KR20090033018A - Dispersing aid, aqueous dispersion of organic pigment nanoparticle using the same, agglomerates, nonaqueous dispersion, colored photosensitive resin composition obtained by the same, color filter using the same and liquid crystal display device - Google Patents

Abstract

A dispersion aid is provided to increase fabrication efficiency while raising the contrast of a color filter, to realize excellent indication characteristic of a liquid crystal display, and to make efficient production of nonaqueous dispersion having stable dispersibility. A dispersion aid has a structure represented by the following chemical formula (1-1) or (1-2). In the chemical formula (1-1), A shows a heterocyclic group bonded with a linker by nitrogen atoms; X shows at least C2~20 divalent linker; R1 and R2 independently show hydrogen atom, alkyl group, aralkyl group or aryl group, or R1 and R2 are connected or can form a heterocyclic containing oxygen atom, nitrogen atom and/or sulfur atom; m shows a natural number of 1 or 2. In the chemical formula (1-2), A^11 shows a heterocyclic group connected to a carbonyl group by a nitrogen atom; and X^11 shows C2~10 divalent alkylene group which may have a substitution group, ether group or polyether group.

Description

Dispersion aid, aqueous dispersion of organic pigment nanoparticles using the same, aggregates, non-aqueous dispersions, colored photosensitive resin compositions obtained thereby, color filters and liquid crystal displays using the same , AGGLOMERATES, NONAQUEOUS DISPERSION, COLORED PHOTOSENSITIVE RESIN COMPOSITION OBTAINED BY THE SAME, COLOR FILTER USING THE SAME AND LIQUID CRYSTAL DISPLAY DEVICE}

The present invention provides a dispersion aid, in particular a basic dispersion aid and an acidic dispersion aid, an aqueous dispersion of organic pigment nanoparticles using the same, an aggregate, a non-aqueous dispersion, a colored photosensitive resin composition obtained thereby, a color filter and a liquid crystal display using the same. Relates to a device.

As nanotechnology, for example, research has been energetically progressed in which particles are downsized to a range of 10 to 100 nm and applied to various applications. The nanometer size is intended to derive new characteristics that could not have been previously predicted by the effect that is expressed for the first time. On the other hand, when it comes to the field of organic pigments, the research and development are progressing in paint, printing ink, electrophotographic toner, inkjet ink, color filter, etc., for example. Particularly, color filters and inkjet inks are coped with for high performance using fine chemical technology, and the results are expected.

In terms of color filters, thinning is required. Thereby, high performance including the high pixel of image related apparatuses, such as a liquid crystal display device, a digital camera, a CCD sensor, can be achieved. In recent years, organic pigments have been used in place of dyes in consideration of weather resistance, heat resistance, and the like as color materials of color filters. And the thickness of the color filter using a pigment largely depends on the particle diameter of the pigment. In other words, the development of fine pigment fine particles holds the key to improving the performance of image-related equipment. Specifically, stable pigment fine particles are required at a nanometer size level and monodisperse.

Here, when looking at the method of refine | miniaturizing organic particle | grains, it was conventionally performed using dispersers, such as a roll mill, a ball mill, and an attritor. In recent years, a gas phase method, a liquid phase method, and a laser ablation method have been studied. Among them, the liquid phase method has attracted attention as a method for producing organic particles excellent in simplicity and productivity. Specifically, a method of depositing nanoparticles by mixing a pigment solution and a poor solvent (see Japanese Patent Laid-Open No. 2004-91560), and a method of adding a predetermined polymer compound at this time is disclosed (Japanese Patent Laid-Open No. 2004-). 43776, International Publication No. WO 2006/121016 Pamphlet, Japanese Patent Publication No. 2007-119586).

An object of the present invention is to provide a dispersion aid (for example, a basic dispersion aid and an acidic dispersion aid) for use in a pigment dispersion capable of improving display characteristics of color filters such as a liquid crystal display device. In particular, a dispersion aid capable of increasing the color filter, increasing its production efficiency, and realizing good display characteristics in a liquid crystal display device, an aqueous dispersion, an aggregate, and a non-aqueous dispersion of organic pigment nanoparticles using the same. And it aims at provision of the coloring photosensitive resin composition obtained by these, the color filter using these, and a liquid crystal display device.

According to the present invention the following means are provided:

(1) It is represented by following General formula (1-1) or (1-2), Dispersion adjuvant characterized by the above-mentioned.

In formula (1-1), A represents a heterocyclic group bonded by a linking group and a nitrogen atom. X represents a divalent linking group having at least 2 to 20 carbon atoms. R ₁ and R ₂ each independently represent a hydrogen atom, an alkyl group, an aralkyl group or an aryl group. R ₁ and R ₂ may be connected to each other or may form a heterocycle further containing an oxygen atom, a nitrogen atom, and / or a sulfur atom. m represents a natural number of 1 or 2.

In formula (1-2), A ¹¹ represents a heterocyclic group which is linked to a carbonyl group by a nitrogen atom. X ¹¹ represents a divalent alkylene group, ether group or polyether group having 2 to 10 carbon atoms which may have a substituent.}

(2) It is a basic dispersion aid represented by the said General formula (1-1), The dispersion aid as described in (1) characterized by the above-mentioned.

(3) Said basic dispersion aid is represented by following General formula (2-1), The dispersion aid as described in (2) characterized by the above-mentioned.

(Wherein A represents a heterocyclic group bonded by a linking group and a nitrogen atom. Y represents an oxygen atom or a sulfur atom. L represents an integer of 0 or 1. n represents a natural number of 1 to 19. R ₁ and R ₂ each independently represent a hydrogen atom, an alkyl group, an aralkyl group or an aryl group, and R ₁ and R ₂ may be linked to each other and further include a heterocyclic ring containing an oxygen atom, a nitrogen atom, and / or a sulfur atom. M may represent a natural number of 1 or 2.)

(4) The dispersing aid according to (2) or (3), wherein dispersibility is imparted to the organic pigment nanoparticles together with the non-aqueous dispersant in the non-aqueous dispersion obtained by switching the medium from the aqueous dispersion.

(5) An aqueous dispersion containing organic pigment nanoparticles and water and the basic dispersion aid according to any one of (2) to (4), wherein the organic pigment nanoparticles are organic pigments in which an organic pigment is dissolved in a good solvent. The solution was mixed with the good solvent to mix the poor solvent for the organic pigment, and the organic pigment was precipitated as fine particles of nanometer size in the presence of the basic dispersion aid in the mixed liquid. Aqueous dispersions.

(6) The average particle diameter of the primary particle of the said organic pigment nanoparticle is 10-500 nm, The aqueous dispersion of organic pigment nanoparticle as described in (5) characterized by the above-mentioned.

(7) An aggregate of organic pigment nanoparticles in an aggregated state in which the pH of the aqueous dispersion described in (5) or (6) is changed to redisperse the organic pigment nanoparticles.

(8) A non-aqueous dispersion of organic pigment nanoparticles in which the aggregates of the aggregates described in (7) are released and redispersed in a non-aqueous medium.

(9) The non-aqueous dispersion of the organic pigment nanoparticles as described in (8) containing at least 1 sort (s) of high molecular compounds of 1000 or more of number average molecular weights which have an acidic group.

(10) The colored photosensitive resin composition containing at least the non-aqueous dispersion as described in (8) or (9), a binder, a monomer or an oligomer, and a photoinitiator or a photoinitiator system.

(11) The color filter produced using the coloring photosensitive resin composition as described in (10).

(12) The liquid crystal display device provided with the color filter as described in (11).

(13) The dispersion aid according to (1), which is an acidic dispersion aid represented by the general formula (1-2).

(14) The dispersion aid according to (13), wherein dispersibility is imparted to the organic pigment nanoparticles together with the non-aqueous dispersant in the non-aqueous dispersion obtained by switching the medium from the aqueous dispersion.

(15) An aqueous dispersion containing organic pigment nanoparticles, water, and the acidic dispersion aid according to (13), wherein the organic pigment nanoparticles are compatible with an organic pigment solution in which an organic pigment is dissolved in a good solvent and the good solvent. Thus, the poor solvent for the organic pigment is mixed, and the organic pigment is precipitated as fine particles of nanometer size in the presence of the acidic dispersion aid in the mixed liquid, wherein the aqueous dispersion of organic pigment nanoparticles.

(16) The aqueous dispersion of organic pigment nanoparticles according to (15), wherein the average particle diameter of the primary particles of the organic pigment nanoparticles is 10 to 500 nm.

(17) Aggregate of organic pigment nanoparticles which were made into the aggregation state which can change the pH of the aqueous dispersion as described in (15) or (16), and can redistribute the said organic pigment nanoparticle.

(18) A non-aqueous dispersion of organic pigment nanoparticles in which the aggregates of the aggregates described in (17) are released and redispersed in a non-aqueous medium.

(19) A non-aqueous dispersion of organic pigment particles according to (18), which contains at least one polymer compound having a number average molecular weight of 1000 or more.

(20) The colored photosensitive resin composition containing at least the non-aqueous dispersion as described in (18) or (19), a binder, a monomer or an oligomer, and a photoinitiator or a photoinitiator system.

(21) It produced using the coloring photosensitive resin composition as described in (20), The color filter characterized by the above-mentioned.

(22) The liquid crystal display device provided with the color filter as described in (21).

Hereinafter, to the dispersion aid according to the above (1) to (4), the aqueous dispersion according to the above (5) to (6), the aggregate according to the above (7), and the above (8) to (9). The non-aqueous dispersion described above, the colored photosensitive resin composition described in the above (10), the color filter described in the above (11), and the liquid crystal display device described in the above (12) are referred to as the first embodiment of the present invention.

Moreover, said dispersion | distribution adjuvant as described in said (1), said (13)-(14), the aqueous dispersion as described in said (15)-(16), the aggregate as described in said (17), said (18) The non-aqueous dispersion according to (19), the colored photosensitive resin composition according to the above (20), the color filter according to the above (21), and the liquid crystal display device according to the above (22), together with the agent of the present invention It is called 2 embodiment.

Here, unless otherwise indicated, this invention means the meaning including both said 1st and 2nd embodiment.

(Effects of the Invention)

Dispersion aids (for example, basic dispersion aids and acidic dispersion aids) of the present invention increase the production efficiency of the color filter produced by the dispersion prepared using the same, increase the production efficiency, and in the liquid crystal display device It shows an excellent effect that good display characteristics can be realized. In addition, the dispersion aid of the present invention maintains a good dispersion state of the organic pigment fine particles even when switching the medium from the aqueous dispersion to the non-aqueous dispersion, thereby enabling efficient production of the non-aqueous dispersion having stable dispersibility. Moreover, the color filter produced using this excellent dispersion shows the said high performance, and when it mounts on a liquid crystal display device and displays an image, it is excellent in the sharpness of black and exhibits the high image display performance.

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail.

In the present invention, the organic pigment is not limited in color, and for example, perylene, perinone, quinacridone, quinacridonequinone, anthraquinone, ananthrone, benzimazolone, disazo condensation, and dis Azo, azo, indanthrone, phthalocyanine, triarylcarbonium, dioxazine, aminoanthraquinone, diketopyrrolopyrrole, thioindigo, isoindolin, isoindolinone, pyrantrone or isobioanthrone compound pigments or their Mixtures;

More specifically, for example, C.I. Pigment Red 190 (C.I. No. 71140), C.I. Pigments of perylene compounds such as Pigment Red 224 (CI No. 71127), CI Pigment Violet 29 (CI No. 71129), CI Pigment Orange 43 (CI No. 71105), or CI Pigment Red 194 (CI No. 71100). Perinone compound pigment, CI pigment violet 19 (CI number 73900), CI pigment violet 42, CI pigment red 122 (CI number 73915), CI pigment red 192, CI pigment red 202 (CI number 73907), Quinacridone compound pigment of CI pigment red 207 (CI number 73900, 73906) or CI pigment red 209 (CI number 73905), CI pigment red 206 (CI number 73900/73920), CI pigment orange 48 (CI Quinacridone quinone compound pigments such as No. 73900/73920 or CI Pigment Orange 49 (CI No. 73900/73920), anthraquinone compound pigments such as CI Pigment Yellow 147 (CI No. 60645), and CI Pigment Red 168 ( Anthrone compounds such as CI No. 59300) Pigment, CI pigment brown 25 (CI number 12510), CI pigment violet 32 (CI number 12517), CI pigment yellow 180 (CI number 21290), CI pigment yellow 181 (CI number 11777), CI pigment orange Benzimazolone compound pigments such as 62 (CI number 11775) or CI pigment red 185 (CI number 12516), CI pigment yellow 93 (CI number 20710), CI pigment yellow 94 (CI number 20038), CI pigment Yellow 95 (CI number 20034), CI pigment yellow 128 (CI number 20037), CI pigment yellow 166 (CI number 20035), CI pigment orange 34 (CI number 21115), CI pigment orange 13 (CI number 21110 CI pigment orange 31 (CI number 20050), CI pigment red 144 (CI number 20735), CI pigment red 166 (CI number 20730), CI pigment red 220 (CI number 20055), CI pigment red 221 (CI number 20065), CI pigment red 242 (CI number 20067), CI pig Disazo condensation compound pigments such as tread 248, CI pigment red 262 or CI pigment brown 23 (CI number 20060), CI pigment yellow 13 (CI number 21100), CI pigment yellow 83 (CI number 21108), or Disazo compound pigments such as CI Pigment Yellow 188 (CI No. 21094), CI Pigment Red 187 (CI No. 12486), CI Pigment Red 170 (CI No. 12475), CI Pigment Yellow 74 (CI No. 11714), CI pigment yellow 150 (CI number 48545), CI pigment red 48 (CI number 15865), CI pigment red 53 (CI number 15585), CI pigment orange 64 (CI number 12760), or CI pigment red 247 Azo compound pigments such as (CI number 15915), indanthrone compound pigments such as CI pigment blue 60 (CI number 69800), CI pigment green 7 (CI number 74260), CI pigment green 36 (CI number 74265), Pigment Green 37 (CI number 74255), Pigment Blue 16 (CI Phthalocyanine compound pigments, such as CI Pigment Blue 75 (CI. No. 74160: 2) or 15 (CI. No. 74160), CI Pigment Blue 56 (CI. No. 42800) or CI Pigment Blue 61 (CI. No. 42765: 1) such as triarylcarbonium compound pigments, dioxazine compound pigments such as CI pigment violet 23 (CI number 51319) or CI pigment violet 37 (CI number 51345), CI pigment red 177 (CI number 65300), and the like. Amino anthraquinone compound pigment, CI pigment red 254 (CI number 56110), CI pigment red 255 (CI number 561050), CI pigment red 264, CI pigment red 272 (CI number 561150), CI pigment orange Diketopyrrolo pyrrole compound pigments such as 71 or CI pigment orange 73, thioindigo compound pigments such as CI pigment red 88 (CI number 73312), CI pigment yellow 139 (CI number 56298), CI pigment orange 66 ( CI number 48210) Isoindolin compound pigments, isoindolinone compound pigments such as CI pigment yellow 109 (CI number 56284) or CI pigment orange 61 (CI number 11295), CI pigment orange 40 (CI number 59700) or CI pig Pyrantrone compound pigments, such as Cement Red 216 (CI. No. 59710), or isobioanthrone compound pigments, such as CI pigment violet 31 (60010). Especially, it is preferable that it is a quinacridone compound pigment, a diketopyrrolopyrrole compound pigment, a dioxazine compound pigment, a phthalocyanine compound pigment, or an azo compound pigment, and a diketopyrrolopyrrole compound pigment, a phthalocyanine compound pigment, and a dioxazine compound pigment are more preferable. Do.

In this invention, you may use combining two or more types of organic pigments or the solid solution of organic pigments. Moreover, you may combine with an organic pigment | dye, a polymeric organic material, etc.

The dispersing aid of the present invention is mixed with an organic pigment solution obtained by dissolving an organic pigment in a good solvent (first solvent), and a solvent which has compatibility with the good solvent and becomes a poor solvent (second solvent) with respect to the organic pigment. It can be used when depositing nanoparticles of an organic pigment. It is preferable that the combination of the good solvent and the poor solvent has 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 any combination can be selected as long as it is a combination which enables this process.

A good solvent can melt | dissolve the organic pigment to be used, and if it is compatible with the said poor solvent or mixed uniformly, it will not specifically limit. It is preferable that the solubility of an organic pigment is 0.2 mass% or more, and, as for the solubility to the good solvent of an organic pigment, it is more preferable that it is 0.5 mass% or more. Although there is no upper limit in particular in the solubility to the good solvent of an organic pigment, when it considers the organic pigment used normally, it is practically 50 mass% or less. This solubility may be solubility when melt | dissolved in presence of an acid or an alkali. Moreover, it is preferable that the amount of melt | dissolution with respect to the poor solvent of a good solvent is 30 mass% or more, and, as for the compatibility or uniform mixing property of a good solvent and a poor solvent, it is more preferable that it is 50 mass% or more. Although there is no upper limit in the dissolution amount of the good solvent in the poor solvent, it is practical to mix with each other in an arbitrary ratio.

As a good solvent, for example, 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, an aliphatic compound solvent , Nitrile compound solvents, sulfoxide compound solvents, halogen compound solvents, ester compound solvents, ionic liquids, mixed solvents thereof, and the like, and 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, and aqueous solvents, alcohol compound solvents, ester compound solvents, sulfoxide compound solvents or amide compound solvents are preferred, and aqueous solvents, sulfoxide compound solvents or amide compounds Solvent is more preferred, sulfoxide compounding Water solvents or amide compound solvents are particularly preferred.

As a sulfoxide compound solvent, dimethyl sulfoxide, diethyl sulfoxide, hexamethylene sulfoxide, sulfolane etc. are mentioned, for example. As the amide compound solvent, for example, N, N-dimethylformamide, 1-methyl-2-pyrrolidone, 2-pyrrolidinone, 1,3-dimethyl-2-imidazolidinone, 2-pyrrolidinone , (epsilon) -caprolactam, formamide, N-methylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, N-methylpropanamide, hexamethylphosphoric triamide, and the like.

Moreover, as a density | concentration of the organic pigment solution which melt | dissolved the organic pigment in a good solvent, the range of the saturated concentration with respect to the good solvent of the organic pigment in the conditions at the time of melt | dissolution, about 1/100 of this is preferable.

There is no restriction | limiting in particular in the preparation conditions of an organic pigment solution, The range of subcritical and supercritical conditions can be selected from normal pressure. -10-150 degreeC is preferable, as for the temperature in normal pressure, -5-130 degreeC is more preferable, and 0-100 degreeC is especially preferable.

The same thing may not be combined as a good solvent and a poor solvent, and what is necessary is just so that the solubility with respect to a good solvent may be sufficiently higher than the solubility with respect to a poor solvent by relationship with each organic pigment employ | adopted. For example, it is preferable that the solubility difference is 0.2 mass% or more, and it is more preferable that it is 0.5 mass% or more. Although there is no upper limit in particular in the difference of solubility with a good solvent and a poor solvent, when it considers the organic pigment used normally, it is practically 50 mass% or less.

When dissolving an organic pigment uniformly in a good solvent, you may melt | dissolve acidicly or alkaline. In general, in the case of a pigment having a group that can be dissociated to be alkaline in the molecule, acid is used when there is no group in which the alkalinity is dissociated to be alkaline and when there are many nitrogen atoms in the molecule to which protons are easily added. For example, quinacridone, diketopyrrolopyrrole, and disazo condensation compound pigments are alkaline, and phthalocyanine compound pigments are dissolved in acid.

When dissolving alkaline, it is preferable to use inorganic bases such as lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, barium hydroxide or organic bases such as trialkylamine, diazabicycloundecene (DBU), metal alkoxide, and the like. Especially, it is more preferable to use an inorganic base.

Although the quantity of the base to be used is not specifically limited, In the case of an inorganic base, it is preferable that it is 1.0-30 mol equivalent with respect to an organic pigment, It is more preferable that it is 1.0-25 mol equivalent, It is especially preferable that it is 1.0-20 mol equivalent. In the case of an organic base, it is preferable that it is 1.0-100 molar equivalent with respect to an organic pigment, It is more preferable that it is 5.0-100 molar equivalent, It is especially preferable that it is 20-100 molar equivalent.

In the case of dissolving acidically, it is preferable to use inorganic acids such as sulfuric acid, hydrochloric acid or phosphoric acid or organic acids such as acetic acid, trifluoroacetic acid, oxalic acid, methanesulfonic acid or trifluoromethanesulfonic acid, and among these, it is preferable to use inorganic acids. And it is more preferable to use sulfuric acid.

Although the amount of the acid to be used is not particularly limited, it is often used in an excessive amount compared to the base. Regardless of the case of the inorganic acid and the organic acid, the amount is preferably 3 to 500 molar equivalents, more preferably 10 to 500 molar equivalents, and particularly preferably 30 to 200 molar equivalents, relative to the organic pigment.

When alkali or acid is mixed with an organic solvent and used as a good solvent for organic pigments, a solvent having high solubility in alkali or acid such as some water or lower alcohol can be added to the organic solvent in order to completely dissolve the alkali or acid. have. 50 mass% or less is preferable with respect to the organic pigment solution whole quantity, and, as for the quantity of water and a lower alcohol, 30 mass% or less is more preferable. Specifically, water, methanol, ethanol, n-propanol, isopropanol, butyl alcohol, etc. can be used.

It is preferable that it is 0.5-80.0 mPa * s, and, as for the viscosity of an organic pigment solution, it is more preferable that it is 1.0-50.0 mPa * s.

Although the 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. There is no particular lower limit to the solubility of the organic pigment in the poor solvent, but considering the organic pigment that is usually used, 0.000001 mass% or more is practical. This solubility may be solubility when melt | dissolved in presence of an acid or an alkali. The preferable range of compatibility or uniform mixing of a poor solvent and a good solvent is as above-mentioned.

As a poor solvent, for example, 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, a nitrile compound solvent Halogen solvents, ester compound solvents, ionic liquids, mixed solvents thereof, and the like, aqueous solvents, alcohol compound solvents, ketone compound solvents, ether compound solvents, ester compound solvents, or mixtures thereof, Aqueous solvents, alcohol compound solvents or ester compound solvents are more preferred.

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

Which solvent becomes a good solvent or a poor solvent is determined according to the kind of organic pigment made into the object. In this invention, a good solvent and a poor solvent do not become the same compound with respect to any one organic pigment.

There is no restriction | limiting in particular in the conditions of the poor solvent at the time of depositing and producing organic particle | grains, The range of subcritical and supercritical conditions can be selected from normal pressure. -30-100 degreeC is preferable, as for the temperature in normal pressure, -10-60 degreeC is more preferable, and 0-30 degreeC is especially preferable.

When mixing an organic pigment solution and a poor solvent, you may add and mix both, but it is preferable to classify and mix an organic pigment solution to a poor solvent, and it is preferable that the poor solvent is stirred at that time. . The stirring speed is preferably 100 to 10000 rpm, more preferably 150 to 8000 rpm, and particularly preferably 200 to 6000 rpm. A pump etc. can also be used for addition. At this time, addition in liquid or extra liquid may be performed, but addition in liquid is more preferable. Moreover, it is preferable to continuously supply in a liquid by a pump through a supply pipe. It is preferable to set it as 0.1-200 mm, and, as for the internal diameter of a supply pipe, it is more preferable to set it as 0.2-100 mm. As a speed | rate supplied from a supply pipe | tube in a liquid, it is preferable to set it as 1-10000 ml / min, and it is more preferable to set it as 5-5000 ml / min.

In the mixing of the organic pigment solution and the poor solvent, by adjusting the Reynolds number, the particle diameter of the organic nanoparticles to be precipitated 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... Formula (1)

In Formula (1), Re represents Reynolds number, rho represents the density [kg / m <3>] of the organic pigment solution, U represents the relative speed [m / s] when the organic pigment solution and the poor solvent meet, L represents the equivalent diameter [m] of the flow path or the supply port of the part where the organic pigment solution and the poor solvent meet, and mu represents the viscosity coefficient [Pa · s] of the organic pigment solution.

The equivalent diameter L means the diameter of the equivalent circular tube when an equivalent circular tube is assumed with respect to the opening diameter and the flow path of the piping of arbitrary cross-sectional shape. The equivalent diameter L is represented by the following formula (2) when the end area of the pipe is A, the wet circumferential length (circumference length) of the pipe or the outer circumference of the flow path is p.

L = 4A / p... Formula (2)

It is preferable to inject | pour an organic pigment solution into a poor solvent through piping, and to form particle | grains, and, when a raw pipe is used for piping, an equivalent diameter matches the diameter of a raw 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 the same as the preferable internal diameter of the supply opening mentioned above.

The relative velocity U when the good solvent solution and the poor solvent of the organic pigment meet is defined as the relative speed in the direction perpendicular to the plane of the portion where the both meet. That is, for example, in the case of injecting and mixing a good solvent solution of an organic pigment into a stationary poor solvent, the rate to be injected from the supply port is 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 according to the kind of material to be selected, but in the range of the material preferably used for the production method of the present invention, it is practically, for example, 0.8 to 2.0 kg / m 3. Moreover, although it is a value determined by the material used, the environmental temperature, etc. also about the viscosity coefficient micro of an organic pigment solution, the preferable range is synonymous with the preferable viscosity of the organic pigment solution mentioned above.

The smaller the Reynolds number (Re) is, 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 Reynolds number can be adjusted to 60 or more, the particle diameter of organic nanoparticles can be controlled and obtained, It is preferable to set it as 100 or more, and it is more preferable to set it as 150 or more. Although there is no upper limit in Reynolds number in particular, it is preferable because it can obtain and control favorable organic nanoparticles by adjusting and controlling in the range of 100000 or less, for example. Or you may make it the 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 said range, organic nanoparticles with a smaller particle size can be controlled and obtained by raising Reynolds number normally.

As for the mixing ratio (good solvent / poor solvent ratio in organic fine particle precipitation liquid) of an organic pigment solution and a poor solvent, 1/50-2/3 are preferable by volume ratio, 1/40-1/2 are more preferable, 1/20 ˜3 / 8 is particularly preferred.

When the organic fine particles are precipitated, the nanoparticle concentration in the dispersion is not particularly limited, but the organic particles are preferably in the range of 10 to 40000 mg, more preferably in the range of 20 to 30000 mg, particularly preferably 1000 ml of the solvent. Is in the range of 50 to 25000 mg.

Moreover, although the preparation scale at the time of producing a pigment nanoparticle is not specifically limited, It is preferable that it is a preparation scale of 10-2000L, and, as for the mixing amount of a poor solvent, it is more preferable that it is a preparation scale of 50-1000L.

The particle size of the organic particles can be quantified by a measurement method to express the average size of the population. However, the particle diameter of the organic particles is well used. (Number average, length average, area average, mass average, volume average, etc.), etc. In this invention, an average particle diameter means a number average diameter unless there is particular notice. It is preferable that the average particle diameter of a pigment nanoparticle (primary particle) is 10-500 nm, It is more preferable that it is 10-200 nm, It is still more preferable that it is 10-100 nm, It is especially preferable that it is 20-80 nm. . In addition, the particle | grains formed by the manufacturing method of this invention may be a crystalline particle, an amorphous particle, or a mixture thereof.

In addition, unless otherwise indicated in this invention as an index which shows monodispersibility of particle | grains, the ratio (Mv / Mn) of volume average particle diameter (Mv) and number average particle diameter (Mn) is used. It is preferable that monodispersibility (Mv / Mn) of organic pigment nanoparticle (primary particle) is 1.0-2.0, It is more preferable that it is 1.0-1.8, It is especially preferable that it is 1.0-1.5.

As a measuring method of the particle diameter of organic particle | grains, a microscopic method, a mass method, the light scattering method, the light blocking method, an electrical resistance method, the acoustic method, the dynamic light scattering method are mentioned, A microscopic method and a dynamic light scattering method are especially preferable. As a microscope used for a microscopic method, a scanning electron microscope, a transmission electron microscope, etc. are mentioned, for example. As a particle | grain measuring apparatus by the dynamic light scattering method, the nano light track UPA-EX 150 by Nikkiso Corporation, the dynamic light scattering photometer DLS-7000 series by Otsuka Denshi Corporation, etc. are mentioned (all brand names).

In this invention, in dispersing organic pigment nanoparticles and preparing a dispersion liquid, you may contain a dispersing agent in at least one of a pigment solution and a poor solvent. At this time, it is preferable to contain at least a dispersing agent (in the present invention, the dispersing agent added to the aqueous dispersion is called an aqueous dispersing agent and may be distinguished from the non-aqueous dispersing agent described later).

As a polymeric dispersing agent used as an aqueous dispersing agent, it is preferable that the mass mean molecular weights are 1,000-500,000, It is more preferable that it is 10,000-500,000, It is especially preferable that it is 10,000-100,000.

Specifically, polyvinylpyrrolidone, polyvinyl alcohol, polyvinyl methyl ether, polyethylene glycol, polypropylene glycol, polyacrylamide, vinyl alcohol-vinyl acetate copolymer, polyvinyl alcohol-part formal, polyvinyl alcohol-part Butyralide, vinylpyrrolidone-vinyl acetate copolymer, polyethylene oxide / propylene oxide block copolymer, polyacrylate, polyvinyl sulfate, poly (4-vinylpyridine) salt, polyamide, polyallylamine salt, Condensed naphthalene sulfonate, a cellulose derivative, a starch derivative, etc. are mentioned. In addition, natural polymers such as alginate, gelatin, albumin, casein, gum arabic, tragacanth rubber and lignin sulfonate can also be used. Especially, polyvinylpyrrolidone is preferable. These high molecular compounds can be used individually by 1 type or in combination of 2 or more types, and can also be used in combination of the low molecular weight dispersing agent. The dispersant used for dispersing the pigment is described in detail on pages 29 to 46 of "Pigment dispersion stabilization and surface treatment technology and evaluation" (Chemical Information Association, December 2001 issue).

Anionic dispersants (anionic surfactants) include N-acyl-N-alkyltaurine salts, fatty acid salts, alkylsulfuric acid ester salts, alkylbenzenesulfonate salts, alkylnaphthalenesulfonate salts, dialkylsulfosuccinic acid salts, alkylphosphate ester salts and naphthalenes. Sulfonic acid formalin condensates, polyoxyethylene alkyl sulfate ester salts, and the like. Especially, N-acyl-N-alkyltaurine salt is preferable. As the N-acyl-N-alkyltaurine salt, those described in JP-A-3-273067 are preferable. These anionic dispersants can be used individually or in combination of 2 or more types.

Cationic dispersants (cationic surfactants) include quaternary ammonium salts, alkoxylated polyamines, aliphatic aminepolyglycol ethers, aliphatic amines, diamines and polyamines derived from aliphatic amines and aliphatic alcohols, imidazolines derived from fatty acids and their cations Contains salts of the sexual substances. These cationic dispersants can be used individually or in combination of 2 or more types.

A cationic dispersant is a dispersant which has both an anionic part which the said anionic dispersant has in a molecule, and a cationic group part which a cationic dispersant has in a molecule.

As a nonionic dispersing agent (nonionic surfactant), polyoxyethylene alkyl ether, polyoxyethylene alkyl aryl ether, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene alkylamine, glycerin fatty acid Ester etc. are mentioned. Especially, polyoxyethylene alkyl aryl ether is preferable. These nonionic dispersants can be used individually or in combination of 2 or more types.

It is preferable that content of a dispersing agent is the range of 0.1-1000 mass parts with respect to 100 mass parts of pigments in order to further improve the uniform dispersibility and storage stability of a pigment nanoparticle, More preferably, it is the range of 1-500 mass parts, Preferably it is the range of 10-300 mass parts. If it is less than 0.1 mass part, the improvement of the dispersion stability of a pigment nanoparticle may not be seen, and when it is larger than 1000 mass parts, a raise of a viscosity may occur. In addition, a dispersing agent may be used independently or may be used in combination of several things.

"Dispersion adjuvant" means the meaning including both a basic dispersion adjuvant and an acidic dispersion adjuvant unless there is particular notice in this invention. The dispersion aid of the present invention is preferably a basic dispersion aid or an acidic dispersion aid, and the basic dispersion aid is more preferably a basic dispersion aid represented by General Formula (1-1) or (2-1). As for a preparation, it is more preferable that it is an acidic dispersion aid which is the said General formula (1-2).

Hereinafter, the basic dispersion aid of the first embodiment of the present invention will be described in detail. The basic dispersion aid of the first embodiment of the present invention is for the purpose of controlling the particle size at the nanoscale level, imparting pH responsiveness, and basic treatment (improving redispersibility) in depositing organic pigment nanoparticles to prepare a dispersion. It is preferable to contain the following basic dispersion adjuvant in at least one of a pigment solution and a poor solvent, and it is more preferable to contain in a pigment solution. Moreover, it is preferable to use in combination with the said dispersing agent.

The basic dispersion aid of the first embodiment of the present invention is represented by the following general formula (1-1).

In the formula, A represents a heterocyclic group bonded by a linking group and a nitrogen atom. X represents a divalent linking group having at least 2 to 20 carbon atoms. R ₁ and R ₂ each independently represent a hydrogen atom, an alkyl group, an aralkyl group or an aryl group. R ₁ and R ₂ may be connected to each other or may form a heterocycle further containing an oxygen atom, a nitrogen atom and / or a sulfur atom. m represents the natural number of 1 or 2.

Examples of A include pyrazole, imidazole, indole, carbazole, 5-aminobenzimidazole, 3-aminoanthraquinone, acridon, 5-aminobenzimidazolone, 5-aminouracil and adenine. And 5-aminobenzimidazole, 3-aminoanthraquinone, acridon, 5-aminobenzimidazole, 5-aminouracil, and more preferably 5-aminobenzimidazole. , 3-aminoanthraquinone, 5-aminobenzimidazolone, and 5-aminouracil.

X includes, for example, a linking group containing alkylene, polyethylene oxide, and polypropylene oxide, preferably alkylene.

The alkyl group in R ₁ or R ₂ is methyl, ethyl, propyl, isopropyl, n-butyl, t-butyl, pentyl, hexyl, cyclohexyl, heptyl, octyl or 2-ethylhex. A practical group etc. are mentioned, Preferably they are a methyl group, an ethyl group, a propyl group, isopropyl group, and n-butyl group, More preferably, they are a methyl group, an ethyl group, and a propyl group.

As the aralkyl group, benzyl group, 4-chlorobenzyl group, 4-methylbenzyl group, 4-butoxybenzyl group, 4-methoxybenzyl methoxyphenyl group, and 4-hydroxybenzyl group are preferable. Especially preferably, they are a benzyl group, 4-chlorobenzyl group, 4-methylbenzyl group, and 4-butoxybenzyl group.

The aryl group is preferably a phenyl group, 4-chlorophenyl group, 4-methylphenyl group, 4-butoxyphenyl group, 4-methoxyphenyl group, or 4-hydroxyphenyl group. Especially preferably, they are a phenyl group, 4-chlorophenyl group, 4-methylphenyl group, and 4-butoxyphenyl group.

Examples of the heterocyclic group in which R ₁ and R ₂ are linked to each other include imidazole and morpholine.

m represents a natural number of 1 or 2, 1 is preferable from the standpoint of granular control, and 2 is preferable from the point of pH control and dispersibility improvement.

It is preferable that the said basic dispersion adjuvant is represented by following General formula (2-1).

In the formula, A represents a heterocyclic group bonded by a linking group and a nitrogen atom. Y represents an oxygen atom or a sulfur atom. l represents the integer of 0 or 1. n represents the natural number of 1-19. R ₁ and R ₂ each independently represent a hydrogen atom, an alkyl group, an aralkyl group or an aryl group. R ₁ and R ₂ may be connected to each other or may form a heterocycle further containing an oxygen atom, a nitrogen atom, and / or a sulfur atom. m represents the natural number of 1 or 2.

In formula, the preferable range of A and m is the same as that of the said General formula (1).

As a group which Y forms, a carbonyl group or a thiocarbonyl group is preferable, and it is more preferable that it is a carbonyl group.

1 represents an integer of 0 or 1, but is suitably selected by the structure of the heterocyclic group of A for synthetic reasons.

As n, it is preferable that it is 4-19, It is more preferable that it is 6-17, It is especially preferable that it is 8-15.

Hereinafter, although the specific compound represented by general formula (1-1) or (2-1) is shown, this invention is not limited to these.

As addition amount of the said basic dispersion adjuvant in an aqueous dispersion, 0.1 mass part-1000 mass parts are preferable with respect to 100 mass parts of pigments, 5 mass parts-500 mass parts are more preferable, 10 mass parts-300 mass parts are especially preferable. . When the addition amount is too small, the aggregation for isolation described later may be insufficient, while when the addition amount is excessive, excessive aggregation occurs, which may make it difficult to redistribute later.

In 1st Embodiment of this invention, the organic pigment nanoparticle can be aggregated so that it may be easy to isolate by neutralizing the aqueous dispersion liquid of the organic pigment nanoparticle mentioned above.

When the good solvent is acidic, the aqueous dispersion of the organic pigment nanoparticles is also acidic, and when the good solvent is basic, the aqueous dispersion is also basic. The basic dispersion aid in the first embodiment of the present invention is most effective when the aqueous dispersion is acidic.

At this time, the basic dispersion aid is coated around the organic pigment nanoparticles in the protonated state, but as the base to be added, it is necessary to neutralize the protons to generate the basic dispersion aid around the organic pigment nanoparticles. Therefore, it is necessary to appropriately select the basicity and the amount of addition that are only for neutralizing the protonation state of the basic dispersion aid.

Examples of the base to be added include inorganic bases such as lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide or barium hydroxide or organic bases such as trialkylamine, diazabicycloundecene (DBU) and metal alkoxides, but are easy to remove and cost. Is preferably an inorganic base. When neutralizing by these, it is preferable to neutralize to pH7 or more as a whole system, More preferably, it is pH9 or more.

In the first embodiment of the present invention, the basic dispersing aid having the basic group described above under acidicity has a tendency to disperse and repel each other by protonating and taking a positive charge. By neutralizing, positive charges disappear and the repulsive force between particles disappears, leading to aggregation.

In addition, in the basic dispersion adjuvant in 1st Embodiment of this invention, since it has a basic group, it interacts strongly with the non-aqueous dispersing agent which has an acidic group mentioned later, and dispersibility improvement and contrast improvement are possible. The basic dispersion aid is coated around the pigment particles, so that the surface of the pigment particles can be in a basic treatment state. This makes it possible to strongly bond the pigment particles and the non-aqueous dispersant having an acidic group by acid-base interaction, and to improve the dispersibility of the pigment particles by the non-aqueous dispersant having the acidic group.

The nanoparticles tending to disperse are inherently small, so even if they are isolated by filter filtration or centrifugal filtration, they are thrown out or clogged, which takes a great deal of time for isolation. However, isolation is greatly improved by forming large aggregates by pH control as described above. Although the width | variety of pH change in 1st Embodiment of this invention is not specifically limited, It is preferable to set the width | variety of pH change to 7-12, and it is more preferable to set it to 9-12. Although the direction of pH change is not specifically limited, It is preferable to change from the (low) pH side to the (high) pH side, ie, to change it to an alkaline direction.

As an aggregate, it is preferable that an average particle diameter is 10000 nm or more, and larger is more preferable. Although there is no upper limit in particular in this average particle diameter, 10 million nm or less is practical. If the average particle diameter of the aggregate is too small, it may take enormous time for isolation of the aggregate, or it may leave the filter paper or the filter, or become clogged even if it is to be filtered. If the average particle diameter of the aggregate is too large, a problem may occur that a large amount of time is required for redispersion.

Next, the acid dispersion adjuvant of 2nd Embodiment of this invention is demonstrated in detail.

The acid dispersing aid of the second embodiment of the present invention is for the purpose of controlling the particle size at the nanoscale level, imparting pH responsiveness, and acidic treatment (improving redispersibility) in depositing organic pigment nanoparticles to prepare a dispersion. It is preferable to contain the following acidic compound in at least one of a pigment solution and a poor solvent, and it is more preferable to contain in a pigment solution. Moreover, it is preferable to use in combination with the said dispersing agent.

The acidic dispersion aid of the second embodiment of the present invention is represented by the following general formula (1-2).

In the formula, A ¹¹ represents a heterocyclic group which is linked to a carbonyl group by a nitrogen atom. X ¹¹ represents a divalent alkylene group, ether group or polyether group having 2 to 10 carbon atoms which may have a substituent T.

Examples of A ¹¹ include pyrazole, imidazole, indole, carbazole, 5-aminobenzimidazole, 3-aminoanthraquinone, acridon, 5-aminobenzimidazolone, 5-aminouracil and adenine. Preferred examples thereof include 5-aminobenzimidazole, 3-aminoanthraquinone, acridon, 5-aminobenzimidazone, and 5-aminouracil, and more preferably 5-aminobenzimidol. Dazole, 3-aminoanthraquinone, 5-aminobenzimidazolone, 5-aminouracil can be mentioned.

As X <^11> , the coupling group containing alkylene, polyethylene oxide, and polypropylene oxide is mentioned, for example, Preferably it is alkylene.

Hereinafter, although a specific structure is shown, it is not limited to these.

As addition amount of the said acid dispersing adjuvant in an aqueous dispersion, 0.1 mass part-1000 mass parts are preferable with respect to 100 mass parts of pigments, 5 mass parts-500 mass parts are more preferable, 10 mass parts-300 mass parts are especially preferable. . When the addition amount is too small, the aggregation for isolation described later may be insufficient, while when the addition amount is excessive, excessive aggregation occurs, which may make it difficult to redistribute later.

In the second embodiment of the present invention, the organic pigment nanoparticles can be aggregated so as to be easily isolated by neutralizing the aqueous dispersion liquid of the organic pigment nanoparticles described above.

When the good solvent is acidic, the aqueous dispersion of the organic pigment nanoparticles is also acidic, and when the good solvent is basic, the aqueous dispersion is also basic. The acidic dispersion aid in the second embodiment of the present invention is most effective when the aqueous dispersion is basic.

If the aqueous dispersion is basic, it can be aggregated by neutralizing from neutral to weakly acidic by addition of acid. At this time, the acid dispersion aid is coated around the organic pigment nanoparticles in an anionized state, but as the acid to be added, it is necessary to neutralize the anion to produce a neutral acid dispersion aid around the organic pigment nanoparticles. Therefore, it is necessary to select the acidity and the addition amount suitably, only to neutralize the anionized state of an acidic dispersion adjuvant.

Examples of the acid to be added include inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid and nitric acid, or organic acids such as acetic acid, propionic acid, butyric acid, valeric acid and hexanoic acid, but are preferably inorganic acids or acetic acid from the viewpoint of ease of removal and cost. When neutralizing by these, it is preferable to neutralize to pH7 or less as a whole system, More preferably, it is pH3 or less.

In addition, in acid dispersing adjuvant in 2nd embodiment of this invention, since it has an acidic group, it interacts strongly with the non-aqueous dispersing agent mentioned later, and dispersibility improvement and contrast improvement are possible. The acid dispersion aid is coated around the pigment particles so that the surface of the pigment particles can be in an acid-treated state. This makes it possible to strongly bind the pigment particles and the non-aqueous dispersant by acid-base interaction, and to improve the dispersibility of the pigment particles by the non-aqueous dispersant. At this time, when the non-aqueous dispersant has an acidic group, the non-aqueous dispersant interacts with a hydrogen bond. When the non-aqueous dispersant has a basic group, the non-aqueous dispersant interacts with the acid-dispersion aid by an acid-base interaction. As a more preferable group which has a non-aqueous dispersing agent, it is a non-aqueous dispersing agent which has a basic group which can expect strong interaction with an acidic dispersing adjuvant.

In the second embodiment of the present invention, under basic conditions, the above-described acidic dispersing aid is anionized to remove negative charges, so that the particles repel each other and tend to be dispersed. By neutralizing, negative charge disappears and the repulsive force between particles disappears, leading to aggregation.

The nanoparticles tending to disperse are inherently small, so even if they are isolated by filter filtration or centrifugal filtration, they are thrown out or clogged, which takes a great deal of time for isolation. However, isolation is greatly improved by forming large aggregates by pH control as described above. Although the width | variety of pH change is not specifically limited in 2nd Embodiment of this invention, It is preferable to set the width | variety of pH change to 1-7, and it is more preferable to set it to 1-3. Although the direction of pH change is not specifically limited, It is preferable to change from the (high) pH side to the (low) pH side, ie, to change it to an acidic direction.

As an aggregate in this invention, it is preferable that average particle diameter is 10000 nm or more, and it is more preferable that it is large. Although there is no upper limit in particular in this average particle diameter, 10 million nm or less is practical. If the average particle diameter of the aggregate is too small, it may take enormous time for isolation of the aggregate, or it may leave the filter paper or the filter, or become clogged even if it is to be filtered. If the average particle diameter of the aggregate is too large, a problem may occur that a large amount of time is required for redispersion.

Hereinafter, the structural requirements, other conditions, etc. which are common in 1st Embodiment and 2nd Embodiment of this invention are demonstrated.

In the present invention, the pH of the aqueous dispersion liquid of the organic pigment nanoparticles described above can be changed or aggregated to the extent that the organic pigment nanoparticles can be redispersed so as to be easily isolated. Here, soft agglomeration is a weak aggregation of the extent which can be redispersed as needed, and the soft agglomerate may be specifically called a floc. By doing in this way, the organic pigment microparticles | fine-particles precipitated in the aqueous dispersion composition, for example, can be isolate | separated quickly by filtration etc. In addition, the separated soft aggregate can be redispersed in an organic solvent suitable for the production of color filters, thereby making it possible to efficiently produce an organic solvent-based dispersion composition. That is, when the mixed solvent of a good solvent and a poor solvent is an aqueous solvent, this can be efficiently substituted by the 3rd solvent which consists of organic solvents, and can switch a dispersion medium (continuous phase). Although the average particle diameter of an aggregate is not specifically limited, It is preferable that it is 10-5000 micrometers in consideration of the filterability mentioned above, and it is more preferable that it is 100-5000 micrometers.

In order to redisperse | distribute the said soft-aggregated state, it may be inadequate in the normal dispersion method. The dispersing aid acts on the formation and formation of the soft aggregate (floc), and can be redispersed quickly even if it is only once agglomerated, so that a good dispersion state can be realized. Therefore, good fine dispersibility (characteristic that uniform and small particle size is realized) and dispersion stability (characteristic that uniform and minute particle diameter are maintained for a long time) when precipitated in the mixed solution of good solvent and poor solvent make the medium suitable for color filter. It is maintained even after switching to the final solvent and redispersing, thereby realizing high performance in the color filter. Moreover, the said dispersing aid can implement | achieve the high performance in a color filter and a liquid crystal display device, without disturbing the optical characteristic etc. of a color filter.

Hereinafter, the isolation method of the aggregated organic pigment nanoparticles is demonstrated.

First, the liquid aggregated before isolation may be allowed to stand for 0.5 to 2 hours. Since the aggregates settle quickly, the supernatant can be removed by decanting or absorbing, making isolation of the aggregates easier. In addition, by centrifugation instead of standing, the aggregates can be settled faster and the time can be shortened.

Various isolation | separation methods are possible as an isolation method, and limit filtration, centrifugal separation, filtration by a filter paper or a filter is mentioned.

In the case of ultrafiltration, for example, a method used for desalting / concentrating a halogenated silver oil agent can be applied. Research Disclosure No. 10208 (1972), No. 13 122 (1975) and No. 16 351 (1977) are known. The pressure difference and the flow rate which are important as the operating conditions can be selected by referring to the characteristic curve described in Harajiko Oya, `` Technology Handbook for Membrane, '' Saiwaibo Publication (1978), p275, but the aggregation of particles in treating the desired organic nanoparticle dispersion. It is necessary to find out the optimum condition in order to suppress the problem. In addition, in the method of replenishing the solvent lost from the membrane permeation, there is a batch formula in which the solvent is added continuously and a batch formula in which the solvent is intermittently added, but a formula having a relatively short desalting time is preferable. The pure water obtained by ion-exchange or distillation is used for the solvent to be supplemented in this way, but the poor solvent of a dispersing agent and a dispersing agent may be mixed in pure water, and may be added directly to an organic nanoparticle dispersion.

Filter filtration can use, for example, a device such as pressure filtration. As a preferable filter, a filter paper, a nano filter, an ultra filter, etc. are mentioned.

The centrifugal separator used for the concentration of the organic nanoparticles by centrifugation may be any device as long as the organic nanoparticles in the organic nanoparticle dispersion (or organic nanoparticle concentrate extract) can be precipitated. Examples of the centrifugal separator include a skimming function (a function of sucking the supernatant layer during the rotation and discharging it out of the system) in addition to the general-purpose apparatus, and a continuous centrifuge for continuously discharging solids.

The centrifugal conditions are preferably 50-10000, more preferably 100-8000, particularly preferably 150-6000, in terms of centrifugal force (a value indicating whether centrifugal acceleration takes several times the gravity acceleration). Although the temperature at the time of centrifugal separation depends on the kind of solvent of a dispersion liquid, -10-80 degreeC is preferable, -5-70 degreeC is more preferable, and 0-60 degreeC is especially preferable.

The isolated aggregates may be washed for the purpose of desalination, dehydration and removal of excess dispersant. The washing operation may be performed by adding the washing liquid as it is after the filtration through the limit filtration, centrifugal separation, the filter paper or the filter, and once the aggregates are taken out and reslurried in the washing liquid, the filtration is performed by the limit filtration, centrifugation, filtration by the filter paper or the filter. Isolation may be performed and washing may be performed in combination of these.

In addition, the washing may be performed not only after isolation as described above, but also before isolation. Agglomeration is achieved by standing the agglomerated nano pigment particle dispersion, removing the supernatant, and adding a washing solution to reslurry. After the slurry, the mixture may be left to stand, and the supernatant may be removed and filtered. If the washing is performed before isolation, the agglomerates are always wet, so that not only the washing efficiency is improved but also the redispersion described later is easier.

The cleaning liquid is not particularly limited as long as it can achieve desalination, dehydration, and removal of excess dispersant and flocculant. Specifically, an aqueous solvent (for example, water or hydrochloric acid, aqueous sodium hydroxide solution), an alcohol compound solvent, and an amide compound solvent , Ketone compound solvent, ether compound solvent, aromatic compound solvent, carbon disulfide solvent, aliphatic compound solvent, nitrile compound solvent, sulfoxide compound solvent, halogen compound solvent, ester compound solvent, ionic liquid, mixed solvent thereof and the like. Aqueous solvents, alcohol compound solvents, ketone compound solvents, ether compound solvents, nitrile compound solvents, sulfoxide compound solvents, ester compound solvents, amide compound solvents or mixtures thereof are preferred, especially aqueous solvents, alcohol compound solvents, esters Compound solvent, nitrile compound solvent It is right.

The washed aggregates may be subjected to redispersion as described later as it is, or to be redispersed after soaking with a redispersion solvent (described later), or may be dried and taken out as a powder of the organic nanoparticle dispersion and then redispersed.

In the present invention, the organic pigment nanoparticles isolated as described above can be redispersed in a non-aqueous medium to form a non-aqueous dispersion, but at this time, organic having a boiling point of 150 ° C. or higher (preferably 180 ° C. to 300 ° C.) It is preferable to disperse in a solvent. In this invention, a "boiling point" means the boiling point in 1 atmosphere, unless there is particular notice. In addition, this organic solvent may be called "high boiling point organic solvent" below. At this time, it is preferable to disperse | distribute the organic pigment nanoparticle in the mixed solvent of the good solvent and poor solvent mentioned above normally, and to substitute this mixed solvent and the said high boiling point organic solvent. Although the whole amount of a solvent may be substituted here, substitution of a whole amount is difficult normally, and when it is called substitution of a solvent in this invention, what is necessary is just to substitute a main solvent.

Although content of a pigment in the non-aqueous dispersion of this invention is not specifically limited, It is preferable that it is 10-20 mass%, and it is more preferable that it is 5-15 mass%. Although content of the said dispersion adjuvant contained in the non-aqueous dispersion of this invention is not specifically limited, It is practical that 0.05-5 mass% is contained.

Although substitution of a solvent may be performed in what order, it can carry out as follows, for example. First, the solvent component of the dispersion liquid containing precipitated fine particles is reduced or removed (hereinafter, this operation may be referred to as "concentration / removal"). Thereby, once, it is set as the concentrate and paste of organic pigment nanoparticle, or it is set as the powder of organic pigment nanoparticle. A predetermined high boiling point organic solvent can be added to it, and it can be set as the dispersion which disperse | distributed the pigment nanoparticle to the said organic solvent. In addition, in this invention, when disperse | distributing to the high boiling point organic solvent, it points out that the high boiling point organic solvent occupies more than half (it exists exceeding 50 mass%) in the solvent component which removed the solid content in the dispersion, and high boiling point organic solvent It is preferable that a solvent is 70 mass% or more.

In the present invention, the particles may be directly substituted with the high boiling point organic solvent after precipitation of the particles, but before the solvent replacement with the high boiling point organic solvent is performed, the first solvent is replaced with a third solvent described later. It is also preferable to reduce or eliminate the substitution with the high boiling point solvent. That is, the first solvent is first substituted with the third solvent from the mixed solvent of the good solvent (the first solvent) and the poor solvent (the second solvent), and then the third high solvent is substituted with the predetermined high boiling point organic solvent ( 2nd substitution), and it is preferable to perform 2 steps of solvent substitution. In addition, in this invention, a "dispersion product" means the composition in which predetermined | prescribed microparticles | fine-particles were disperse | distributed, The form is not specifically limited, It is used by the meaning containing a liquid composition (dispersion liquid), a paste composition, and a solid composition. do.

The organic solvent of boiling point 150 degreeC or more can be selected and used among the solvents shown below: glycol ester compounds, such as the glycol ether compound, such as diethylene glycol monomethyl ether, diethylene glycol monomethyl ether acetate, or propylene glycol diacetate, Aliphatic carboxylic acid compounds such as butyric acid or acid anhydrides thereof, butyl butyrate, aliphatic or aromatic ester compounds such as propyl benzoate, dicarboxylic acid diester compounds such as diethyl malonic acid, alkoxycar such as methyl 3-methoxypropionate Ketocarboxylic acid ester compounds such as acid ester compounds and ethyl acetoacetate; Halogenated carboxylic acid compounds such as chloroacetic acid and dichloroacetic acid; Alcohol compounds such as lauryl alcohol, phenol or phenol compounds; Ether compounds such as anisole; Alkoxyalcohol compounds such as 3-methoxybutanol; Glycol oligomer compounds such as diethylene glycol and tripropylene glycol; Aminoalcohol compounds such as triethanolamine; Alkoxyalcohol ester compounds such as 3-methoxybutyl acetate; Ketone compounds such as dibutyl ketone; Morpholine compounds such as N-phenylmorpholine; Aliphatic or aromatic amine compounds such as 1-octylamine, dicyclohexylamine, aniline.

Especially, in this invention, it is preferable to use a glycol ether compound, a glycol ester compound, or a carboxylic acid ester compound.

Specific examples of the organic solvent having a boiling point of 150 ° C. or higher include ethylene glycol monobutyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, 1,3-butylene glycol dibutyl ether, diethylene glycol dibutyl ether, and di Ethylene glycol monoethyl ether, tripropylene glycol n-butyl ether, diethyl adipic acid, dibutyl oxalate, dimethyl malonic acid, diethyl malonic acid, dimethyl succinate and diethyl succinate.

The organic solvent of 150 degreeC or more of boiling point may be used individually or in mixture with the solvent normally used for preparation of pigment dispersions, such as 3-methoxybutyl acetate and a propylene glycol monomethyl ether acetate (PGMEA).

Moreover, although you may use only one type of organic solvent of boiling point 150 degreeC or more, you may consist of multiple types.

Although the addition amount of the organic solvent of boiling point 150 degreeC or more is not specifically limited, It is preferable that it is 50-30000 mass parts with respect to 100 mass parts of pigment nanoparticles, and it is more preferable that it is 500-1000 mass parts.

Although the form of concentration and removal at the time of substituting a solvent is not specifically limited, For example, the extraction solvent is added and mixed to a pigment nanoparticle dispersion liquid, and the pigment nanoparticles are concentrated and extracted by the filter solvent, etc. Form of nanoparticle liquid, form of precipitated and concentrated pigment nanoparticles by centrifugation, form of desalination concentration by ultrafiltration, form of spray drying, form of sublimation of solvent by vacuum freeze-drying The form which dries and concentrates the solvent by heating to reduced pressure, the form which combined these, etc. Among these, the form which concentrates by centrifugation, the form using spray drying, and the solvent is dried by heating to reduced pressure, Concentrated form is preferred.

The extraction solvent used for the concentrated extraction is not particularly limited, but is not substantially mixed with the dispersion solvent (for example, the aqueous solvent) of the pigment nanoparticle dispersion (not substantially mixed with each other in the present invention). That is, the amount of dissolution is preferably 50% by mass or less, and more preferably 30% by mass or less, although there is no particular lower limit to this dissolution amount, considering the solubility of ordinary solvents, it is practically 1% by mass or more). It is preferable that it is a solvent which forms an interface, if left still. In addition, the extraction solvent is preferably a solvent that generates weak aggregation (floc which can be redispersed without applying high shearing force such as milling or high-speed stirring) in which the pigment nanoparticles can be redispersed in the extraction solvent. Such a state is preferable in that it is possible to wet the desired pigment nanoparticles with the extraction solvent without causing strong aggregation which changes the particle size, and can easily remove the dispersion solvent such as water by filter filtration or the like. As the extraction solvent, an ester compound solvent, an alcohol compound solvent, an aromatic compound solvent, an aliphatic compound solvent is preferable, an ester compound solvent, an aromatic compound solvent or an aliphatic compound solvent is more preferable, and an ester compound solvent is particularly preferable.

As an ester compound solvent, 2- (1-methoxy) propyl acetate, ethyl acetate, ethyl lactate, etc. are mentioned, for example. As an alcohol compound solvent, n-butanol, isobutanol, etc. are mentioned, for example. As an aromatic compound solvent, benzene, toluene, xylene, etc. are mentioned, for example. As an aliphatic compound solvent, n-hexane, cyclohexane, etc. are mentioned, for example. The extraction solvent may be a pure solvent of the above preferred solvent or a mixed solvent of a plurality of solvents.

The amount of the extraction solvent is not particularly limited as long as the pigment nanoparticles can be extracted, but is preferably smaller than the pigment nanoparticle dispersion in consideration of concentrated extraction. When this is represented by a volume ratio, when the pigment nanoparticle dispersion liquid is 100, it is preferable that the extraction solvent added is in the range of 1-100, More preferably, it is the range of 10-90, and the range of 20-80 is especially preferable. Too many requires enormous time for concentration, and too little, insufficient extraction results in nanoparticles remaining in the dispersion solvent.

After adding the extraction solvent, it is preferable to stir and mix so as to be in sufficient contact with the dispersion. Stirring mixing can use a conventional method. Although there is no restriction | limiting in particular in the temperature at the time of adding and mixing an extraction solvent, It is preferable that it is 1-100 degreeC, and it is more preferable that it is 5-60 degreeC. Any device may be used as long as the extraction solvent can be added and mixed preferably, but for example, a separation lot type device may be used.

Ultrafiltration, filter filtration, and centrifugal separation can be used as described above.

Freeze-drying is not specifically limited, Any thing may be employ | adopted as long as it is a normal method. For example, a refrigerant direct expansion method, a redundant freezing method, a fruit circulation method, a triple heat exchange method, an indirect heating freezing method, but preferably a refrigerant direct expansion method, an indirect heating freezing method, more preferably an indirect heating freezing method. It is good to use the method. In either method, it is preferable to perform freeze drying after preliminary freezing. Although the conditions of preliminary freezing are not specifically limited, The sample which performs freeze drying needs to be frozen evenly.

Apparatuses of the indirect heating freeze method include small freeze dryers, FTS freeze dryers, LYOVAC freeze dryers, laboratory freeze dryers, research freeze dryers, triple heat exchange vacuum freeze dryers, mono-cooled freeze dryers, and HULL freeze dryers. Small freeze dryers, laboratory freeze dryers, research freeze dryers, mono-cooled freeze dryers, more preferably small freeze dryers, mono-cooled freeze dryers are preferred.

Although the temperature of freeze drying is not specifically limited, For example, it is -190--4 degreeC, Preferably it is -120--20 degreeC, More preferably, it is about -80-60 degreeC. The pressure of the lyophilization is not particularly limited, but can be appropriately selected by those skilled in the art. For example, the pressure is preferably 0.1 to 35 Pa, preferably 1 to 15 Pa, more preferably about 5 to 10 Pa. The freeze drying time is, for example, 2 to 48 hours, preferably 6 to 36 hours, more preferably about 16 to 26 hours. Naturally, these conditions can be suitably selected by those skilled in the art. For lyophilization methods, see, for example, Formulation Machine Technology Handbook: Formulation Machine Technology Study Group, Chijinshokan, p. 120-129 (September 2000); Vacuum Handbook: Nippon Shinkogizu Co., Ltd., Omusa, p.328-331 (1992); Journal of Freezing and Drying Research Society: Ito Koji et al., No. 15, p. 82 (1965), and the like.

Drying under reduced pressure is not particularly limited as long as the solvent can be evaporated. For example, a general purpose vacuum dryer, a rotary pump, the apparatus which can heat-drying under reduced pressure, stirring a liquid, the apparatus which can be made to continuously dry by passing a liquid through the heat-reduced pipe | tube, etc. are mentioned.

30-230 degreeC is preferable, 35-200 degreeC is more preferable, and 40-180 degreeC of heating under reduced pressure drying temperature is especially preferable. 100-100000 Pa is preferable, as for the pressure at the time of reduced pressure, 300-90000 Pa is more preferable, 500-80000 Pa is especially preferable.

Moreover, you may dry by the following aspects. For example, as a dryer using hot air, a drum dryer, a multi-tube dryer, a cylindrical dryer or the like is preferably used as a dryer using heat conduction such as a shelf dryer, a band dryer, a stirring dryer, a fluidized bed dryer, a spray dryer, an airflow dryer, and the like. . In addition, depending on the solvent composition, a freeze dryer or an infrared dryer can also be used.

Among these means, from the viewpoint of being suitable for obtaining the powder dried directly from the dispersion, a spray dryer {for example, Okawara Kakoki Co., Ltd. COC-12}, a fluidized bed drier {for example, Naraki Kasei Co., Ltd. Sakusho MSD-100} is particularly preferably used. In addition, in order to produce the pigment powder with a small amount of residual solvent, you may use combining several drying means, for example, the process of obtaining the powder by fully drying the pigment dispersion preconcentrated with a cylindrical drier with a drum drier. Can be used.

It is possible to evaporate the solvent with respect to the drying conditions, and if the material such as pigment or dispersant is not modified, it is not particularly limited. In addition, for the purpose of increasing the drying rate, it is possible to combine means such as reduced pressure, stirring, and multistage according to the type of the dryer.

Although the quantity which reduces or removes a solvent component is not specifically limited, In the form which reduces a solvent component, it is preferable to remove 50 mass% or more of all solvent components, and it is more preferable to remove 75 mass% or more. In the form which removes a solvent component, it is preferable to remove 80 mass% or more of all the solvent components, and it is more preferable to remove 90 mass% or more.

When the solvent content is reduced by the concentration and removal process, the water content in the remaining dispersion is not particularly limited, but is preferably 0.01 to 3% by mass, more preferably 0.01 to 1% by mass. Under the present circumstances, it is preferable to remove the solvent component by the said drying method etc., for example, and to make it the powder of pigment nanoparticle, for example, it is preferable to make content of solid content into 50-100 mass%, for example, 70-100 mass. It is more preferable to set it as%. In addition, you may perform a concentration and removal process in multiple times.

In the present invention, it is preferable to redisperse the organic particles in the aggregated state by the concentration and removal step. The organic particles contained in the organic particle liquid may cause aggregation by isolation and solvent replacement. Although it is intentionally flocculated because rapid filter filtration is possible, in order to obtain a good dispersion state again, it is preferable to use a flocculated flocculation to the extent of redispersion.

In addition, in order to disperse | distribute the said aggregated state, the normal dispersing method may be inadequate. Even in the case of organic particles in such an aggregated state, in the present invention, the organic particles can be preferably redispersed by containing a predetermined dispersant in the non-aqueous dispersion together with the aforementioned dispersing aid. At this time, the dispersing agent added in order to make it a non-aqueous dispersion may be specifically called a non-aqueous dispersing agent.

As the non-aqueous dispersant, it is preferable to use a polymer compound having a mass average molecular weight of 1000 or more, more preferably a polymer compound represented by the following general formula (1).

In General Formula (1), A ¹ represents 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 The monovalent organic group containing the organic pigment | dye structure or heterocycle which may have a monovalent organic group or substituent which has group chosen from hydroxyl group is shown. n pieces of A ¹ may be the same or different.

The Specifically, A ¹ is not particularly limited, for example, as the "monovalent organic group having an acidic group" described above, a carboxylic acid group, a sulfonic acid group, a mono sulfuric acid ester group, an acid group, a mono-phosphate ester group, boric acid group, etc. The monovalent organic group which has is mentioned. In addition, having, for example, an amino group (-NH ₂₎ a monovalent organic group, a substituted imino group ^{(-NHR 8, -NR 9 R 10} ) having, as the "monovalent organic group having a basic group having a nitrogen atom" Monovalent organic groups (wherein R ⁸ , R ⁹ and R ¹⁰ each independently represent 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), Monovalent organic group which has a guanidyl group represented by the following general formula (a1) [In general formula (a1), R <^a1> and R <^a2> are respectively independently C1-C20 alkyl groups, C6-C20 aryl Group or a C7-C30 aralkyl group.], 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, an aryl group having 6 to 20 carbon atoms, or carbon Aralkyl groups of a number 7 or more and 30 or less.] Etc. are mentioned.

Wherein, for example, as the "monovalent organic group having a urea", -NHCONHR ¹⁵ (here, R ¹⁵ is an aryl group having a carbon number of 7 or more, or 30 or less in the alkyl group, having a carbon number of less than 620 of the hydrogen atoms, having a carbon number of less than 120 And aralkyl groups.) And the like.

Examples of the "monovalent organic group having a urethane group" include -NHCOOR ¹⁶ and -OCONHR ¹⁷ (herein, R ¹⁶ and R ¹⁷ each independently represent an alkyl group having 1 to 20 carbon atoms, and an aryl having 6 to 20 carbon atoms. Group or a C7-C30 aralkyl group.) Etc. are mentioned.

As said "monovalent organic group which has a" group which has a coordinating oxygen atom "", the group which has an acetylacetonato group, the group which has a crown ether, etc. are mentioned, for example.

As said "monovalent organic group which has a C4 or more hydrocarbon group", an C4 or more alkyl group (for example, an octyl group, a dodecyl group, etc.), a C6 or more aryl group (for example, a phenyl group, a naphthyl group, etc.), C7 The aralkyl group (for example, benzyl group etc.) mentioned above is mentioned. Although there is no upper limit in carbon number at this time, it is preferable that it is 30 or less.

As said "monovalent organic group which has an alkoxy silyl group", group which has a trimethoxy silyl group, a triethoxy silyl group, etc. is mentioned, for example.

As said "monovalent organic group which has an epoxy group", group which has glycidyl group etc. is mentioned, for example.

As said "monovalent organic group which has an isocyanate group", 3-isocyanatopropyl group etc. are mentioned, for example.

As said "monovalent organic group which has a hydroxyl group", 3-hydroxypropyl group etc. are mentioned, for example.

It is preferable that it is monovalent organic group which has an acidic group, a basic group which has a nitrogen atom, a urea group, or a C4 or more hydrocarbon group as said A <^1> .

The organic pigment structure or heterocycle is not particularly limited, and more specifically, as the organic pigment structure, for example, a phthalocyanine compound, an insoluble azo compound, an azolake compound, an anthraquinone compound, a quinacridone compound, a dioxazine compound, A diketopyrrolopyrrole compound, an anthrapyridine compound, an anthrone compound, an indanthrone compound, a flavantron compound, a perinone compound, a perylene compound, a thioindigo compound, etc. are mentioned. As the heterocycle, for example, thiophene, furan, xanthene, pyrrole, pyrroline, pyrrolidine, dioxolane, pyrazole, pyrazoline, pyrazolidine, imidazole, oxazole, thiazole, oxadia Sol, triazole, thiadiazole, pyran, pyridine, piperidine, dioxane, morpholine, pyridazine, pyrimidine, piperazine, triazine, trithiane, isoindolin, isoindolinone, benzimadzolone , Succinimide, phthalimide, naphthalimide, hydantoin, indole, quinoline, carbazole, acridine, acridon, anthraquinone and the like.

Moreover, the said organic pigment | dye structure or heterocycle may have substituent T, As said substituent T, C6-C16 aryl, such as a C1-C20 alkyl group, such as a methyl group and an ethyl group, a phenyl group, a naphthyl group, for example C1-C6 alkoxy groups, such as an acyloxy group, a methoxy group, and an ethoxy group, such as a group and an acetoxy group, halogen atoms, such as chlorine and a bromine, a methoxycarbonyl group, an ethoxycarbonyl group, and a cyclohexyl Carbonic acid ester groups, such as a C2-C7 alkoxycarbonyl group, a cyano group, t-butyl carbonate, a hydroxyl group, an amino group, a carboxyl group, a sulfonamide group, N-sulfonylamide group, such as an oxycarbonyl group, etc. are mentioned.

In addition, A <^1> can be represented by following General formula (4).

In General Formula (4), B ¹ represents 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 which may have a group, or a substituent selected from a hydroxyl group represents a good organic dye structure or a heterocyclic ring, R ¹⁸ represents a single bond or a linking group of a1-valent organic or inorganic. a1 represents a 1 ~ 5, a1 of B ¹ may be the same or different. The preferable aspect in group represented by General formula (4) is synonymous with said A <^1> .

R <^18> represents a single bond or an a1 + monovalent coupling group, and a1 represents 1-5. The linking group R ¹⁸ contains a group formed by 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 even if unsubstituted, a substituent is added. You may have it. R ¹⁸ is preferably an organic linking group.

As a specific example of R <^18> , the following structural unit or group comprised by combining these structural units is mentioned. In addition, the linking group R ¹⁸ may have the substituent T.

In said general formula (1), R <^1> represents a (m + n) valent coupling group. m + n satisfies 3-10.

Examples of the (m + n) valence 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 0 to 20 sulfur atoms. The group to be contained is contained and may have a substituent even if it is unsubstituted. R ¹ is preferably an organic linking group.

As a specific example of R <^1> , group (the ring structure may be formed.) Comprised by combining the group of said (t-1)-(t-34) or its plurality is mentioned. When the connecting group R ¹ has a substituent, the substituent T can be given as the above substituents.

R ² represents a single bond or a divalent linking group. R ² contains 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 further has a substituent even if unsubstituted. You may be. As a specific example of R <^2> , the group comprised by combining the said t-3-5, 7-18, 22-26, 32, 34 or its plurality is mentioned. It is preferable that R <^2> has a sulfur atom in the connection position with R <^1> . When said R <^2> has a substituent, the said substituent T is mentioned as said substituent.

M represents 1-8 in the said General formula (1). As m, 1-5 are preferable, 1-3 are more preferable, and 1-2 are especially preferable.

In addition, n represents 2-9. As n, 2-8 are preferable, 2-7 are more preferable, and 3-6 are especially preferable.

In said general formula (1), P <^1> represents a high molecular compound residue (polymer skeleton), and it can select suitably from a normal polymer etc.

Among the polymers, polymers or copolymers of vinyl monomers, ester compound polymers, ether compound polymers, urethane compound polymers, amide compound polymers, epoxy compound polymers, silicone compound polymers, and modified or copolymers thereof [Examples For example, a copolymer of a polyether / polyurethane copolymer, a polymer of a polyether / vinyl monomer, or the like (random copolymer, block copolymer, graft copolymer may be used), or the like. At least 1 sort (s) is preferable, At least 1 sort (s) chosen from the group which consists of a polymer or copolymer of a vinyl monomer, an ester compound polymer, an ether compound polymer, a urethane compound polymer, and these modified or copolymers is more preferable, Polymer or Polymer is particularly preferred.

In addition, the polymer is preferably soluble in an organic solvent. When the affinity with an organic solvent is low, when used as a pigment dispersant, for example, affinity with a dispersion medium may become weak and it may become impossible to ensure the adsorption layer sufficient for dispersion stabilization.

In addition, P ¹ preferably has a sulfur atom at a linking position with R ¹ .

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

In the said General formula (2), A <^2> is synonymous with A <^1> in the said General formula (1), and its specific preferable aspect is also the same. In addition, A ² may have a substituent and can illustrate the said substituent T.

In said general formula (2), R <^3> represents a (x + y) valent coupling group. R <^3> is synonymous with R <^1>, and its preferable range is also the same. In this case, R ³ is a x + y valence group, but the value of x and its preferred range are the same as n in general formula (1), the value of y and its preferred range are the same as m, and the value of x + y And the preferred range thereof is the same as m + n.

It is preferable that the coupling group represented by R <^3> is an organic coupling group, and the preferable specific example of this organic coupling group is shown below. However, this invention is not limited by these.

Among the above, from the viewpoints of availability of raw materials, ease of synthesis, and solubility in various solvents, (r-1), (r-2), (r-10), (r-11), (r-16), The group of (r-17) is preferable.

Moreover, when said R <^3> has a substituent, the said substituent T is mentioned as said substituent.

In said general formula (2), R <^4> and R <^5> represents a single bond or a bivalent coupling group each independently.

As a "bivalent coupling group" represented by said R <^4> , R <^5> , it 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 a divalent group combining two or more of these groups is preferable (R ¹⁹ And R ²⁰ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.). Especially, it is preferable that it is an organic coupling group.

Examples of the R ⁴ a straight-chain or branched alkylene group or an aralkyl 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 or aralkylene group, -O-, -C (= O)-, -N (R ¹⁹ )-or Particular preference is given to -CO ₂ -or divalent groups in which two or more of these groups are combined.

Examples of the R ⁵ a single bond, a linear or branched alkylene group, an aralkyl 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, aralkylene group, -O-, -C (= O)-, -N (R ¹⁹⁾ )-Or -CO ₂ -or divalent groups in combination of two or more of these groups are particularly preferred.

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

In addition, P <^2> in General formula (2) represents a polymer skeleton, and can be selected suitably from a normal polymer etc. For the preferred form of the polymer, and P ¹ and agreed in the general formula (1), it is preferred that the same type.

Of 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), and (r-16). Or (r-17), R ⁴ is a single bond, a linear or branched alkylene group or an aralkylene group, -O-, -C (= 0)-, -N (R ¹⁹ )-or -CO ₂ -or and these groups two or more divalent organic group in combination, R ⁵ is a single bond, an ethylene group, a propylene group or to a linking group represented by formula (sa) or (sb), polymer or copolymer of the P ^second vinyl monomers Particularly preferred are high molecular compounds which are copolymers, ester compound polymers, ether compound polymers, urethane polymers or modified substances thereof, y is 1 to 2 and x is 3 to 6. In addition, in the following group, R <^21> represents a hydrogen atom or a methyl group, and l represents 1 or 2.

It is preferable that the mass mean molecular weight of the said high molecular compound is 1000 or more, It is more preferable that it is 3000-100000 in a mass mean molecular weight, It is still more preferable that it is 5000-80000, It is especially preferable that it is 7000-60000. When the mass average molecular weight is in the above range, the effect of the plurality of functional groups introduced at the ends of the polymer is sufficiently exerted, thereby exhibiting excellent adsorption to the solid surface, micelle-forming ability, and surfactant activity, and achieving good dispersibility and dispersion stability. can do.

The specific example of the compound represented by General formula (1) is shown below. However, this invention is not limited to these specific examples at all.

The high molecular compound represented by the said General formula (1) or (2) can be synthesize | combined by each of the following methods, for example.

1.A acid halide or a plurality of functional groups (A in the general formula) having a polymer having a functional group selected from a carboxyl group, a hydroxyl group, an amino group, and the like at the terminal, and a plurality of functional groups (A ¹ or A ² in the general formula) alkyl halide or a plurality of functional groups having ¹ or a ²⁾ (a method of reacting a polymer such as an isocyanate having a ¹ or a ²⁾ in the formula.

2. at the terminal carbon-functional groups and the introduction of a carbon double bond polymer, a plurality of methods of a mercaptan having a (A ¹ or A ² in the formula), the Michael addition reaction.

3. A method of reacting a polymer having a carbon-carbon double bond introduced at its terminal with a mercaptan having a plurality of functional groups (A ¹ or A ² in the general formula) in the presence of a radical generator.

4. A method in which a polymer having a plurality of mercaptans introduced at its terminal and a functional group (A ¹ or A ² in the above general formula) having introduced a carbon-carbon double bond are reacted in the presence of a radical generator.

5. A method of radically polymerizing a vinyl monomer using a mercaptan compound having a plurality of functional groups (A ¹ or A ² in the general formula) as a chain transfer agent.

Especially, 2, 3, 4, and 5 are preferable from a synthetic | combination ease, 3, 4 and 5 are more preferable, and 5 is especially preferable. In addition, about these synthesis methods, Paragraph 0184 of Unexamined-Japanese-Patent No. 2006-129714-description of 0216 can be referred to.

As the polymer compound having a molecular weight of 1000 or more, a polymer compound having the following acidic group (hereinafter, the compound may be referred to as an "acid group-containing polymer compound") may be used, and the polymer compound is a polymer compound having a carboxyl group as the polymer compound. It is preferable that the copolymer compound containing at least 1 sort (s) of the repeating unit introduce | transduced from the compound which has (A) carboxyl group, and (B) the repeating unit introduced from the compound which has the carboxylic acid ester group is more preferable.

It is preferable that it is a repeating unit represented with the following general formula (I) as a repeating unit introduce | transduced from the compound which has the said (A) carboxyl group, It is more preferable that it is a repeating unit introduce | transduced from acrylic acid or methacrylic acid, and said (B) As a repeating unit introduced from the compound which has a carboxylic ester group, it is preferable that it is a repeating unit represented with the following general formula (II), It is more preferable that it is a repeating unit represented with the following general formula (IV), Benzyl acrylate It is particularly preferable that they are repeating units introduced from benzyl methacrylate, phenethyl acrylate, phenethyl methacrylate, 3-phenylpropyl acrylate or 3-phenylpropyl methacrylate.

In formula, R <_1> represents a hydrogen atom or a C1-C5 alkyl group. 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 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 the number of 1-5.

Moreover, as a polymerization ratio of the repeating unit introduce | transduced from the compound which has (A) carboxyl group, and the repeating unit introduce | transduced from the compound which has the said (B) carboxylic acid ester group, the quantity ratio with respect to the total number of repeating units of a repeating unit (A) It is preferable that it is 3-40, and it is more preferable that it is 5-35.

In the manufacturing method of this invention, a molecular weight means a mass average molecular weight unless there is particular notice. As a measuring method of molecular weight, a chromatography method, a viscosity method, a light scattering method, a sedimentation rate method, etc. are mentioned, but unless otherwise specified in the present invention, polystyrene measured by gel permeation chromatography method (carrier: tetrahydrofuran) A mass average molecular weight in terms of weight is used.

The high molecular compound may be both water-soluble and oil-soluble, and may be water-soluble or oil-soluble.

The method of adding the high molecular compound may be a solution dissolved in an aqueous solvent or an organic solvent, may be in a solid state, or a combination thereof. As a method of adding in a solution dissolved in a solvent, for example, a method of adding to a cohesive organic particle liquid in a state dissolved in the same solvent as the solvent of a cohesive organic particle liquid, or dissolving in another solvent compatible with the solvent of the coagulated organic particle liquid. The method of adding in the state which was made is mentioned. Although the density | concentration of the high molecular compound in the case of adding in the solution melt | dissolved in the solvent is not restrict | limited, 1-70 mass% is preferable, 2-65 mass% is more preferable, 3-60 mass% is especially preferable.

The addition of the high molecular compound may be added at any time during or after the precipitation generation of the pigment nanoparticles, at the time of concentration or before and after the dispersion, or at the time of dispersion of the aggregated organic particles after the concentration, or before or after these steps are completed, You may add in multiple times. Especially, in this invention, it is preferable to add a polymer compound with a mass mean molecular weight 1000 or more simultaneously with the 3rd solvent mentioned later, mix this polymer compound with a 3rd solvent, and add the liquid mixture to the concentrated pigment nanoparticle liquid It is more preferable to do. The amount of the polymer compound added is preferably 0.1 to 1000 parts by mass, more preferably 5 to 500 parts by mass, and particularly preferably 10 to 300 parts by mass with respect to 100 parts by mass of the pigment.

As 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-partial formalization, polyvinyl alcohol-part butyralide, vinylpyrrolidone-vinyl acetate copolymer, polyethylene oxide / propylene oxide block copolymer, polyamide, cellulose derivative, starch derivative and the like. Can be. In addition, natural polymer compounds such as alginate, gelatin, albumin, casein, gum arabic, tragacanth gum and lignin sulfonate can also be used. Moreover, as a high molecular compound which has an acidic group, polyvinyl sulfuric acid, condensation naphthalene sulfonic acid, etc. are mentioned.

As a high molecular compound which has a carboxyl group, polyacrylic acid, polymethacrylic acid, the cellulose derivative which has a carboxyl group in a side chain, etc. are mentioned, for example. As a copolymer compound containing at least 1 type of the repeating unit introduced from the compound which has (A) carboxyl group, and (B) the repeating unit introduced from the compound which has the carboxylic acid ester group, Unexamined-Japanese-Patent No. 59-44615. JP-A-54-34327, JP-A-58-12577, JP-A-54-25957, JP-A-59-53836 and JP-A-59-71048 Methacrylic acid copolymers, acrylic acid copolymers, itaconic acid copolymers, crotonic acid copolymers, maleic acid copolymers, partially esterified maleic acid copolymers, and the like as described in Japanese Patent Application Publication. As a particularly preferred example, acrylic acid-acrylic acid ester copolymers, methacrylic acid-acrylic acid ester copolymers, acrylic acid-methacrylic acid ester copolymers, methacrylic acid-methacrylic acid ester copolymers described in US Pat. And polyunsaturated copolymers of acrylic acid or methacrylic acid, acrylic acid esters or methacrylic acid esters, and other vinyl compounds.

Examples of the vinyl compound include styrene or substituted styrene (for example, vinyltoluene, vinylethylbenzene), vinylnaphthalene or substituted vinylnaphthalene, acrylamide, methacrylamide, acrylonitrile, methacrylonitrile, and the like. And styrene is preferred.

Only 1 type may be used for the high molecular compound of 1000 or more molecular weight, may be used for it in combination of 2 or more type, and may be used together with the compound of molecular weight less than 1000.

In the manufacturing method of the pigment nanoparticle of this invention, it is preferable to contain a 3rd solvent after precipitation of a pigment nanoparticle. 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, and an ester compound solvent and a ketone compound are preferable. Solvents are particularly preferred.

In addition, in this invention, in the meaning containing the said 3rd solvent and the 4th solvent mentioned later, the 1st solvent and the 2nd solvent which finally become a desired dispersion medium (continuous phase) collectively refer to another solvent, and the "third solvent It is called.

As an ester compound solvent, 2- (1-methoxy) propyl acetate, ethyl acetate, ethyl lactate, etc. are mentioned, for example. As an alcohol compound solvent, methanol, ethanol, n-butanol, isobutanol, etc. are mentioned, for example. As an aromatic compound solvent, benzene, toluene, xylene, etc. are mentioned, for example. As an aliphatic compound solvent, n-hexane, cyclohexane, etc. are mentioned, for example. As a ketone compound solvent, methyl ethyl ketone, acetone, cyclohexanone, etc. are mentioned, for example.

Especially, ethyl lactate, ethyl acetate, acetone, and ethanol are preferable, and ethyl lactate is more preferable. These may be used individually by 1 type and may use 2 or more types together. In addition, a good solvent (1st solvent), a poor solvent (2nd solvent), a 3rd solvent, and the said high boiling point organic solvent are not the same as each other.

Although the addition time of a 3rd solvent will not be specifically limited if precipitation of a pigment nanoparticle is carried out, It is preferable to, after depositing a pigment nanoparticle, concentrate and remove and add it. As described above, after passing through the first concentration / removal process, it is preferable to add the third solvent, and then reduce and remove the solvent content again by the second concentration / removal process. And after that, it is preferable to add a predetermined high boiling point organic solvent.

Although the addition amount of a 3rd solvent is not specifically limited, It is preferable that it is 100-30000 mass parts with respect to 100 mass parts of pigment nanoparticles, and it is more preferable that it is 500-1000 mass parts.

If necessary, the organic pigment nanoparticles in the aggregated state can be finely dispersed (in the present invention, the fine dispersion refers to loosening of the particles in the dispersion to increase the degree of dispersion).

In order to enable rapid filter filtration and to obtain a good dispersion state again, it is preferable to obtain the flocculated organic pigment nanoparticles described above as flocs which are flocculated to the extent of redispersibility.

Therefore, the degree of dispersion using a conventional dispersing method is insufficient for micronization and a method with high micronization efficiency is required.

As a method of finely dispersing aggregates of such nanoparticles, for example, a dispersion method by ultrasonic waves or a method of adding physical energy can be used.

It is preferable that the ultrasonic irradiation apparatus used has a function which can apply the ultrasonic wave 10kHz or more, For example, an ultrasonic homogenizer, an ultrasonic cleaner, etc. are mentioned. When liquid temperature rises during ultrasonic irradiation, since thermal coagulation of nanoparticles arises, it is preferable to make liquid temperature 1-100 degreeC, and 5-60 degreeC is more preferable. The control method of temperature can be performed by control of dispersion temperature, temperature control of the temperature adjusting layer which controls temperature of a dispersion liquid, etc.

There is no restriction | limiting in particular as a disperser used when disperse | distributing the concentrated organic nanoparticle by adding physical energy, For example, dispersers, such as a kneader, a roll mill, an attorney, a super mill, a dissolver, a homo mixer, and a sand mill, are mentioned. Can be. Moreover, the dispersion method by the use of a high pressure dispersion method and a microparticle beads is also mentioned as a preferable thing.

As a preferable manufacturing method of an organic nanoparticle dispersion, a kneading | dispersion processing is carried out so that the viscosity in 25 degreeC after kneading-dispersing-processing a coloring agent with a resin component may be comparatively high viscosity of 10,000 mPa * s or more, Preferably it is 100,000 mPa * s or more, Subsequently, the method of microdispersion processing is preferable so that the viscosity after a microdispersion process may add a solvent and it may be comparatively low viscosity of 1,000 mPa * s or less, Preferably it is 100 mPa * s or less.

The machines used in the redispersion process are two rolls, three rolls, ball mills, trom mills, dispersers, kneaders, kneaders, homogenizers, blenders, single- and twin-screw extruders, and disperse with high shear. . Subsequently, a solvent is added and it disperse | distributes with the beads of glass, zirconia, etc. of the particle diameter of 0.1-1 mm mainly using a longitudinal or horizontal sand grinder, a pin mill, a slit mill, an ultrasonic dispersion machine, a high pressure dispersion machine, etc. Further, precision dispersion treatment can also be performed using fine particle beads of 0.1 mm or less.

Furthermore, after disperse | distributing a main pigment and an auxiliary pigment, respectively, it is also possible to mix and disperse | distribute both dispersion liquids, or to disperse | distribute a main pigment and an auxiliary pigment together.

In addition, the details of the dispersion are described in T.C. Patton Flow and Pigment Dispersion (between John Wiley and Sons, 1964), and the like, may be used.

Pigment nanoparticles can be used, for example in the state disperse | distributed in the vehicle. The vehicle refers to a portion of the medium in which the pigment is dispersed when in a liquid state, and is liquid, and a portion (binder) which is combined with the pigment to harden the coating film and a component (organic solvent) that dissolves and dilutes the coating film. It contains.

The pigment nanoparticle concentration of the dispersion composition of the pigment nanoparticles after redispersion is suitably determined according to the objective, Preferably, it is preferable that pigment nanoparticles are 2-30 mass% with respect to the dispersion composition whole quantity, and are 4-20 mass% It is more preferable, 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 the dissolved dilution component is appropriately determined according to the type of the organic pigment, etc., but it is preferable that the binder is 1 to 30% by mass, and 3 to 20% by mass based on the total amount of the dispersion composition. More preferably, it is especially preferable that it is 5-15 mass%. It is preferable that it is 5-80 mass%, and, as for a melt | dissolution dilution component, it is more preferable that it is 10-70 mass%.

In the organic nanoparticle dispersion composition, the particles obtained by finely dispersing the organic nanoparticles (primary particles) after redispersion can be used, the particle diameter can be preferably 10 to 1000 nm, and more preferably 10 to 500 nm. 10-50 nm is especially preferable. Moreover, it is preferable that Mv / Mn of the particle | grains after redispersion is 1.0-2.0, It is more preferable that it is 1.0-1.8, It is especially preferable that it is 1.0-1.5.

According to the manufacturing method of this invention, even if the pigment particle contained in the organic pigment nanoparticle dispersion composition and the coloring photosensitive resin composition mentioned later is a small particle size of nanometer size (for example, 10-100 nm), for example, Concentrated redistribution. For this reason, when used for a color filter, optical density is high, the uniformity of the filter surface is excellent, contrast is high, and image noise can be reduced.

In addition, since the organic pigment nanoparticles contained in the organic pigment nanoparticle dispersion composition and the colored photosensitive composition can be highly and uniformly finely dispersed, the film thickness is thin and exhibits a high coloring density, for example, a color filter. It is to enable thinning of the back.

Moreover, it is excellent as an image forming material for producing a color proof, a color filter, etc. by containing the pigment which shows vivid color tone and high coloring power in organic pigment nanoparticle dispersion composition and colored photosensitive resin composition.

In addition, soluble in an alkaline aqueous solution can be used as the binder (binder) in the organic nanoparticle dispersion composition and the colored photosensitive resin composition for the alkaline developing solution used for exposure and development in forming a colored image, and it can meet environmental requirements. .

Moreover, the organic solvent which has moderate dryness can be used as a solvent (dispersion medium of a pigment) used for an organic pigment nanoparticle dispersion composition and a coloring photosensitive resin composition, and the requirement can be satisfied also from the point of drying after application | coating.

The colored photosensitive resin composition of this invention contains the dispersion of the said organic pigment nanoparticle, a binder, a monomer or oligomer, a photoinitiator, or a photoinitiator system. Hereinafter, each component of a coloring photosensitive resin composition is demonstrated.

The procedure for producing the organic pigment nanoparticles and their dispersions has already been described in detail. As for content of a pigment nanoparticle, 3-90 mass% is preferable with respect to the total solid in a coloring photosensitive resin composition (total solid content in this invention means the composition total except an organic solvent.), And 20-80 mass% More preferably, 25-60 mass% is more preferable. When this amount is too large, the viscosity of a dispersion liquid may rise and may become a problem in manufacture aptitude. Too little will not be sufficient. As pigment nanoparticle (pigment particle) which functions as a coloring agent, it is preferable that it is 0.1 micrometer or less in particle diameter, especially 0.08 micrometer or less in particle size. Moreover, you may use it in combination with a normal pigment for coloring. The pigment can use what was described above.

It is preferable that it is a polyfunctional monomer which has two or more ethylenically unsaturated double bonds and add-polymerizes by light irradiation as a monomer or oligomer. As such a monomer and an oligomer, the compound which has an ethylenically unsaturated group which can carry out at least 1 addition polymerization in a molecule | numerator, and whose boiling point is 100 degreeC or more at normal pressure is mentioned. Examples thereof include monofunctional acrylates and monofunctional methacrylates such as dipentaerythritol hexa (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate and phenoxyethyl (meth) acrylate. Rate; Polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, trimetholethane triacrylate, trimetholpropane tri (meth) acrylate, trimetholpropane diacrylate, neopentyl glycol di (Meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, hexanediol di (meth) Acrylate, trimetholpropane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) isocyanurate, tri (acryloyloxyethyl) cyanurate, glycerin tri (meth) acrylate; After addition of ethylene oxide or propylene oxide to polyfunctional alcohols, such as trimetholol propane and glycerin, polyfunctional acrylates and polyfunctional methacrylates, such as the thing (meth) acrylated, are mentioned. Furthermore, as described in General Formulas (1) and (2) in Japanese Patent Application Laid-Open No. 10-62986, a compound obtained by adding ethylene oxide or propylene oxide to a polyfunctional alcohol and then (meth) acrylated is also preferable. It can be mentioned as one.

Urethane acrylates described in JP-A-48-41708, JP-A-50-6034, and JP-A-51-37193; Polyester acrylates described in Japanese Patent Application Laid-Open No. 48-64183, Japanese Patent Publication No. 49-43191 and Japanese Patent Publication No. 52-30490; Polyfunctional acrylates and methacrylates, such as epoxy acrylates which are reaction products of an epoxy resin and (meth) acrylic acid, are mentioned.

Among these, trimetholpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and dipentaerythritol penta (meth) acrylate are preferable.

In addition, "polymerizable compound B" described in Unexamined-Japanese-Patent No. 11-133600 is also mentioned as a preferable thing.

A monomer or an oligomer may be used individually or in mixture of 2 or more types, As for content with respect to the total solid of a coloring photosensitive resin composition, 5-50 mass% is common, and 10-40 mass% is preferable. If the amount is too large, control of developability becomes difficult, resulting in problems in manufacturing aptitude. If too small, the curing power at the time of exposure will be insufficient.

As a binder, the binder which has an acidic group is preferable, Although it can add at the time of preparation of the inkjet ink for color filters or a coloring photosensitive resin composition, it is also preferable to add at the time of manufacturing the said pigment nanoparticle dispersion composition, or at the time of pigment nanoparticle formation. . A binder may be added to both or one side of the poor solvent for adding the organic pigment solution and the organic pigment solution to produce the pigment nanoparticles. Or it is also preferable to add a binder solution at the time of pigment nanoparticle formation with another system.

As a binder, the alkali-soluble polymer which has polar groups, such as a carboxylic acid group and a carboxylic acid base, in a side chain is preferable. Examples include Japanese Patent Application Laid-Open No. 59-44615, Japanese Patent Publication No. 54-34327, Japanese Patent Publication No. 58-12577, Japanese Patent Publication No. 54-25957, and Japanese Patent Publication No. 59-53836 Methacrylic acid copolymers, acrylic acid copolymers, itaconic acid copolymers, crotonic acid copolymers, maleic acid copolymers, partially esterified maleic acid copolymers and the like as described in Japanese Patent Application Laid-Open No. 59-71048; Can be. Moreover, the cellulose derivative which has a carboxylic acid group, a carboxylate, etc. in a side chain can also be mentioned, In addition, what added the cyclic acid anhydride to the polymer which has a hydroxyl group can also be used preferably. Further preferred examples include copolymers of benzyl (meth) acrylate and (meth) acrylic acid and polyunsaturated copolymers of benzyl (meth) acrylate with (meth) acrylic acid and other monomers described in US Pat. No. 4,139,391. have.

A binder may be used independently or may be used in the state of the composition used together with a normal film formation polymer, The addition amount with respect to 100 mass parts of pigment nanoparticles is 10-200 mass parts is common, and 25-100 mass parts is preferable. Do.

In addition, in order to improve crosslinking efficiency, you may have a polymeric group in a side chain, and UV curable resin, a thermosetting resin, etc. are also useful. As the binder resin, an organic polymer having a water-soluble atomic group in a part of the side chain can be used.

As a photoinitiator or a photoinitiator system (in this invention, a photoinitiator system refers to the mixture which expresses photoinitiation function by the combination of several compound.) Bisinal polyketaldonyl disclosed by the specification of US Patent 2367660. Compound, acyl inether compound described in US Pat. No. 2448828, aromatic acyloin compound substituted with α-hydrocarbon as described in US Pat. No. 2722512, US Pat. No. 3046127, and 2951758. Multinuclear quinone compound described in the specification, a combination of triarylimidazole dimer and p-aminoketone described in US Pat. No. 3549367, benzothiazole compound and trihalomethyl described in Japanese Patent Publication No. 51-48516 -s-triazine compound, trihalomethyl-triazine compound described in US Pat. No. 4,239,850, US Trihaloalkyl described in Patent No. 4,212,976 specification and methyl oxadiazole compound. In particular, trihalomethyl-s-triazine, trihalomethyloxadiazole and triarylimidazole dimers are preferred.

In addition, 1-phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) oxime and O-benzoyl as "polymerization initiator C" and oxime system described in Unexamined-Japanese-Patent No. 11-133600 are also mentioned. -4 '-(benzmercapto) benzoyl-hexyl-ketoxime, 2,4,6-trimethylphenylcarbonyl-diphenylphosphonyl oxide, hexafluorophosphoro-trialkylphenylphosphonium salt, etc. are also mentioned as a preferable thing. have.

Although a photoinitiator or a photoinitiator system may be used individually or in mixture of 2 or more types, it is preferable to use 2 or more types especially. Use of at least two photopolymerization initiators can reduce display characteristics, in particular, non-uniformity of display.

As for content of a photoinitiator or a photoinitiator system with respect to the total solid of a coloring photosensitive resin composition, 0.5-20 mass% is common, and 1-15 mass% is preferable. If the amount is too large, the sensitivity becomes too high, making control difficult. Too small an exposure sensitivity becomes too low.

In a coloring photosensitive resin composition, you may use the organic solvent (4th solvent) for resin composition preparation other than the said component further. Examples of the organic solvent include, but are not particularly limited to, esters, ethers and ketones. Of these solvents, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, ethylcarbitol 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 thereof. Moreover, the said high boiling point organic solvent can be used as this 4th solvent, For example, the solvent whose boiling point is 180 degreeC-250 degreeC can be used as needed. As for content of a 4th solvent, 10-95 mass% is preferable with respect to resin composition whole quantity.

Moreover, it is preferable to contain an appropriate surfactant in a coloring photosensitive resin composition. As surfactant, surfactant disclosed by Unexamined-Japanese-Patent No. 2003-337424 and Unexamined-Japanese-Patent No. 11-133600 is mentioned as a preferable thing. As for content of surfactant, 5 mass% or less is preferable with respect to resin composition whole quantity.

It is preferable that a coloring photosensitive resin composition contains a thermal polymerization inhibitor. Examples of the thermal polymerization inhibitor include hydroquinone, hydroquinone monomethyl ether, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4'-thiobis (3-methyl-6-t-butylphenol), 2,2'-methylenebis (4-methyl-6-t-butylphenol), 2-mercaptobenzimidazole, phenothiazine, etc. are mentioned. As for content of a thermal-polymerization inhibitor, 1 mass% or less is preferable with respect to resin composition whole quantity.

A coloring agent (dye, pigment) can be added to a coloring photosensitive resin composition as needed in addition to the said coloring agent (pigment). When using a pigment in a coloring agent, it is preferable to disperse | distribute uniformly in a coloring photosensitive resin composition, Therefore, it is preferable that particle diameter is 0.1 micrometer or less, especially 0.08 micrometer or less.

As dyes or pigments, specifically, as the pigment, the color material described in Japanese Patent Application Laid-Open Nos. 2005-17716 and the pigment or Japanese Patent Patent Publication No. 2005-361447 in [0068] to [0072]. The coloring agent of Unexamined-Japanese-Patent No. 2005-17521 [0080]-[0088] can be used preferably. As for content of the dye or pigment used auxiliary, 5 mass% or less is preferable with respect to resin composition whole quantity.

The coloring photosensitive resin composition can contain a ultraviolet absorber as needed. As a ultraviolet absorber, salicylate type, a benzophenone type, a benzotriazole type, a cyanoacrylate type, a nickel chelate type, a hindered amine type, etc. are mentioned besides the compound of Unexamined-Japanese-Patent No. 5-72724.

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

In addition, in a coloring photosensitive resin composition, the "adhesion adjuvant" of Unexamined-Japanese-Patent No. 11-133600, other additives, etc. can be contained in addition to the said additive.

The color filter of this invention is excellent in contrast. In the present invention, the contrast refers to the ratio of the amount of transmitted light when the polarization axes are parallel to each other between the two polarizing plates and when they are vertical ("7th Color Optical Conference, 1990, 512 Color Display 10.4" Size TFT- LCD color filters, Ueki, Ozeki, Fukunaga, Yamanaka, etc.).

The high contrast of the color filter means that the contrast of the contrast when combined with the liquid crystal can be increased, which is very important for the liquid crystal display to be replaced by CRT.

When the color filter of the present invention is used for a television, all monochromatic chromaticities of red (R), green (G), and blue (B) each by the F10 light source are shown in the values shown in the following table (hereinafter, " Target chromaticity ”.), Preferably within 5 or less, more preferably within 3, particularly preferably 2 or less.

In the present invention, chromaticity is measured by a microscopic spectrophotometer (Olympusko Gaku Co., Ltd .; OSP100 or 200), calculated as a result of 2 degrees F10 light source field of view, and represented by the xyY value of the xyz colorimeter. The difference from the target chromaticity is represented by the color difference of the La * b * color system.

It is preferable that the liquid crystal display device provided with the color filter of this invention is high in contrast, excellent in descriptive power, such as black sharpness, and especially VA system. It can be used suitably also as a liquid crystal display device of big screens, such as a display for laptops and a television monitor. Moreover, the color filter of this invention can be used for a CCD device, and shows the outstanding performance.

(Example)

EMBODIMENT OF THE INVENTION Hereinafter, although this invention is demonstrated in detail based on embodiment, this invention is limited and interpreted by this.

Synthesis Example 1 Synthesis of Basic Dispersion Aid

Thionyl chloride (20.0 mass parts) was added to bromodecanoic acid (10.0 mass parts), and it heated and refluxed for 1 hour, and excess thionyl chloride was distilled off under reduced pressure. This was dripped at the NMP (made by Wako Pure Chemical Industries, Ltd.) (100 mass parts) solution which melt | dissolved 5-aminobenzimazolone (7.0 mass part) and triethylamine (3.8 mass part), and it heated at 100 degreeC for 1 hour. Water (200 parts by mass) was added, and the precipitated solid was collected by filtration and washed with water and methanol to obtain BA-1 precursor (12.6 parts by mass) in yield 83%. BA-1 precursor (5 mass parts) was dissolved in NMP (40 mass parts), 50% dimethylamine aqueous solution (20 mass parts) was added to this, and it heated at 100 degreeC for 3 hours. Methanol (100 mass parts) was added, and the precipitated solid was collected by filtration and washed with methanol to obtain Exemplary Compound BA-1 (3.5 parts by mass) in a yield of 78% (m. P.> 300 ° C).

¹ H NMR (300MHz, DMSO-d ₆ ) δ1.2 (s, 12H), 1.2-1.4 (m, 2H), 1.5-1.6 (m, 2H), 2.0 (s, 6H), 2.1 (t, 2H ), 2.2 (t, 2H), 6.8 (d, 1H), 7.0 (d, 1H), 7.4 (s, 1H), 9.6 (s, 1H), 10.4 (s, 1H), 10.5 (s, 1H) .

A BA-1 precursor (3 parts by mass) synthesized in the same manner as in the synthesis of the above-described compound BA-1 was dissolved in NMP (24 parts by mass), and morpholine (6.5 parts by mass) was added thereto, followed by 4.5 hours at 100 ° C. Heated. Methanol (100 mass parts) was added, and the precipitated solid was collected by filtration and washed with methanol to give the exemplified compound BA-2 (2.6 mass parts) in a yield of 86% (m. P.> 300 ° C).

¹ H NMR (300MHz, DMSO-d ₆ ) δ1.2 (s, 12H), 1.3-1.4 (m, 2H), 1.5-1.6 (m, 2H), 2.2-2.3 (m, 8H), 3.5 (t , 4H), 6.8 (d, 1H), 7.0 (d, 1H), 7.4 (s, 1H), 9.6 (s, 1H), 10.4 (s, 1H), 10.5 (s, 1H).

The BA-1 precursor (3 parts by mass) synthesized in the same manner as in the synthesis of the exemplary compound BA-1 was dissolved in NMP (24 parts by mass), imidazole (5.1 parts by mass) was added thereto, and the mixture was 6.5 at 100 ° C. Heated for hours. Acetonitrile (200 parts by mass) was added, and the precipitated solid was collected by filtration and washed with acetonitrile to give Example Compound BA-3 (2.3 parts by mass) in a yield of 80% (m. P. 276-278 ° C).

¹ H NMR (300MHz, DMSO-d ₆ ) δ1.2 (s, 12H), 1.5-1.6 (m, 2H), 1.6-1.7 (m, 2H), 3.9 (t, 2H), 6.8 (d, 1H ), 6.9-7.0 (m, 2H), 7.2 (s, 1H), 7.4 (s, 1H), 7.8 (s, 1H), 9.7 (s, 1H), 10.4 (s, 1H), 10.5 (s, 1H).

Thionyl chloride (20.0 parts by mass) was added to bromohexanoic acid (7.4 parts by mass), and the mixture was heated and refluxed for 1 hour, and then excess thionyl chloride was distilled off under reduced pressure. This was dripped at the NMP (100 mass part) solution which melt | dissolved 5-aminobenzimazolone (7.0 mass part) and triethylamine (3.8 mass part), and heated at 100 degreeC for 1 hour. Water (200 parts by mass) was added, and the precipitated solid was collected by filtration and washed with water to obtain a BA-4 precursor (12.0 parts by mass) in yield 88%. BA-4 precursor (5 mass parts) was dissolved in NMP (46 mass parts), 50% dimethylamine aqueous solution (22 mass parts) was added to this, and it heated at 100 degreeC for 3 hours. Acetone nitrile (100 parts by mass) was added, and the precipitated solid was collected by filtration and washed with acetonitrile to give Example Compound BA-4 (3.4 parts by mass) in a yield of 85% (m. P.> 300 ° C).

¹ H NMR (300MHz, DMSO-d ₆ ) δ1.2-1.3 (m, 2H), 1.3-1.4 (m, 2H), 1.5-1.6 (m, 2H), 2.0 (s, 6H), 2.1 (t , 2H), 2.2 (t, 2H), 6.8 (d, 1H), 7.0 (d, 1H), 7.4 (s, 1H), 9.7 (s, 1H), 10.4 (s, 1H), 10.5 (s, 1H).

Thionyl chloride (20.0 mass parts) was added to bromodecanoic acid (10.0 mass parts), and it heated and refluxed for 1 hour, and excess thionyl chloride was distilled off under reduced pressure. This was dripped at the NMP (100 mass part) solution which melt | dissolved 2-aminobenzimidazole (5.0 mass part) and triethylamine (3.8 mass part), and it heated at 100 degreeC for 3 hours. Water (200 parts by mass) was added, and the precipitated solid was collected by filtration and washed with water to obtain a BA-5 precursor (11.5 parts by mass) in a yield of 80%. BA-5 precursor (5 mass parts) was dissolved in NMP (43 mass parts), 50% dimethylamine aqueous solution (21 mass parts) was added to this, and it heated at 100 degreeC for 3.5 hours. Water (100 parts by mass) was added, and the precipitated solid was collected by filtration and washed with water to obtain exemplary compound BA-5 (4.0 parts by mass) in a yield of 88% (m. P. 137-139 ° C).

¹ H NMR (300MHz, DMSO-d ₆ ) δ1.2-1.4 (m, 14H), 1.5-1.6 (m, 2H), 2.0 (s, 6H), 2.1 (t, 2H), 2.4 (t, 2H ), 6.8 (d, 1H), 7.0-7.1 (m, 2H), 7.4-7.5 (m, 2H).

Thionyl chloride (20.0 mass parts) was added to bromodecanoic acid (10.0 mass parts), and it heated and refluxed for 1 hour, and excess thionyl chloride was distilled off under reduced pressure. This was dripped at the NMP (100 mass part) solution which melt | dissolved 3-aminoanthraquinone (8.4 mass part) and triethylamine (3.8 mass part), and it heated at 100 degreeC for 3 hours. Water (200 parts by mass) was added, and the precipitated solid was collected by filtration and washed with water to obtain a BA-6 precursor (15.0 parts by mass) in yield 85%. BA-6 precursor (5 mass parts) was melt | dissolved in NMP (35 mass parts), 50% dimethylamine aqueous solution (17 mass parts) was added to this, and it heated at 100 degreeC for 6.5 hours. Acetone nitrile-water 1: 1 solution (100 parts by mass) was added to precipitate the solid, and the precipitated solid was washed with acetonitrile-water 1: 1 solution to yield Example Compound BA-6 (3.8 parts by mass) in 82% yield. It was obtained (mp 176-178 ° C).

¹ H NMR (300MHz, DMSO-d ₆ ) δ1.2-1.3 (m, 14H), 1.6-1.7 (m, 2H), 2.0 (s, 6H), 2.1 (t, 2H), 2.4 (t, 2H ), 7.8-7.9 (m, 2H), 8.0-8.2 (m, 4H), 8.4 (s, 1H), 10.5 (s, 1H).

Thionyl chloride (20.0 mass parts) was added to bromodecanoic acid (10.0 mass parts), and it heated and refluxed for 1 hour, and excess thionyl chloride was distilled off under reduced pressure. This was dripped at the NMP (100 mass part) solution which melt | dissolved 5-aminouracil (4.8 mass part) and triethylamine (3.8 mass part), and it heated at 100 degreeC for 3 hours. Water (200 parts by mass) was added, and the precipitated solid was collected by filtration and washed with water to obtain BA-7 precursor (11.8 parts by mass) in yield 84%. BA-7 precursor (5 mass parts) was dissolved in NMP (44 mass parts), 50% dimethylamine aqueous solution (21 mass parts) was added to this, and it heated at 100 degreeC for 4 hours. Acetone nitrile (100 parts by mass) was added, and the precipitated solid was collected by filtration and washed with acetonitrile to give Example Compound BA-7 (3.0 parts by mass) in a yield of 66% (b. P. 183-185 ° C).

¹ H NMR (300MHz, DMSO-d ₆ ) δ1.2 (s, 12H), 1.3-1.4 (m, 2H), 1.4-1.5 (m, 2H), 2.0 (s, 6H), 2.1 (t, 2H ), 2.3 (t, 2H), 8.0 (s, 1H), 9.0 (s, 1H).

<Example 1-1-1>

45 parts by mass of pigment CI pigment violet 23 (manufactured by Kurarianto Co., Hostaperm Violet RL-NF) and 1000 mV of methanesulfonic acid (made by Wako Pure Chemical Industries, Ltd.) and the above-described compound BA-1 (manufactured by Tokyo Kasei Co., 4.5 parts by mass) was added to prepare a pigment solution A-1.

Apart from this, 4000 parts by mass of water was prepared as a poor solvent.

Here, NP-KX was pigment-controlled A-1 which made temperature 80 degreeC to the poor solvent which temperature-controlled at 25 degreeC, and stirred at 500 rpm by GK-0222-10 type Ramondstara (brand name, Fujisawa Yakuhin Kogyo KK). It injected | injected using the -500 type large capacity no aneurysm pump (brand name, the Nippon Seimitsu Chemical Co., Ltd. product). The flow path diameter and the feed port diameter of the feed solution pipe of the pigment solution A-1 are set to 2.2 mm, the feed port is placed in a poor solvent, and 220 ml is injected at a flow rate of 200 ml / min to form organic pigment particles to thereby form a pigment dispersion A-1. Prepared. The particle diameter of this pigment dispersion liquid was measured using the nano track UPA-EX150 (brand name) by a Nikki Corporation.

As a result of measuring the pH of this pigment dispersion liquid by pH test paper (made by ADVANTEC company), it was 1, and it neutralized by adding 48% sodium hydroxide aqueous solution until pH became 9. The generated aggregates were observed by an optical microscope.

The above-mentioned aggregate was collected by filtration by filter paper (ADVANTEC Co., No. 2), and the time required for filtration at this time was measured. The organic nano pigment collected by filtration was washed with water (300 parts by mass).

A solution obtained by adding 80 parts by mass of a non-aqueous dispersant C-1 (the above-described high molecular compound C-1) to 300 parts by mass of ethyl lactate was added to the pigment nanoparticle concentrate paste, followed by stirring at 1500 rpm for 60 minutes by a dissolver. 25 mass parts of ethyl acetate were added, and it stirred further by 500 rpm and 10 minutes by the resolver, and obtained pigment nanoparticle lactic-acid ethyl dispersion A-1. The organic pigment powder A-1 of the present invention was obtained by solvent removal of the said pigment nanoparticle lactic acid ethyl dispersion A-1 by the evaporator.

Pigment dispersion composition A-1 of the following composition was prepared using said organic pigment powder A-1.

1 mass part of said organic pigment powder A-1

1,3 butylene glycol diacetate 4 parts by mass

The pigment dispersion composition A-1 of the said composition was disperse | distributed for 1 hour at circumferential speed of 9 m / s using zirconia beads of diameter 0.65 mm with motor mill M-50 (made by Eiger Japan).

The following evaluation was performed about the obtained pigment dispersion composition. The results are shown in Table 1.

(1) Average Particle Diameter of Organic Nanoparticle Aqueous Dispersion

The number average particle diameter was measured using the nano track UPA-EX150 by Nikkiso.

(2) diameter of aggregates

The aggregate was observed with an optical microscope, and the diameter of the aggregate was measured with reference to the criteria observed separately. About the diameter of the aggregate here, the length of the stage was measured from the stage of the aggregate, and the part with the longest length was defined as the diameter. The agglomerate here is a nanoparticle which is a primary particle which is not originally seen by the naked eye, gathers more, grows large, and becomes a secondary particle.

(3) filtration time

The filtration time per 1 g of pigment was measured by filtration under reduced pressure with an aspirator using a nutche of 9 cm in diameter and a filter paper (No. 2 (trade name) manufactured by Adovantech Co., Ltd.).

(4) contrast evaluation

The obtained pigment dispersion compositions A-1 to F-1 were coated on the glass substrate so that the thickness became 2 µm, respectively, to prepare a sample. As a backlight unit, a diffuser plate was installed in a three-wavelength cold cathode light source (FWL18EX-N manufactured by Toshiba Raitech Co., Ltd.), and a two-layered polarizer plate was used between the polarizing plates HLC2-2518 made by Sanritsu Co., Ltd. With the sample, the amount of transmitted light when the polarization axes were parallel and vertical was measured, and the ratio was contrasted ("7th Color Optical Conference in 1990, 512 Color Display 10.4" Size Filter for TFT-LCD, Ueki, Ozeki, Fukunaga, Yakunaka, etc.). Two polarizing plates, a sample, and a color luminance meter are installed at a position of 13 mm from the backlight, and a cylinder having a diameter of 11 mm and a length of 20 mm is disposed at a position of 40 mm to 60 mm. The measurement sample provided in the position of 65 mm was irradiated, and the transmitted light was measured by the color luminance meter installed in the position of 400 mm through the polarizing plate provided in the position of 100 mm. The measurement angle of the color luminance meter was set to 2 degrees. The light quantity of the backlight was set so that the brightness | luminance at the time of installing two polarizing plates in parallel nicol in the state which does not provide a sample is 1280 cd / m <2>.

<Example 1-1-2>

The above exemplary compound BA-1 of Example 1-1-1 was changed to exemplary compound BA-6, and the same operation as in Example 1-1-1 was performed. The obtained organic nanoparticle non-aqueous dispersion is also called pigment dispersion composition B-1. Table 1 shows the results of the same evaluation test as in Example 1-1-1 on the pigment dispersion composition B-1.

<Example 1-1-3>

The exemplary compound BA-1 of Example 1-1-1 was changed to exemplary compound BA-7, and the same operation as in Example 1-1-1 was performed. The obtained organic nanoparticle non-aqueous dispersion is also called pigment dispersion composition C-1. The result of having performed the evaluation test similar to Example 1-1-1 about pigment dispersion composition C-1 is shown in Table 1.

<Example 1-1-4>

Polyvinylpyrrolidone (K-25, a brand name, Wako Pure Chemical Industries, Ltd., 90 mass parts) is also added with the said exemplary compound BA-1 of Example 1-1-1, and it is the same as that of Example 1-1-1. The operation was performed. The obtained organic nanoparticle non-aqueous dispersion is also called pigment dispersion composition D-1. The result of having performed the evaluation test similar to Example 1-1-1 about pigment dispersion composition D-1 is shown in Table 1.

<Comparative Example 1-1-1>

Polyvinylpyrrolidone (K-25, brand name, Wako Pure Chemical Industries, Ltd., 90 mass parts) is added instead of the said polymeric compound BA-1 of Example 1-1-1, and meta is substituted for the said polymeric compound C-1. The same operation as in Example 1-1-1 was carried out except for using a methacrylic acid / methacrylic acid benzyl copolymer. The obtained organic nanoparticle non-aqueous dispersion is also called pigment dispersion composition E-1. The result of having performed the evaluation test similar to Example 1-1-1 about pigment dispersion composition E-1 is shown in Table 1.

<Reference Example 1-1-1>

The aqueous pigment dispersion was adjusted by the same operation as in Example 1-1-1, and isolated without performing the pH operation to obtain the dispersion composition F-1. The filtration time at this time was evaluated. The results are shown in Table 1.

As shown in Table 1, according to the basic dispersion aid of the present invention, a high contrast is realized in the non-aqueous dispersion in which the fine particles are aggregated once in the aqueous dispersion, the medium is switched and redispersed with an organic solvent, and the filterability is further improved. It can be seen that the separation time is greatly reduced, and the characteristics and productivity of the desired dispersion and color filter are significantly improved.

<Example 1-2>

Hereinafter, the manufacturing method of a coloring photosensitive resin composition and a color filter is demonstrated.

[Formation of black (K) image]

After washing an alkali free glass substrate with a UV washing apparatus, it brush-cleaned using a detergent and ultrasonic-cleaned again by ultrapure water. The substrate was heat-treated at 120 ° C. for 3 minutes to stabilize the surface state.

After cooling the said board | substrate and adjusting the temperature to 23 degreeC, the coloring photosensitive resin composition K1 which consists of a composition of following Table 2 is apply | coated by the coater for glass substrates (AFS Asia company make, brand name: MH-1600) which has a slit-shaped nozzle. did. Subsequently, VCD {vacuum drying device; After a part of the solvent was dried for 30 seconds to remove the fluidity of the coating layer by Tokyo Oka Kogyo Co., Ltd.), it was prebaked at 120 ° C. for 3 minutes to obtain a photosensitive resin layer K1 having a thickness of 2.4 μm.

The distance between the exposure mask surface and the photosensitive resin layer in a state where the substrate and the mask (a quartz exposure mask having an image pattern) are vertically set by a proximity type exposure machine (manufactured by Hitachi High-Tech Engineering Co., Ltd.) having an ultra-high pressure mercury lamp. Was set to 200 µm, and the pattern was exposed at an exposure dose of 300 mJ / cm 2.

Subsequently, pure water was sprayed with a shower nozzle to uniformly wet the surface of the photosensitive resin layer K1, and then to a KOH-based developer (KOH, containing a nonionic surfactant, trade name: CDK-1, manufactured by FUJIFILM Materials). Thereby, shower development was carried out at 23 ° C. for 80 seconds at a flat nozzle pressure of 0.04 MPa to obtain a patterned image. Subsequently, ultrapure water was sprayed at a pressure of 9.8 MPa with an ultrahigh pressure washing nozzle to remove residue to obtain an image K of black (K). Subsequently, it heat-processed at 220 degreeC for 30 minutes.

[Formation of red (R) pixel]

The colored photosensitive resin composition R1 which consists of a composition of the following Table 3 was used for the board | substrate with which the said image K was formed, and the pixel R heat-treated by the same process as formation of the said black (K) image was formed. The film thickness of the photosensitive resin layer R1 and the coating amount of the pigments (C. I. P. R. 254 and C. I. P. R. 177) are shown below.

Photosensitive resin film thickness (μm) 1.60

Pigment Coating Amount (g / ㎡) 1.00

C. I. P.R. 254 Coating amount (g / ㎡) 0.70

C. I. P. R. 177 Coating amount (g / ㎡) 0.30

[Formation of Green (G) Pixel]

The colored photosensitive resin composition G1 which consists of a composition of the following Table 4 was used for the board | substrate which formed the said image K and the pixel R, and the pixel G heat-treated by the same process as formation of the said black (K) image was formed. The film thickness of the photosensitive resin layer G1 and the coating amount of the pigments (C. I. P. G. 36 and C. I. P. Y. 150) are shown below.

Photosensitive resin film thickness (μm) 1.60

Pigment application amount (g / ㎡) 1.92

C. I. P. G. 36 Coating amount (g / ㎡) 1.34

C. I. P. Y. 150 Coating amount (g / ㎡) 0.58

[Formation of Blue (B) Pixel]

By using the coloring photosensitive resin composition B1 which consists of a composition of Table 5 to the board | substrate which formed the said image K, the pixel R, and the pixel G, the pixel B heat-treated by the same process as formation of the said black (K) image is formed The desired color filter A was obtained.

The film thickness of the said photosensitive resin layer B1 and the coating amount of a pigment (C.I.P.B.15: 6 and C.I.P.V.23) are shown below.

Photosensitive resin film thickness (μm) 1.60

Pigment Coating Amount (g / ㎡) 0.75

C. I. P. B. 15: 6 Coating amount (g / ㎡) 0.45

C. I. P. V. 23 Coating amount (g / ㎡) 0.30

Here, preparation of the coloring photosensitive resin composition K1, R1, G1, B1 of the said Tables 2-5 is demonstrated in more detail.

The coloring photosensitive resin composition K1 first weighs K pigment dispersion 1 and propylene glycol monomethyl ether acetate in the amounts shown in Table 2, mixed at a temperature of 24 ° C. (± 2 ° C.), stirred at 150 rpm for 10 minutes, and then the table. Methyl ethyl ketone, binder 2, hydroquinone monomethyl ether, DPHA liquid of the amount described in 2, polymerization initiator A (2,4-bis (trichloromethyl) -6- [4'-N, N-bisethoxycarb Carbonyl methyl) amino-3'-bromophenyl] -s-triazine) and Surfactant 1 were weighed and added in this order at a temperature of 25 ° C (± 2 ° C) and at a temperature of 40 ° C (± 2 ° C) It obtained by stirring for 30 minutes at 150 rpm.

Moreover, the composition was shown below about the following component in the composition of Table 2.

<K Pigment Dispersion 1>

Carbon black {brand name: Nipex 35, made by Deg's Japan Co., Ltd.} 13.1 parts by mass

0.65 parts by mass of pigment dispersant A (the following compound C-1 synthesized according to Japanese Patent Application Laid-Open No. 2000-239554)

(See Japanese Patent Application Laid-Open No. 2000-239554.)

6.72 parts by mass of polymer (benzyl methacrylate / methacrylic acid = random copolymer of 72/28 molar ratio, molecular weight 370,000)

79.53 parts by mass of propylene glycol monomethyl ether acetate

<Surfactant 1>

[Megapack F-780-F {manufactured by Dainippon Ink and Chemical Industries, Inc.]

C ₆ F ₁₃ CH ₂ CH ₂ OCOCH = CH ₂ : 40 parts by mass

H (OCH (CH ₃ ) CH ₂ ) ₇ OCOCH = CH ₂ : with 55 parts by mass

H (OCH ₂ CH ₂ ) ₇ OCOCH = CH ₂ : 5 parts by mass of copolymer (molecular weight 30,000) 30 parts by mass

<Binder 2>

Polymer (benzyl methacrylate / methacrylic acid = 78/22 molar ratio

         Of random copolymer, molecular weight 3.8 million) 27 parts by mass

Propylene glycol monomethyl ether acetate 73 parts by mass

<DPHA liquid>

-Defentaerythritol hexaacrylate {contains 500 ppm of polymerization inhibitor MEHQ, manufactured by Nippon Kayaku Co., Ltd., product name: KAYARAD DPHA} 76 parts by mass

24 parts by mass of propylene glycol monomethyl ether acetate

The coloring photosensitive resin composition R1 first weighs R pigment dispersion 1, R pigment dispersion 2, and propylene glycol monomethyl ether acetate in the amounts shown in Table 3, mixed at a temperature of 24 ° C (± 2 ° C) for 10 minutes at 150 rpm. After stirring, the methyl ethyl ketone, the binder 1, the DPHA liquid and the polymerization initiator B (2-trichloromethyl-5- (p-styrylstyryl) -1,3,4-oxadia in the amounts shown in Table 3 were then added. Sol), polymerization initiator A (2,4-bis (trichloromethyl) -6- [4 '-(N, N-bisethoxycarbonylmethyl) amino-3'-bromophenyl] -s-triazine ), Phenothiazine is weighed, added in this order at a temperature of 24 ° C. (± 2 ° C.), stirred at 150 rpm for 30 minutes, and the surfactant 1 in the amount shown in Table 3 is weighed, and a temperature of 24 ° C. (± 2 degreeC), and it stirred for 5 minutes at 30 rpm, and obtained by filtering by nylon mesh # 200.

In addition, in the composition of Table 3, R pigment dispersion 1 and 2 are each prepared so that the composition may be the following mass part using the method of Example 1 of the international publication WO 2006/121016 pamphlet.

<R Pigment Dispersion 1>

10 parts by mass of C. I. P. R. 254 {brand name: Irgaphor Red BT-CF Chivas Specialty Chemicals Co., Ltd.}

1 part by mass of pigment dispersant A

Polymer (benzyl methacrylate / methacrylic acid = 72/28 molar ratio

                  Of random copolymer, molecular weight 30,000) 10 parts by mass

79 parts by mass of propylene glycol monomethyl ether acetate

Polymer (benzyl methacrylate / methacrylic acid = 72/28 molar ratio

                  Of random copolymer, molecular weight 30,000) 15 parts by mass

Propylene glycol monomethyl ether acetate 62.5 parts by mass

<Binder 1>

Polymer (benzyl methacrylate / methacrylic acid / methyl methacrylate

= 38/25/37 mole ratio random copolymer, molecular weight 40,000) 27 parts by mass

Propylene glycol monomethyl ether acetate 73 parts by mass

<R Pigment Dispersion 2>

C. I. P. R. 177 {A brand name: Cromophtal Red A2B, Chiba Specialty Chemicals Co., Ltd.} 22.5 parts by mass

Polymer (benzyl methacrylate / methacrylic acid = 72/28 molar ratio

                 Of random copolymer, molecular weight 30,000) 15 parts by mass

Propylene glycol monomethyl ether acetate 62.5 parts by mass

The coloring photosensitive resin composition G1 first weighs G pigment dispersion 1, Y pigment dispersion 1, and propylene glycol monomethyl ether acetate in the amounts shown in Table 4, mixed at a temperature of 24 ° C (± 2 ° C) for 10 minutes at 150 rpm. After stirring, methyl ethyl ketone, cyclohexanone, binder 2, DPHA liquid, polymerization initiator B (2-trichloromethyl-5- (p-styrylstyryl) -1,3, 4-oxadiazole), polymerization initiator A (2,4-bis (trichloromethyl) -6- [4 '-(N, N-bisethoxycarbonylmethyl) amino-3'-bromophenyl]- s-triazine) and phenothiazine were weighed, added in this order at a temperature of 24 ° C. (± 2 ° C.), stirred at 150 rpm for 30 minutes, and the surfactant 1 in the amount shown in Table 4 was weighed and It obtained by adding at 24 degreeC (+/- 2 degreeC), stirring for 5 minutes at 30 rpm, and filtering by nylon mesh # 200.

In addition, in the composition of Table 4, the G pigment dispersion 1 used "brand name: GT-2" made from FUJIFILM Electronics. The Y pigment dispersion 1 used "brand name: CF yellow EX3393" by the Mikunishikiso company.

The colored photosensitive resin composition B1 first weighs B pigment dispersion 1, V pigment dispersion composition 1, and propylene glycol monomethyl ether acetate in the amounts shown in Table 5, mixed at a temperature of 24 ° C. (± 2 ° C.) for 10 minutes at 150 rpm. After stirring, the methyl ethyl ketone, the binder 3, the DPHA liquid and the polymerization initiator B (2-trichloromethyl-5- (p-styrylstyryl) -1,3,4-oxadia in the amounts shown in Table 5 were then added. Sol) and phenothiazine were weighed and added in this order at a temperature of 25 ° C. (± 2 ° C.), stirred at 150 rpm at a temperature of 40 ° C. (± 2 ° C.) for 30 minutes, and the positive interface shown in Table 5. The activator 1 was weighed, added at a temperature of 24 ° C. (± 2 ° C.), stirred at 30 rpm for 5 minutes, and obtained by filtration with nylon mesh # 200.

In addition, in the composition of Table 5, B pigment dispersion 1 used the "brand name: CF blue EX3357" by the Mikunishikiso company. As the V pigment dispersion composition 1, the pigment dispersion composition A-1 was used.

The composition of the binder 3 is as follows.

<Binder 3>

27 parts by mass of polymer (benzyl methacrylate / methacrylic acid / methyl methacrylate = random copolymer of 36/22/42 molar ratio, molecular weight 370,000)

Propylene glycol monomethyl ether acetate 73 parts by mass

The color filter A-1 was produced as mentioned above. Color filters B-1 to E by the same operation as the color filter A-1 except that the pigment dispersion composition A-1 used as the V pigment dispersion composition 1 in the color filter A-1 was replaced with B-1 to E-1, respectively. Produced -1.

Table 6 shows the results of measuring the contrast in the same manner as the above-described contrast measurement for each color filter.

From the said result, all the color filters of this invention were high contrast and were favorable color filters.

<Example 1-3>

The liquid crystal display device was produced using color filter A-1-E-1, and the display characteristic was evaluated.

(Formation of ITO Electrodes)

The glass substrate in which the said color filter was formed was put into the sputter apparatus, 1300 micrometers of ITO (indium tin oxide) was vacuum-deposited at 100 degreeC, and it annealed at 240 degreeC for 90 minutes, and ITO was crystallized and the ITO transparent electrode was formed.

(Formation of spacer)

The spacer was formed on the above-mentioned ITO transparent electrode by the method similar to the spacer formation method of [Example 1] of Unexamined-Japanese-Patent No. 2004-240335.

(Formation of projection for liquid crystal orientation control)

Using the coating liquid for positive type photosensitive resin layers below, the processus | protrusion for liquid crystal orientation control was formed on the ITO transparent electrode in which the said spacer was formed.

However, the following method used the exposure, image development, and baking process.

Proximity exposure machine (made by Hitachi High-Tech Engineering Co., Ltd.) is arrange | positioned so that a predetermined photomask may be 100 micrometers from the surface of the photosensitive resin layer, and it is irradiated with 150 mJ / cm <2> of ultra-high pressure mercury lamps via the said photomask. Proximity exposure.

Subsequently, a 2.38% tetramethylammonium hydroxide aqueous solution was developed while spraying onto the substrate at 33 ° C. for 30 seconds with a shower developing device. Thus, the unnecessary part (exposure part) of the photosensitive resin layer was image-removed, and the board | substrate for liquid crystal display devices with which the processus | protrusion for liquid crystal orientation control which consists of the photosensitive resin layer patterned in the desired shape on the color filter side board | substrate was obtained.

Next, the cured liquid crystal alignment control protrusion was formed on the liquid crystal display device substrate by baking the liquid crystal display device substrate having the liquid crystal alignment control protrusion formed at 230 ° C. for 30 minutes.

<Prescription of coating liquid for positive photosensitive resin layer>

Positive resist liquid {FH-2413F made by Fujifilm Electronics Co., Ltd.}: 53.3 parts by mass

Methyl ethyl ketone: 46.7 parts by mass

Mega Pack F-780F {manufactured by Dainippon Ink and Chemical Industries, Inc .: 0.04 parts by mass

The alignment film which consists of polyimide was further formed on the board | substrate for liquid crystal display devices obtained above.

Thereafter, a sealing agent of an epoxy resin was printed at a position corresponding to the black matrix outer frame formed around the pixel group of the color filter, and the liquid crystal for MVA mode was added dropwise and attached to the counter substrate. The substrate was heat treated to cure the sealing agent. The polarizing plate HLC2-2518 by Sanlitz Corporation was attached to both surfaces of the liquid crystal cell obtained in this way. Subsequently, the backlight of the three wavelength cold cathode tube light source (FWL18EX-N by Toshiba Raitech Co., Ltd.) was comprised, and it was arrange | positioned at the side used as the back surface of the liquid crystal cell in which the said polarizing plate was provided, and it was set as the liquid crystal display device.

About the liquid crystal display device using the color filter of the comparative example It was confirmed that the liquid crystal display device using the color filter of this invention was excellent in black clarity and blue portability, and showed favorable display characteristics.

Synthesis Example-2 Synthesis of Acidic Compound

5-aminobenzimazolone (30.0 parts by mass) was dissolved in NMP (manufactured by Wako Pure Chemical Industries, Ltd.) (160 parts by mass), and glutaric anhydride (18.6 parts by mass) was added thereto and stirred at room temperature for 1.5 hours. Water (100 mass parts) was added, and the precipitated solid was collected by filtration and washed with water and methanol to give Exemplary Compound A-1 (39 parts by mass) in a yield of 80% (m. P.> 300 ° C).

¹ H NMR (300MHz, DMSO-d ₆ ) δ1.7-1.9 (m, 2H), 2.2-2.4 (m, 4H), 6.8 (d, 1H), 7.0 (d, 1H), 7.4 (s, 1H ), 9.7 (s, 1H), 10.4 (s, 1H), 10.5 (s, 1H).

5-aminobenzimazolone (10.0 parts by mass) was dissolved in NMP (55 parts by mass), diglycolic acid anhydride (6.3 parts by mass) was added thereto, and the mixture was stirred at room temperature for 1 hour. Water (100 parts by mass) was added, and the precipitated solid was collected by filtration and washed with water and methanol to give Exemplary Compound A-2 (9.8 parts by mass) in a yield of 60% (mp 290-291 ° C. (dec)). .

¹ H NMR (300 MHz, DMSO-d ₆ ) δ4.1 (s, 2H), 4.2 (s, 2H), 6.8 (d, 1H), 7.1 (d, 1H), 7.5 (s, 1H), 9.7 ( s, 1 H), 10.4 (s, 1 H), 10.5 (s, 1 H).

5-aminobenzimidazole (10.0 parts by mass) was dissolved in NMP (75 parts by mass), glutaric anhydride (8.6 parts by mass) was added thereto, and the mixture was heated at 60 ° C for 6 hours. Water (100 mass parts) was added, and the precipitated solid was collected by filtration and washed with water and methanol to give Exemplary Compound A-4 (9.8 parts by mass) in a yield of 60% (m. P. 284-286 ° C).

¹ H NMR (300MHz, DMSO-d ₆ ) δ1.8-1.9 (m, 2H), 2.2-2.3 (m, 2H), 2.4-2.5 (m, 2H), 7.0-7.1 (m, 2H), 7.4 -7.5 (m, 2 H).

5-aminouracil (10.0 parts by mass) was dissolved in NMP (80 parts by mass), glutaric anhydride (9.0 parts by mass) was added thereto, and the mixture was heated at 60 ° C. for 6 hours. Water (100 mass parts) was added, and the precipitated solid was collected by filtration and washed with water to obtain Exemplified Compound A-5 (12.5 parts by mass) in a yield of 66% (m.p. 265-267 ° C).

¹ H NMR (300MHz, DMSO-d ₆ ) δ1.7-1.8 (m, 2H), 2.2-2.3 (m, 2H), 2.3-2.4 (m, 2H), 8.0 (d, 1H), 9.0 (s , 1H), 10.8 (brs, 1H), 11.4 (s, 1H), 12.0 (brs, 1H).

<Example 2-1-1>

C.I. Pigment Red 254 (45 parts by mass) and Example Compound A-1 (4.5 parts by mass) were added to dimethyl sulfoxide (DMSO) (953 parts by mass) and stirred. 28 mass% sodium methoxymethanol solution (30 volume parts) was added to this solution, and the pigment solution A-2 was prepared. On the other hand, water (4000 mass parts) was prepared as the pigment insoluble solvent B.

Nippon Seimitsu Kagaku Co., Ltd. The pigment solution A-2 was added to the pigment insoluble solvent B while stirring the pigment insoluble solvent B at 500 rpm with GK-0222-10 type Ramond Stara (trade name) manufactured by Fujisawa Seiyaku Co., Ltd. at 30 ° C. It injected | poured at the flow rate of 100 mL / min by the NP-KX-500 type large-capacity no-flow pump (brand name) made from Corporation, and crystallized the organic pigment nanoparticle, and obtained the aqueous organic nano aqueous dispersion. The particle diameter of this pigment dispersion liquid was measured using the nano track UPA-EX150 by Nikkiso.

As a result of measuring the pH of this pigment dispersion liquid by pH test paper (made by ADVANTEC company), it was 12 and neutralized by adding concentrated hydrochloric acid until pH became 3. The generated aggregates were observed by an optical microscope.

The aggregates were collected by filtration with filter paper (ADVANTEC Co., No. 2), and the time required for filtration at this time was measured. The organic nano pigment collected by filtration was washed with water (300 parts by mass).

A solution obtained by adding 80 parts by mass of a non-aqueous dispersant C-1 (the above-described high molecular compound C-1) to 300 parts by mass of ethyl lactate was added to the pigment nanoparticle concentrate paste, followed by stirring at 1500 rpm for 60 minutes by a dissolver. 25 mass parts of ethyl acetate were added, and also it stirred for 500 rpm and 10 minutes by the resolver, and obtained pigment nanoparticle lactic-acid ethyl dispersion A-2. The organic pigment powder A-2 of the present invention was obtained by solvent removal of the said pigment nanoparticle lactic acid ethyl dispersion A-2 by the evaporator.

Pigment dispersion composition A-2 of the following composition was prepared using said organic pigment powder A-2.

1 mass part of said organic pigment powder A-2

4 parts by mass of 1-methoxy-2-propyl acetate

The pigment dispersion composition A of the above composition was dispersed at a circumferential speed of 9 m / s for 1 hour using a motor mill M-50 (manufactured by Eiger Japan) using zirconia beads having a diameter of 0.65 mm, thereby dispersing the pigment dispersion composition A-2 of the organic pigment nanoparticles. Got it.

The obtained pigment dispersion composition was evaluated in the same manner as in Example 1-1-1. The results are shown in Table 7.

<Example 2-1-2>

Instead of the non-aqueous dispersant C-1 of Example 2-1-1, the same operation as in Example 2-1-1 was carried out using the following non-aqueous dispersant C-9 (the above-described polymer compound C-9). The obtained organic nanoparticle non-aqueous dispersion is also called pigment dispersion composition B-2. Table 7 shows the results of the same evaluation tests as in Example 2-1-1 on Pigment Dispersion Composition B-2.

<Example 2-1-3>

At the time of addition of the above-described compound A-1 of Example 2-1-2, polyvinylpyrrolidone (K-25, trade name, manufactured by Wako Pure Chemical Industries, Ltd., 90 parts by mass) was also added together and Example 2-1-1 The same operation was performed. The obtained organic nanoparticle non-aqueous dispersion is also called pigment dispersion composition C-2. Table 7 shows the results of the same evaluation tests as in Example 2-1-1 on the pigment dispersion composition C-2.

<Example 2-1-4>

The same operation as in Example 2-1-1 was carried out using A-4 instead of the above-mentioned Compound A-1 of Example 2-1-1. The obtained organic nanoparticle non-aqueous dispersion is also called pigment dispersion composition D-2. The result of having performed the evaluation test similar to Example 2-1-1 about pigment dispersion composition D-2 is shown in Table 7.

<Comparative Example 2-1-1>

Polyvinylpyrrolidone (K-25, brand name, Wako Pure Chemical Industries, Ltd., 90 mass parts) is added instead of the said exemplary compound A-1 of Example 2-1-1, and it replaces the said exemplary high molecular compound C-1 The same operation as in Example 2-1-1 was carried out except that the methacrylic acid / methacrylic acid benzyl copolymer was used. However, the isolation was carried out by a filter (H010A 047A, brand name, manufactured by Adovantech Co., Ltd.) because the pigment leaked on the filter paper (filter paper No. 2 (trade name) manufactured by Adovantech Co., Ltd.).

The obtained organic nanoparticle non-aqueous dispersion is also called pigment dispersion composition E-2. Table 7 shows the results of the same evaluation tests as in Example 2-1-1 on Pigment Dispersion Composition E-2.

<Comparative Example 2-1-2>

By the same operation as in Example 2-1-1, an aqueous pigment dispersion was prepared, isolated without performing a pH operation, and the filtration time was evaluated. The results are shown in Table 7. As a result of filtration with filter paper {filter paper No. 2 (brand name) made by Adovantech Co., Ltd.), since a pigment leaked out, it filtered with a filter (H010A047A, brand name by Adovantech Co., Ltd.), and disperse composition F-2. Prepared.

As shown in Table 7, according to the acidic dispersing aid of the present invention, high contrast is realized in the non-aqueous dispersion in which the fine particles are aggregated once in the aqueous dispersion, the medium is switched and redispersed with an organic solvent, and the filterability is achieved. It can be seen that this very good significantly reduces the isolation time and significantly improves the characteristics and productivity of the desired dispersion and color filter.

<Example 2-2>

A colored photosensitive resin composition and the color filter were produced like Example 1-2 except the following points.

The following were used as R pigment dispersion.

<R Pigment Dispersion 1>

Pigment Dispersion Composition A-2

Polymer (benzyl methacrylate / methacrylic acid = 72/28 molar ratio

                     Of random copolymer, molecular weight 30,000) 15 parts by mass

Propylene glycol monomethyl ether acetate 62.5 parts by mass

In addition, CF blue EX3383 by Mikunishikiso Corporation was used as a V pigment dispersion in the composition of Table 5.

Color filter A-2 was produced as mentioned above. Except substituting pigment dispersion composition A-2 used as R pigment dispersion 1 by color filter A-2 with B-2 to E-2, respectively, color filter B-2 to the same operation as color filter A-2. E-2 was produced.

Table 8 shows the results of measuring the contrast in the same manner as the above-described contrast measurement for each color filter.

From the said result, all the color filters of this invention were high contrast and were favorable color filters.

<Example 2-3>

Except using the color filters A-2 to E-2, the liquid crystal display device was produced like Example 1-3, and the display characteristic was evaluated.

About the liquid crystal display device using the color filter of the comparative example It was confirmed that the liquid crystal display device using the color filter of this invention was excellent in black clarity and red delineation power, and showed favorable display characteristics.

Claims (22)

It is represented by following General formula (1-1) or (1-2).

In formula (1-1), A represents a heterocyclic group bonded by a linking group and a nitrogen atom. X represents a divalent linking group having at least 2 to 20 carbon atoms. R ₁ and R ₂ each independently represent a hydrogen atom, an alkyl group, an aralkyl group or an aryl group. R ₁ and R ₂ may be connected to each other or may form a heterocycle further containing an oxygen atom, a nitrogen atom and / or a sulfur atom. m represents a natural number of 1 or 2.

In formula (1-2), A ¹¹ represents a heterocyclic group which is linked to a carbonyl group by a nitrogen atom. X ¹¹ represents a divalent alkylene group, ether group or polyether group having 2 to 10 carbon atoms which may have a substituent.} The dispersion aid according to claim 1, which is a basic dispersion aid represented by the general formula (1-1). The dispersion assistant according to claim 2, wherein the basic dispersion assistant is represented by the following General Formula (2-1).

(Wherein A represents a heterocyclic group bonded by a linking group and a nitrogen atom. Y represents an oxygen atom or a sulfur atom. L represents an integer of 0 or 1. n represents a natural number of 1 to 19. R ₁ and R ₂ each independently represent a hydrogen atom, an alkyl group, an aralkyl group or an aryl group, and R ₁ and R ₂ may be connected to each other to form a heterocycle further containing an oxygen atom, a nitrogen atom and / or a sulfur atom M may represent a natural number of 1 or 2.) The dispersing aid according to claim 2 or 3, wherein the dispersibility is imparted to the organic pigment nanoparticles together with the non-aqueous dispersant in the non-aqueous dispersion obtained by switching the medium from the aqueous dispersion. An aqueous dispersion containing organic pigment nanoparticles and water and the basic dispersion aid according to any one of claims 2 to 4, wherein the organic pigment nanoparticles contain an organic pigment solution in which an organic pigment is dissolved in a good solvent. An aqueous dispersion of organic pigment nanoparticles, which is compatible with a good solvent and mixed with a poor solvent for the organic pigment, and the organic pigment is precipitated as fine particles of nanometer size in the presence of the basic dispersing aid. . The aqueous dispersion of organic pigment nanoparticles according to claim 5, wherein the average particle diameter of the primary particles of the organic pigment nanoparticles is 10 to 500 nm. The aggregate of organic pigment nanoparticles characterized by changing the pH of the aqueous dispersion according to claim 5 or 6 to bring the organic pigment nanoparticles into redispersed state. A non-aqueous dispersion of organic pigment nanoparticles, wherein the aggregates of the aggregates according to claim 7 are released and redispersed in a non-aqueous medium. The non-aqueous dispersion of organic pigment nanoparticles according to claim 8, wherein the non-aqueous dispersion of organic pigment nanoparticles is characterized by containing at least one polymer compound having a number average molecular weight of 1000 or more having an acidic group. The non-aqueous dispersion of Claim 8 or 9, the binder, the monomer or oligomer, and the photoinitiator or the photoinitiator system are contained at least. The coloring photosensitive resin composition characterized by the above-mentioned. It produced using the coloring photosensitive resin composition of Claim 10, The color filter characterized by the above-mentioned. The color filter of Claim 11 was provided. The liquid crystal display device characterized by the above-mentioned. The dispersion aid according to claim 1, which is an acid dispersion aid represented by the general formula (1-2). The dispersing aid according to claim 13, wherein the dispersibility is imparted to the organic pigment nanoparticle together with the non-aqueous dispersant in the non-aqueous dispersion obtained by switching the medium from the aqueous dispersion. An aqueous dispersion containing organic pigment nanoparticles and water and the acidic dispersing aid according to claim 13, wherein the organic pigment nanoparticles are compatible with the organic solvent and an organic pigment solution in which an organic pigment is dissolved in a good solvent. An aqueous dispersion of organic pigment nanoparticles, wherein the poor solvent for the pigment is mixed and the organic pigment is precipitated as fine particles of nanometer size in the presence of the acidic dispersion aid. The aqueous dispersion of organic pigment nanoparticles according to claim 15, wherein the average particle diameter of the primary particles of the organic pigment nanoparticles is 10 to 500 nm. The aggregate of organic pigment nanoparticles characterized by changing the pH of the aqueous dispersion according to claim 15 or 16 to bring the organic pigment nanoparticles into redispersed state. A non-aqueous dispersion of organic pigment nanoparticles, wherein the aggregates of the aggregates according to claim 17 are released and redispersed in a non-aqueous medium. 19. The non-aqueous dispersion of organic pigment particles according to claim 18, which contains at least one polymer compound having a number average molecular weight of 1000 or more. The non-aqueous dispersion of Claim 18 or 19, the binder, the monomer or oligomer, and the photoinitiator or the photoinitiator system are contained at least. The coloring photosensitive resin composition characterized by the above-mentioned. It produced using the coloring photosensitive resin composition of Claim 20, The color filter characterized by the above-mentioned. The color filter of Claim 21 was provided. The liquid crystal display device characterized by the above-mentioned.