be suitably redispersed, for example, by containing the following polymer compound.

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

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

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

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

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

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

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

Specific examples of R ¹⁸ include the following structural units or groups formed by combining the structural units. The linking group R ¹⁸ may have the substituent T.

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

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

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

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

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

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

In the general formula (2), A ² has the same meaning as A ¹ in the general formula (1), the same applies its specific preferred embodiment. A ² may have a substituent, and examples thereof include the substituent T.

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

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

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

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

In the general formula (2), R ⁴ and R ⁵ each independently represents a single bond or a divalent linking group.
The “divalent linking group” represented by R ⁴ and R ⁵ is a linear, branched, or cyclic alkylene group, arylene group, or aralkylene group, which may have a substituent, — O -, - S -, - C (= O) -, - N (R 19) -, - SO -, - SO 2 -, - CO 2 -, or _{^{-N (R 20) SO 2 -}} , or they A divalent group in which two or more groups are combined is preferable (the R ¹⁹ and R ²⁰ each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms). Of these, an organic linking group is preferred.

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

R ⁵ is a single bond, straight chain or branched alkylene group, aralkylene group, —O—, —C (═O) —, —N (R ¹⁹ ) —, —SO ₂ —, —CO _2. —, Or —N (R ²⁰ ) SO ₂ —, or a divalent group obtained by combining two or more of these groups is more preferable, and a linear or branched alkylene group, aralkylene group, —O—, —C (= O) —, —N (R ¹⁹ ) —, or —CO ₂ —, or a divalent group in which two or more of these groups are combined is particularly preferable.

Moreover, when said R < ⁴ >, R < ⁵ > has a substituent, the said substituent T is mentioned as this substituent.

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

Among the polymer compounds represented by the general formula (2), in particular, R ³ represents the specific examples (r-1), (r-2), (r-10), (r-11), (r -16) or (r-17), wherein R ⁴ is a single bond, linear or branched, alkylene group or aralkylene group, —O—, —C (═O) —, —N (R ¹⁹ ) -, or -CO 2 _-, or a divalent organic group formed by combining two or more of these groups, R ⁵ is a single bond, an ethylene group, a propylene group, or the following general formula (s-a) or A linking group represented by (s-b), wherein P ² is a polymer or copolymer of a vinyl monomer, an ester compound polymer, an ether compound polymer, a urethane 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 production method of 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, more preferably 7000 Particularly preferred is 60000. When the mass average molecular weight is within the above range, the effects of the multiple functional groups introduced at the polymer ends are sufficiently exhibited, and the performance of adsorbing to a solid surface, micelle forming ability, and surface activity is excellent. Good dispersibility and dispersion stability can be achieved.

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

The polymer compound represented by the general formula (1) or (2) can be synthesized, for example, by the following methods.
1. A polymer in which a functional group selected from a carboxyl group, a hydroxyl group, an amino group and the like is introduced at the terminal, an acid halide having a plurality of functional groups (A ¹ or A ² in the general formula), or a plurality of functional groups ( A method in which an alkyl halide having A ¹ or A ² ) in the general formula or an isocyanate having a plurality of functional groups (A ¹ or A ² in the general formula) is polymerized.
2. A method in which a polymer having a carbon-carbon double bond introduced at the terminal and a mercaptan having a plurality of functional groups (A ¹ or A ² in the above general formula) are subjected to a Michael addition reaction.
3. A method in which a polymer having a carbon-carbon double bond introduced at a terminal thereof and a mercaptan having a plurality of functional groups (A ¹ or A ² in the above general formula) are reacted in the presence of a radical generator.
4). A method of reacting a polymer having a plurality of mercaptans introduced at its terminal and a functional group having a carbon-carbon double bond introduced (A ¹ or A ² in the above general formula) in the presence of a radical generator.
5. A method of radical polymerization of a vinyl monomer using a mercaptan compound having a plurality of functional groups (A ¹ or A ² in the above general formula) as a chain transfer agent.
Of these, 2, 3, 4, 5 are preferable, 3, 4, 5 are more preferable, and 5 is particularly preferable because of ease of synthesis. As for these synthesis methods, the contents described in paragraphs 0184 to 0216 of Japanese Patent Application No. 2006-129714 can be referred to.

In addition, as a polymer compound having a molecular weight of 1000 or more, a polymer compound having the following acidic group (hereinafter, this compound may be referred to as “acidic group-containing polymer compound”) may be used. It is preferably a polymer compound having a group, and (A) at least one repeating unit derived from a compound having a carboxyl group and (B) at least one repeating unit derived from a compound having a carboxylic ester group. More preferred are copolymer compounds containing seeds.
The repeating unit derived from the compound (A) having a carboxyl group is preferably a repeating unit represented by the following general formula (I), preferably a repeating unit derived from acrylic acid or methacrylic acid. More preferably, the repeating unit derived from the compound (B) having a carboxylic acid ester group is preferably a repeating unit represented by the following general formula (II), and represented by the following general formula (IV). A repeating unit is more preferable, and a repeating unit derived from benzyl acrylate, benzyl methacrylate, phenethyl acrylate, phenethyl methacrylate, 3-phenylpropyl acrylate, or 3-phenylpropyl methacrylate is particularly preferable.

In the formula, R ₁ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. R ₂ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. R ₃ represents a group represented by the following general formula (III). R ₄ represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a hydroxy group, a hydroxyalkyl group having 1 to 5 carbon atoms, or an aryl group having 6 to 20 carbon atoms. R ₅ and R ₆ each represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. i represents the number of 1-5. R ₇ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. R ₈ represents a group represented by the following general formula (V). R ₉ represents an alkyl group having 2 to 5 carbon atoms or an aryl group having 6 to 20 carbon atoms. R ₁₀ and R ₁₁ represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. j represents a number from 1 to 5;

Further, in terms of the polymerization ratio of the repeating unit derived from the compound having (A) carboxyl group and the repeating unit derived from the compound having (B) carboxylate group, all of the repeating units (A) The quantity ratio% to the number of repeating units is preferably 3 to 40, more preferably 5 to 35.
In the production method of the present invention, the molecular weight means a mass average molecular weight unless otherwise specified. Examples of the molecular weight measuring method include chromatography, viscosity, light scattering, sedimentation rate, etc. In the present invention, unless otherwise specified, polystyrene measured by gel permeation chromatography (carrier: tetrahydrofuran). The converted mass average molecular weight is used.

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

The polymer compound may be water-soluble or oil-soluble, and may be water-soluble and oil-soluble.
The polymer compound may be added by a solution in an aqueous solvent or an organic solvent, a solid state, or a combination thereof. As a method of adding in a solution dissolved in a solvent, for example, a method of adding to an aggregated organic particle liquid in a state dissolved in a solvent similar to the solvent of the aggregated organic particle liquid, compatible with the solvent of the aggregated organic particle liquid, The method of adding in the state melt | dissolved in a different solvent is mentioned. The concentration of the polymer compound when added in a solution dissolved in a solvent is not particularly limited, but is preferably 1 to 70% by mass, more preferably 2 to 65% by mass, and particularly preferably 3 to 60% by mass.
The polymer compound may be added at any time during or after the precipitation of pigment nanoparticles, during or after concentration, when or after the dispersion of aggregated organic particles after concentration, or after the completion of these steps. It may be added, or may be added in a plurality of times. In the production method of the present invention, a polymer compound having a mass average molecular weight of 1000 or more may be contained in the composition as a binder to be described later. For example, after concentrating the organic fine particle deposit, finely dispersing the aggregated organic particles It is preferable to add to.

  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 production method of the present invention, it is preferable to contain a substitution solvent (third solvent) after the pigment fine particles are precipitated. Although the kind of 3rd solvent is not specifically limited, It is preferable that it is an organic solvent, for example, an ester compound solvent, an alcohol compound solvent, an aromatic compound solvent, an aliphatic compound solvent, a ketone compound solvent is preferable, an ester compound solvent, a 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 n-butanol and isobutanol. Examples of the aromatic compound solvent include benzene, toluene, xylene and the like. Examples of the aliphatic compound solvent include n-hexane and cyclohexane. Examples of the ketone compound solvent include methyl ethyl ketone, acetone, and cyclohexanone.

  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).

The timing of adding the substitution solvent is not particularly limited as long as it is after the precipitation of pigment fine particles, 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 solution in which the organic nanoparticles are deposited 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), a 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. Then, a desired pigment dispersion composition can be obtained by adding a binder and / or a solvent thereafter.
Although the addition amount of the substitution solvent is not particularly limited, it is preferably 100 to 300,000 parts by mass and more preferably 500 to 10,000 parts by mass with respect to 100 parts by mass of the pigment fine particles.

  The pigment fine particles can be used, for example, in a dispersed state in a vehicle. The vehicle refers to a portion of a medium in which a pigment is dispersed when it is in a liquid state, a portion that is liquid and binds to the pigment to harden a coating film (binder). And a component (organic solvent) to be dissolved and diluted. In the present invention, the binder used for nanoparticle formation and the binder used for redispersion may be the same or different.

  The pigment nanoparticle concentration of the pigment nanoparticle dispersion composition after redispersion is appropriately determined according to the purpose, but preferably the pigment nanoparticle content is 2 to 30% by mass with respect to the total amount of the dispersion composition. More preferably, it is 4-20 mass%, and it is especially preferable that it is 5-15 mass%. In the case of dispersing in the vehicle as described above, the amount of the binder and dissolved dilution component is appropriately determined depending on the type of the organic pigment and the like, but the binder is 1 to 30% by mass with respect to the total amount of the dispersion composition. Preferably, it is 3-20 mass%, More preferably, it is 5-15 mass%. It is preferable that a dissolution dilution component is 5-80 mass%, and it is more preferable that it is 10-70 mass%.

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

  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 the nanometer-sized organic pigment fine particles and the dispersion thereof has already been described in detail. The content of the pigment fine particles is preferably 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). 20-80 mass% is more preferable, and 25-60 mass% is further more preferable. If this amount is too large, the viscosity of the dispersion increases, which may cause problems in production suitability. If the amount is too small, the coloring power is not sufficient. The pigment nanoparticles (pigment fine 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.
Monomers or oligomers may be used alone or in admixture of two or more. The content of the colored photosensitive resin composition with respect to the total solid content is generally 5 to 50% by mass, and 10 to 40% by mass. Is preferred. If this amount is too large, it becomes difficult to control the developability, which causes a problem in production suitability. If the amount is too small, the curing power at the time of exposure is insufficient.

As the binder, a binder having an acidic group is preferable, and it can be added at the time of preparing the inkjet ink for color filter or the colored photosensitive resin composition, but when producing the pigment nanoparticle dispersion composition, or the pigment nanoparticle It is also preferable to add at the time of formation. 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.
The binder may be used alone 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 fine particles is generally 10 to 200 parts by mass. Yes, 25-100 mass parts is preferable.

As a photopolymerization initiator or a photopolymerization initiator system (in the present invention, a photopolymerization initiator system means a mixture that exhibits a photopolymerization initiation function by a combination of a plurality of compounds). The compound used can be used.
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 photopolymerization initiator system with respect to the total solid content of the colored photosensitive resin composition is generally 0.5 to 20% by mass, and preferably 1 to 15% by mass. If this amount is too large, the sensitivity becomes too high and control becomes difficult. If the amount is too small, the exposure sensitivity becomes too low.

  In the colored photosensitive resin composition, in addition to the above components, an organic solvent for preparing a resin composition (fourth solvent) may be further used. Examples of the fourth solvent include, but are not limited to, esters, ethers, and ketones. Among these solvents, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, ethyl carbitol acetate, butyl carbitol Acetate, propylene glycol methyl ether acetate and the like are preferably used as the solvent. 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.

  The colored photosensitive resin composition can contain a surfactant, a thermal polymerization inhibitor, a colorant (dye, pigment), an ultraviolet absorber, an adhesion aid, other additives, and the like.

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

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.

  In the present invention, it is preferable that a partition wall is prepared in advance and ink is applied to a portion surrounded by the partition wall before forming a pixel 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.

  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 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. An example of the structure of the integral film is a structure in which a temporary support / thermoplastic resin layer / intermediate layer / photosensitive resin layer / protective film are laminated in this order.

  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.

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 TFT-LCD, Ueki, Koseki, Fukunaga, Yamanaka "etc.).
The high contrast of the color filter means that the bright and dark discrimination when combined with the liquid crystal can be increased, which is a very important performance in order to replace the liquid crystal display with a CRT.

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

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

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

  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 970 ml of 1-methyl-2-pyrrolidone (manufactured by Wako Pure Chemical Industries, Ltd.), 61.0 ml of a 30% sodium methoxide methanol solution, pigment C.I. I. A pigment solution A to which 30 g of Pigment Green 36 (Lionol Green 6YK, trade name, manufactured by Toyo Ink Co., Ltd.) and 50 g of polyvinylpyrrolidone (K-30, trade name, manufactured by Wako Pure Chemical Industries, Ltd.) was added was prepared. Separately, 1000 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 A was added to 1200 ml of poor solvent water stirred at 600 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 at a flow rate of 110 ml / min using a large-capacity non-pulsating flow pump (trade name, manufactured by Nippon Seimitsu Chemical Co., Ltd.) to prepare pigment dispersion A. 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 15 nm and Mv / Mn was 1.30. The decomposition rate and decomposition rate of the pigment in the pigment solution A were determined by the procedure described in [Measurement and calculation method of decomposition rate] and [Measurement and calculation method of decomposition rate]. Each value in the calculation at this time was as follows. The results are shown in Table 2.

Pigment powder amount X: 10.9 mg
Absorption wavelength λ: 860 nm
Value A: 0.0367
Dilution factor K: 214
Absorbance ODna: 0.404
Pigment powder amount Y: 2910 mg
Value B: 0.0308
Absorbance ODp: 0.28

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 that settled down was recovered. When the pigment content of the paste was measured using an 8453 type spectrophotometer (trade name, manufactured by Agilent), it was 25% by mass.
13.0 g of the above pigment nanoparticle concentrated paste, 1.0 g of the following pigment dispersant A synthesized in 50.0 ml of ethyl lactate according to JP 2000-239554 A and compounds represented by the general formula (1) (C -16) After adding the solution to which 6.1 g was added and stirring at 3000 rpm for 60 minutes with a dissolver, the mixture was filtered using an FP-010 type filter (trade name, manufactured by Sumitomo Electric Fine Polymer Co., Ltd.). Concentrated pigment liquid A (nano pigment concentration 28 mass%) was obtained.

[Preparation of G pigment dispersion A]
Using the paste, G pigment dispersion A having the following composition was prepared.
12.8 g of the concentrated pigment liquid A in the form of paste
1-methoxy-2-propyl acetate (Wako Pure Chemical Industries, Ltd.) 19.8 g

The pigment dispersant A was synthesized according to Japanese Patent Laid-Open No. 2000-239554.
G 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 2. 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, manufactured by Nippon Kayaku Co., Ltd., trade name: KAYARAD DPHA) 76 parts by mass Propylene glycol monomethyl ether acetate 24 parts by mass <Surfactant 1>
Megafac F-780-F (Dainippon Ink and Chemicals, Inc.): composition below _{· C 6 F 13 CH 2 CH} 2 OCOCH = CH 2 40 parts by weight and _{H (OCH (CH 3) CH} 2) Copolymer of 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 R1 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 R1 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 ) 0.80
C. I. P. R. 177 coating amount (g / m ² ) 0.20

[Table 1-2]
--------------------------------------
R pigment dispersion 1 (CIPR254) 40 parts by mass R pigment dispersion 2 (CIPR177) 4.5 parts by mass Propylene glycol monomethyl ether acetate 7.6 parts by mass Methyl ethyl ketone 37 parts by mass Binder 1 0.7 parts by mass DPHA liquid 3.8 Parts by mass polymerization initiator B 0.12 parts by mass polymerization initiator A 0.05 parts by mass phenothiazine 0.01 parts by mass surfactant 1 0.06 parts by mass -------------- ------------------------

<R pigment dispersion 1>
・ C. I. P. R. 254 (trade name: Irgaphor Red B-CF,
Ciba Specialty Chemicals Co., Ltd.) 8 parts by weight, dispersant (compound 1) 0.8 parts by weight, polymer (benzyl methacrylate / methacrylic acid = 72/28 molar ratio)
(Random copolymer of 30,000) 8 parts by mass / 83 parts by mass of propylene glycol monomethyl ether acetate <R pigment dispersion 2>
・ C. I. P. R. 177 (Product name: Chromophthal Red A2B,
Ciba Specialty Chemicals Co., Ltd.) 18 parts by mass Polymer (benzyl methacrylate / methacrylic acid = 72/28 molar ratio)
Random copolymer of, molecular weight 30,000) 12 parts by mass / 70 parts by mass of propylene glycol monomethyl ether acetate <Binder 1>
・ Polymer (benzyl methacrylate / methacrylic acid = 78/22 molar ratio
(Random copolymer, 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 A (CIPG36) 28 parts by mass Y pigment dispersion 1 (CIPI 150) 15 parts by mass Propylene glycol monomethyl ether acetate 29 parts by mass Methyl ethyl ketone 26 parts by mass Cyclohexanone 1.3 parts by mass Binder 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 ------------ -------------------------

<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 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

<Production of color filters B1, C1, and D1>
After preparing the pigment solution A used in the production of the color filter A1, G pigment dispersions B, C, and D were prepared in the same manner except that the decomposition rate of the pigment was changed by shortening the addition start time to the poor solvent. Then, color filters B1, C1, and D1 were produced. Table 2 below shows the results of determining the decomposition rate and decomposition rate of the pigment in the same manner as in the case of the color filter A1.

<Preparation of color filter E1>
To 1000 ml of dimethyl sulfoxide (manufactured by Wako Pure Chemical Industries, Ltd.), pigment C.I. I. A pigment dispersion B was prepared by adding 30 g of Pigment Green 36 (Lionol Green 6YK, trade name, manufactured by Toyo Ink Co., Ltd.) and 50 g of polyvinylpyrrolidone (K-30, trade name, manufactured by Wako Pure Chemical Industries, Ltd.). Separately, 1000 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, NP-KX-500 type large capacity non-pulsating flow pump (trade name, manufactured by Nippon Seimitsu Chemical Co., Ltd.) and pigment dispersion E fed at a flow rate of 106.7 ml / min, another NP-KX -Three-way joint (JON-16S-ON (trade name), Japan) with a sodium methoxide 30% methanol solution with a flow rate of 3.3 ml / min sent through a separate flow path using a 500-type large capacity non-pulsating pump The mixture was injected from two inlets of Seimitsu Chemical Co., Ltd., and the solution was discharged from one outlet while being a pigment solution E in a three-way joint. By controlling the temperature to 18 ° C. and injecting 100 ml of the above pigment solution B into 1200 ml of poor solvent water stirred at 600 rpm by a GK-0222-10 type Lamond Stirrer (trade name, manufactured by Fujisawa Pharmaceutical Co., Ltd.) Organic pigment particles were formed, and a pigment dispersion E was prepared. Other than that, G pigment dispersion E was prepared similarly to preparation of color filter A1, and color filter E1 was produced. Table 2 shows the results obtained by similarly determining the pigment decomposition rate and the pigment decomposition rate in the pigment solution B.

<Preparation of color filter F1>
The pigment dispersion E obtained in the production of the color filter E1 is transferred to an eggplant-shaped flask and dried under reduced pressure at 70 ° C. for 1.5 hours with an evaporator to obtain a pigment dispersion dried powder F (pigment concentration 55.4% by mass). Obtained. A solution obtained by adding 1.0 g of pigment dispersant A and 6.1 g of the exemplary compound (C-16) represented by the general formula (1) to 50.0 cc of ethyl lactate was added to 10.0 g of the above pigment dispersion dry powder F. In addition, after stirring at 3000 rpm for 80 minutes with a dissolver, the mixture was filtered using a FP-010 filter (trade name, manufactured by Sumitomo Electric Fine Polymer Co., Ltd.) to obtain a paste-like concentrated pigment solution F (nano pigment concentration 25). G Pigment Dispersion F was prepared in the same manner except that (mass%) was obtained, and a color filter F1 was produced. Table 2 shows the decomposition rate of the pigment and the decomposition rate of the pigment in the pigment solution.

<Production of color filter G1>
13.0 g of pigment nanoparticle concentrated paste obtained in the production of the color filter E1, 50.0 cc of ethyl lactate, 1.0 g of pigment dispersant A, and exemplified compound (C-16) 6 represented by the general formula (1) 1 g of the solution was added, stirred at 3000 rpm for 60 minutes with a dissolver, transferred to an eggplant-shaped flask, and dried under reduced pressure at 70 ° C. for 1.5 hours with an evaporator to obtain a pigment dry powder G (pigment concentration 50. 0% by mass) was obtained. Table 2 shows the decomposition rate and decomposition rate of the pigment.

[Preparation of G pigment dispersion G]
A G pigment dispersion G having the following composition was prepared.
8.8 g of the pigment dry powder G
1-methoxy-2-propyl acetate (Wako Pure Chemical Industries, Ltd.) 19.8 g

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

  A color filter G1 was produced using the G pigment dispersion G in the same manner as the color filter A1.

<Preparation of color filters H1, I1, J1>
After preparing the pigment solution A used in the production of the color filter A1, G pigment dispersions H, I, and J were prepared in the same manner except that the decomposition rate was changed by increasing the addition start time to the poor solvent. Color filters H1, I1, and J1 were produced. The pigment decomposition rate and decomposition rate at this time are shown in Table 2 below.

[Table 2]
------------------------------------
Color filter Decomposition rate Φ Decomposition rate index V
------------------------------------
A1 19% 0.3
B1 18% 0.3
C1 16% 0.3
D1 8% 0.3
E1 3% 0.3
F1 3% 0.3
G1 3% 0.3
H1 25% 0.3
I1 22% 0.3
J1 21% 0.3
------------------------------------
[Measurement of contrast of color filters A1 to J1]
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 the ratio was taken as contrast (Ueki, Koseki, Fukunaga, Yamanaka) , "512 color display 10.4" size TFT-LCD color filter ", 7th Color Optical Conference (1990), etc.).
Table 5 shows the measurement results of the contrast of the color filters A1 to J1.

[Evaluation of uneven color]
A transparent electrode film was formed on the produced color filters A1 to J1 by sputtering of ITO.
(Spacer production)
On the ITO film of the color filter substrate on which the ITO film produced above is formed by sputtering, using the following spacer prescription A having the composition shown in Table 3 below, by the same process as the formation of the black (K) image, A transfer material was prepared, exposed and developed to form a spacer pattern. The obtained spacer pattern was columnar with a diameter of 16 μm and an average height of 3.7 μm.
Next, the color filter substrate provided with the spacer pattern was subjected to heat treatment at 230 ° C. for 30 minutes (heat treatment step) to produce a spacer.

[Table 3] Spacer prescription A
------------------------------------
Pigment 1 120 parts by weight 1-methoxy-2-propyl acetate 436 parts by weight Methyl ethyl ketone 343 parts by weight Methanol 17 parts by weight Binder 4 80 parts by weight DPHA solution 79 parts by weight Polymerization initiator A 2.2 parts by weight Hydroquinone monomethyl ether 0.100 parts by weight Parts Surfactant 1 0.86 parts by weight Colored dye 15 parts by weight --------------------------------- −−

<Pigment 1>
・ 30% methyl isobutyl ketone dispersion of silica sol (trade name: MIBK-ST, manufactured by Nissan Chemical Industries, Ltd.)
<Binder 4>
・ Methacrylic acid / allyl methacrylate copolymer (= 20/80 [molar ratio], mass average molecular weight 36,000; polymer substance)
<Coloring dye>
・ Victoria Pure Blue BOH-M (Hodogaya Chemical Co., Ltd.)
The DPHA liquid, the surfactant 1, and the polymerization initiator A are the same as described above.

(Preparation of liquid crystal alignment control protrusions)
On the side of the color filter substrate on which the ITO film is provided (on the color filter) on which the spacer obtained from the above is formed, the following liquid crystal alignment control projection formulation B having the composition shown in Table 4 below is used, and the black ( K) A transfer material was prepared, transferred and exposed by the same process as the image formation. The exposure amount was 50 mJ / cm ² .

[Table 4] Protrusion prescription B for liquid crystal alignment control
---------------------------------------
Positive resist solution FH-2413F 53.3 parts by mass (manufactured by FUJIFILM Electronics Materials Co., Ltd.)
Methyl ethyl ketone 46.7 parts by mass Surfactant 1 0.04 parts by mass --------------------------------- ------

Then, it developed with the method similar to color filter A1 except having used the following developing solution instead of the sodium carbonate type developing solution.
(Developer)
An aqueous solution containing 0.085 mol / L sodium carbonate, 0.085 mol / L sodium bicarbonate, and 1% sodium dibutylnaphthalenesulfonate.

As a result, a liquid crystal alignment control projection made of a photosensitive resin layer for liquid crystal alignment control projection patterned in a desired shape was formed on the color filter (RGB pixel).
Next, the color filter substrate on which the liquid crystal alignment control protrusions are formed is baked at 240 ° C. for 50 minutes, so that the liquid crystal alignment is 1.5 μm in height and has a vertical cross-sectional shape on the color filter (RGB pixel). A control protrusion was formed.

Apart from the above, a TFT substrate was prepared as a counter substrate. On one surface of the TFT substrate, an ITO (Indium Tin Oxide) film is formed by sputtering.
Subsequently, an alignment film made of polyimide was provided on the ITO film of the TFT substrate and the ITO film on the side of the color filter substrate on which the spacers were provided.
Thereafter, an epoxy resin sealant was printed at a position corresponding to an outer frame of a black matrix provided around the pixel group of the color filter, and the color filter substrate was bonded to the TFT substrate.
Next, the two bonded substrates were heat-treated to cure the sealing agent to obtain a laminate of the two substrates. The laminate was degassed under vacuum, then returned to atmospheric pressure, and liquid crystal was injected into the gap between the two glass substrates. After completion of the injection, a liquid crystal cell was obtained by applying an adhesive to the injection port portion and sealing by irradiation with ultraviolet rays.
A polarizing plate (HLC2-2518, manufactured by Sanritsu Co., Ltd.) was attached to both surfaces of the liquid crystal cell thus obtained. Next, although not shown in the drawing, a side light type back using FR1112H as a red (R) LED, DG1112H as a green (G) LED, and DB1112H as a blue (B) LED (both are chip-type LEDs manufactured by Stanley Corporation). An MVA mode liquid crystal display device was manufactured by composing a light and disposing it on the back side of the liquid crystal cell provided with the polarizing plate.

  The display characteristics of each manufactured liquid crystal display device were evaluated from the viewpoint of the presence or absence of color unevenness when green was displayed in a single color. Evaluation was performed by 10 panelists, and an average of 10 persons was used as an evaluation value in the following stage evaluation. Table 5 shows the evaluation results of the color unevenness of the color filters A1 to J1.

(Green color unevenness)
5: No unevenness is seen at all (very good)
4: I don't care about unevenness (good)
3: Unevenness is felt slightly (normal)
2: Unevenness can be clearly recognized (slightly bad)
1: Unevenness is noticeable (very bad)

[Table 5]
----------------------------
Color filter Contrast Color unevenness evaluation -----------------------------
A1 8030 3.3
B1 8030 3.1
C1 8030 3.3
D1 7800 3.4
E1 8000 4.5
F1 8500 5.0
G1 9200 5.0
H1 8100 1.0
I1 8100 1.8
J1 8100 1.2
------------------------------

As shown in Table 5, in the color filters H1, I1, and J1, color unevenness occurred when an image was displayed by being incorporated in a liquid crystal display device.
On the other hand, the color filters A1 to G1 of the present invention were able to sufficiently suppress the occurrence of color unevenness practically. Further, the color filters F1 and G1 prepared by once powdering the organic pigment fine particles showed higher contrast and color unevenness suppressing effect.
From this result, it can be seen that according to the present invention, a color filter exhibiting high contrast can be obtained, and furthermore, when mounted on a liquid crystal display device, display defects due to color unevenness can be suppressed and high display quality can be realized.

(Example 2 and Comparative Example 2)
<Production of Color Filters A2 to J2 (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. Further, the colored photosensitive resin composition K1 is applied and dried, and a thermoplastic resin layer having a dry film thickness of 14.6 μm, an intermediate layer having a dry film thickness of 1.6 μm, and a dry layer are dried on the temporary support. A photosensitive resin layer having a film thickness of 2.4 μm was provided, and a protective film (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: prescription P1>
・ PVA205 (polyvinyl alcohol, manufactured by Kuraray Co., Ltd.,
Degree of saponification = 88%, degree of polymerization 550) 32.2 parts by mass / polyvinylpyrrolidone (manufactured by ASP Japan Co., Ltd.)
K-30) 14.9 parts by mass, 524 parts by mass of distilled water, 429 parts by mass of methanol

  Next, the colored photosensitive resin composition K101 used in the production of the photosensitive resin transfer material K1 is composed of the following colored photosensitive resin compositions R101 and G101 having the compositions described in Tables 6-1 to 6-3 below. Photoresin transfer materials R101, G101, and B101 were prepared in the same manner as described above except that they were changed to B101 and B101. In addition, the preparation method of colored photosensitive resin composition R101, G101, and B101 is based on the preparation method of the said colored photosensitive resin composition R1, G1, and B1, respectively.

[Table 6-1] R101
--------------------------------------
R pigment dispersion 1 (CIPR254) 40 parts by mass R pigment dispersion 2 (CIPR177) 4.5 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 2-trichloromethyl- (p-styrylstyryl)
1,3,4-oxadiazole 0.14 parts by weight Polymerization initiator A 0.06 parts by weight Phenothiazine 0.01 parts by weight Additive 1 0.52 parts by weight Surfactant 1 0.06 parts by weight ---- ----------------------------------

[Table 6-2] G101
--------------------------------------
G pigment dispersion A (CIPG36) 28 parts by mass Y pigment dispersion 1 (CIPI150) 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 mass 2-trichloromethyl- (p-styrylstyryl)
1,3,4-oxadiazole 0.15 parts by mass Polymerization initiator A 0.06 parts by mass Phenothiazine 0.01 parts by mass Surfactant 1 0.07 parts by mass ----------- --------------------------

[Table 6-3] 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 2-trichloromethyl- (p-styrylstyryl)
1,3,4-oxadiazole 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 6-1, Additive 1 was a phosphate ester special activator (Takamoto Kasei Co., Ltd., trade name: HIPLAAD ED152).

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

Next, 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 using a rotating brush to obtain a black (K) image, and then post-exposure to the substrate from the resin layer side with an ultrahigh pressure mercury lamp at 500 mJ / cm <2> light, and then 220 [deg.] C. For 15 minutes.
The substrate on which this image K was formed was again cleaned with a brush as described above, and after pure water shower cleaning, the silane coupling solution was not used and was sent to a substrate preheating device.

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

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

[Formation of blue (B) pixels]
Using the photosensitive resin transfer material B101, heat-treated blue (B) pixels B were obtained in the same process as the photosensitive resin transfer material R101. However, the exposure amount was 30 mJ / cm ² , and development with a sodium carbonate developer was 36 ° C. for 40 seconds. The film thickness of the photosensitive resin layer B101 and the coating amounts of pigments (CIPB15: 6 and CIPVV23) are shown below.
Photosensitive resin film thickness (μm) 2.00
Pigment application amount (g / m ² ) 0.75
C. I. P. B. 15: 6 coating amount (g / m ² ) 0.705
C. I. P. V. 23 coating amount (g / m ² ) 0.045
The substrate on which the pixel R, pixel G, pixel B, and image K were formed was baked at 240 ° C. for 50 minutes to obtain a color filter A2.

  In contrast to the method for producing the color filter A2, the G pigment dispersion A was changed to G pigment dispersions B to J, respectively, and color filters B2 to J2 were produced.

  The contrast and color unevenness evaluation of the obtained color filters A2 to J2 were evaluated in the same manner as in Example 1 and Comparative Example 1. The results are shown in Table 7.

[Table 7]
----------------------------
Color filter Contrast Color unevenness evaluation ----------------------------
A2 7030 3.6
B2 6900 3.6
C2 7830 4.2
D2 7700 4.4
E2 7600 4.5
F2 8500 5.0
G2 8700 5.0
H2 7100 1.8
I2 7700 1.2
J2 7500 2.2

----------------------------

  As shown in Table 7, the color filters A2 to G2 of the present invention showed high contrast, and effectively suppressed color unevenness when incorporated in a liquid crystal display device to display an image. From this result, it can be seen that according to the present invention, a high-contrast color filter can be produced even by a laminate method, and a liquid crystal display device with high display quality can be obtained.

(Example 3 and Comparative Example 3)
<Production of Color Filters A3 to J3 (Production by Inkjet)>
About the preparation procedure of the said photosensitive resin transfer material K1, except having replaced the colored photosensitive resin composition K1 with the colored photosensitive resin composition K2 of the following Table 8-1, the photosensitive resin transfer material K2 was similarly used. Produced.

[Table 8-1] 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 1, 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 convex 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 mixture was diluted with a ratio) to develop a shower at 30 ° C. for 50 seconds and a flat nozzle pressure of 0.04 MPa to remove the thermoplastic resin layer and the intermediate layer (oxygen barrier layer).
Subsequently, sodium carbonate developer (0.38 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. 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 8-R]
--------------------------------------
Composition component Content (parts by mass) R ink 1
--------------------------------------
R pigment dispersion 1 (PR.254) 68
R pigment dispersion 2 (PR.177) 7
Polymer dispersant (Solsperse 20000 manufactured by AVECIA) 1.0
Polymer 1 0
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 8-G]
--------------------------------------
Composition component Content (parts by mass) G ink 1
--------------------------------------
G Pigment Dispersion A (PG 36) 35
Y pigment dispersion 1 (P.Y.150) 32
Polymer dispersant (Solsperse 20000 manufactured by AVECIA) 1.0
Polymer 1 2.0
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 8-B]
--------------------------------------
Composition component Content (parts by mass) B ink 1
--------------------------------------
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 manufactured by AVECIA) 1.0
Polymer 1 0
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 the components in Tables 1-R, 1-G, and 1-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 101 was produced using the ink R-1, 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 three colors of ink R-1, ink G-1, and ink B-1 described above are filled in different heads, each head is fixed on an XY stage, and each ink is predetermined. The three heads were independently controlled by the discharge control device so that they landed at the positions.
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.

  G pigment dispersion A was changed to G pigment dispersions B to F, respectively, for the production procedure of the color filter A3, and color filters B3 to J3 were produced.

  The contrast and color unevenness of the obtained color filters A3 to J3 were evaluated in the same manner as in Example 1 and Comparative Example 1. The results are shown in Table 9.

[Table 9]
------------------------
Color filter Contrast Color unevenness evaluation ------------------------
A3 9100 3.6
B3 9250 3.6
C3 10030 4.2
D3 8800 4.4
E3 9200 4.5
F3 11500 5.0
G3 12200 5.0
H3 9100 1.8
I3 9300 1.2
J3 8900 2.2
------------------------

  As shown in Table 9, the color filters A3 to G3 of the present invention exhibited high contrast and were mounted on a liquid crystal display device to effectively suppress color unevenness. From this result, it can be seen that according to the present invention, a color filter exhibiting high contrast can be obtained even by an inject method, and a liquid crystal display device having high display quality can be obtained.

Claims (12)

  An organic pigment solution in which an organic pigment is dissolved in a good solvent and a solvent that is a poor solvent for the organic pigment are mixed before the decomposition rate of the pigment in the organic pigment solution reaches 20% or more, A method for producing organic pigment nanoparticles, wherein the organic pigment is precipitated as nanometer-sized fine particles in a mixed solution.   The method for producing organic pigment nanoparticles according to claim 1, wherein the decomposition rate index of the pigment in the organic pigment solution is 0.02 or more.   An organic pigment fine particle powder obtained by precipitating the organic pigment fine particles by the production method according to claim 1 or 2 and then removing the solvent from the mixed solution to powder the fine particles.   3. The organic pigment fine particles are precipitated by the production method according to claim 1 or 2, and then the solvent content of the mixed solution is replaced with a replacement solvent, and then the solvent content including the replacement solvent is removed to form powder. Organic pigment fine particle powder characterized by   A pigment dispersion comprising the mixed liquid having organic pigment fine particles precipitated by the production method according to claim 1 or 2, or the organic pigment fine particle powder according to claim 3 or 4.   6. The pigment dispersion according to claim 5, further comprising a polymer compound having a mass average molecular weight of 1000 or more. The pigment dispersion according to claim 6, 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. ]   An ink-jet ink for a color filter, comprising the pigment dispersion according to any one of claims 5 to 7, and a polymerizable monomer and / or a polymerizable oligomer.   A colored photosensitive resin composition comprising the pigment dispersion according to any one of claims 5 to 7, a binder, a monomer or an oligomer, and a photopolymerization initiator or a photopolymerization initiator system. object.   A photosensitive resin transfer material, wherein a photosensitive resin layer containing at least the colored photosensitive resin composition according to claim 9 is provided on a temporary support.   A color filter produced using the inkjet ink according to claim 8, the colored photosensitive resin composition according to claim 9, and / or the photosensitive resin transfer material according to claim 10.   A liquid crystal display device comprising the color filter according to claim 11.