JP5315608B2 - Pigment dispersion and colored resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a pigment dispersion, which can sufficiently achieve an effect of dispersion stabilization of ultrafine pigment particles by using an aqueous suspension of a pigment derivative, and which has pigment particles being dispersed in a stable and low viscous state, and also a method for producing the pigment dispersion. <P>SOLUTION: The pigment dispersion comprises an organic pigment, a pigment derivative, a water-insoluble resin, and a water-insoluble solvent. The pigment dispersion can be obtained by mixing an aqueous suspension containing the organic pigment, an aqueous suspension of the pigment derivative, and a resin solution in which the water-insoluble resin is dissolved in the water-insoluble solvent, and then flushing the resultant mixture. <P>COPYRIGHT: (C)2007,JPO&amp;INPIT

Description

The present invention relates to a colored resin composition for color filter.

    Various color material materials using a colored resin composition of an organic pigment are widely used in various fields as industrial color materials for printing, resin compositions, automotive paints, electronics, and the like. In recent years, there has been an increasing demand for color materials that achieves both higher quality in coloring effects such as coloring power, transparency, and hue, and improved handling properties such as low viscosity and high fluidity. Furthermore, in addition to these requirements, it is desired that the pigment dispersion has a high versatility and a multi-purpose property that also satisfies the physical properties of a product using a color material.

  The pigment dispersion is used as an optical material, for example, as a resist coloring resin composition in a color filter for liquid crystal display. In recent years, resist-colored resin compositions have been further improved in color filters such as coloring power, transparency, hue, contrast, and brightness, improved handling properties such as low viscosity and high fluidity, and storage stability such as quality. There is an increasing demand for improvement. Further, in addition to these requirements, it is desired that the resist coloring resin composition has physical properties, that is, characteristics that satisfy alkali developability, development speed, and the like. Currently, as a method for producing a resist colored resin composition, a pigment dispersion obtained by a method called a pigment dispersion method using a pigment having excellent light resistance and heat resistance as a colorant has various target physical properties such as a photosensitive resin. It is obtained by adding a filling additive. Therefore, it is considered that various physical properties of the resist colored resin composition are greatly affected by the physical properties of the pigment dispersion.

  In order to obtain the target color and quality on the color filter obtained by the resist-colored resin composition, the coating film formed by the resist-colored resin composition to be applied must be adjusted to the target thickness. In general, as a method for uniformly applying a dispersion of a pigment in a transparent resin solution to a transparent substrate such as glass, a method using a spin coater is generally used. In order to form a coating film having a desired thickness using this method, it is important to control the viscosity of the resist-colored resin composition to be applied. However, current pigment dispersions often vary in viscosity after storage depending on the conditions such as different types of resist coloring resin composition additives used. Therefore, it is necessary to carry out an operation for examining the coating conditions in accordance with the viscosity at the time of the coating operation, which is a great problem as a productivity and as a product. Therefore, for the purpose of preventing viscosity variation after storage, it is necessary to prepare a pigment dispersion that matches the conditions of the resist additive according to the type of additive, which is a big problem in terms of productivity and profitability. Yes.

  Generally, a pigment dispersion is obtained by dispersing fine pigment particles in a colorant carrier such as varnish. As a method of further improving the quality of coloring effects such as coloring power, transparency and hue in recent years, there is a method of obtaining pigment particles having a further refined primary particle size in a state of being uniformly dispersed in the vicinity of the primary particle size. Are listed. However, it is difficult to obtain pigment particles in a stably dispersed state, and the viscosity often increases with time and fluidity is lost. Furthermore, the viscosity of the dispersion tends to increase as the primary particle size of the pigment decreases. Moreover, it is requested | required that the physical property of the product using a pigment dispersion should be satisfy | filled, and it exists in the tendency which cannot increase a colorant carrier easily. That is, it has become extremely difficult to obtain a pigment dispersion that simultaneously satisfies the improvement in quality, the reduction in viscosity, and the high versatility.

  Conventionally, such a pigment dispersion is generally produced by the following method. A method in which a dry powder of a pigment having a fine primary particle size is premixed with a predetermined organic medium and dispersed using a disperser such as a sand mill or a three-roll mill, and a predetermined resin is dispersed in the organic medium. After using it to make a chip, dissolve it in an organic solvent and disperse it with a disperser, etc., mix an aqueous suspension of organic pigment with an oily varnish or water-insoluble resin, and flush it to change the pigment from an aqueous phase to an oily phase. An example is a method of dispersing a processed pigment composition obtained by drying after phase inversion with a disperser or the like.

  Among these methods, in the method using a dry powdered pigment, the pigment is strongly agglomerated during the drying process, and in order to return to the primary particles by the dispersion treatment, it is necessary to use a high amount together with an organic medium such as a resin and a solvent. A long dispersion process with energy applied is required. Furthermore, the aggregation of the pigment powder of very fine primary particles is much stronger than before, and the dispersion process requires more energy and time than before, and the primary particles of the pigment are destroyed by this excessive dispersion treatment process. However, there is a problem that it is difficult to obtain a low-viscosity pigment dispersion because the particle size distribution becomes wide as measured by a wet particle size distribution diameter, and the broken pigment particles cause a further increase in viscosity.

  As a method of obtaining a pigment dispersion that is uniformly dispersed in the vicinity of the primary particle diameter using a dry powdered pigment while suppressing the destruction of the primary particles, a method of performing a dispersion treatment with a sand mill filled with a minute medium has been proposed. ing. However, this is difficult to use from the viewpoint of productivity, such as that the dispersion processing time is remarkably longer than the conventional method, the medium is very small, and handling such as replacement and washing is difficult.

  In the method by flushing, an aqueous suspension of a pigment such as a wet cake pigment is flushed with a varnish or the like used for printing ink, and the pigment is phase-inverted from an aqueous phase to an oil phase. Thereby, since the pigment is included and dispersed with a dispersion stabilizer such as a resin in a finely dispersed state, a processed pigment with weak aggregation can be obtained without causing strong aggregation in the drying step. By further dispersing this in an organic medium, a colored resin composition in which the pigment is dispersed in the vicinity of the primary particle diameter can be produced.

  However, the conventional methods (for example, Patent Documents 1 to 3) use an aqueous suspension of a pigment to be used or a low concentration of pigment in an aqueous suspension, resulting in poor productivity. There are various problems such as the point that physical properties as industrial color materials later deteriorate, and the amount of water in the resulting pigment dispersion is difficult to use later. It was not satisfactory in terms of quality. In addition, in conventional flushing, pigment particles are crystal-grown because a resin (varnish) dissolved in a solvent is used without using a pigment derivative. For this reason, there is a problem that the effect of using fine particles cannot be obtained. Since Patent Document 1, Patent Document 2, and Patent Document 3 use a resin (varnish) dissolved in a solvent without using a pigment derivative, a direction for improving quality in recent years using extremely fine pigment particles. It was difficult to say that it was a method that satisfactorily satisfied the sex.

  Furthermore, Patent Document 4 is cited as a method of using a resin without dissolving it in a solvent. However, in this method, the usable resin is limited by the molecular weight or the viscosity, so that the versatility of the obtained processed pigment is extremely inferior and the practicality is poor.

Examples of the method using a dye derivative and a resin dissolved in a solvent include the methods of Patent Document 5 and Patent Document 6. However, in either method, a method of adding the pigment derivative in an aqueous suspension is not mentioned. That is, it is difficult to obtain a sufficient effect of the dye derivative on a pigment in an aqueous suspension in a fine state with little dry aggregation. For this reason, there has been a problem that it is difficult to obtain a sufficiently stable dispersion state with respect to the direction in which pigment particles are extremely finely dispersed in order to improve the quality in recent years.
JP-A-63-43960 Japanese Patent Publication No. 5-69147 Japanese Patent Application Laid-Open No. 11-100541 JP 2003-41179 A Japanese Patent Publication No. 6-45761 JP 2004-35655 A

The present invention has been made in view of such problems, and by using an aqueous suspension of a dye derivative, it is possible to obtain a sufficient dispersion stabilization effect for extremely fine pigment particles, An object of the present invention is to provide a colored resin composition for a color filter in which pigment particles are stably dispersed with a low viscosity and a method for producing the same.

The present invention provides an aqueous suspension containing an organic pigment, an aqueous suspension of a pigment derivative, and a resin solution obtained by dissolving a water-insoluble resin in a water-insoluble solvent, and flushing from water. A pigment dispersion produced by the method is dispersed using chromium, titanium, stainless steel, steel, sodaless hard glass, silicon nitride, alumina or zirconia beads having a diameter of 1.5 mmφ or less in the dispersion step. The present invention relates to a method for producing a colored resin composition for a filter.

Moreover, this invention relates to the colored resin composition for color filters manufactured by the said manufacturing method.

  The present invention also relates to the above colored resin composition, wherein the residual water content is 0.5% by weight or more and 3.0% by weight or less of the entire colored resin composition.

  As an effect of the present invention, a pigment having a high degree of freedom in selecting a water-insoluble resin, in which an extremely fine pigment is stably dispersed with a low viscosity without crystal growth of pigment particles after phase inversion from an aqueous phase to an oil phase. A dispersion can be provided efficiently. Furthermore, since the viscosity is low, a base ink having a high pigment concentration can be produced. Further, the outflow of the pigment and the dye derivative into the waste water during the flushing can be made extremely small. Further, the obtained pigment dispersion is dispersed with chromium, titanium, stainless steel, steel, sodaless hard glass, silicon nitride, alumina, or zirconia beads having a diameter of 1.5 mmφ or less to provide a colored resin composition of any desired purpose. be able to.

First, the pigment dispersion in the present invention will be described. Pigment dispersions, organic pigment, pigment derivative include a non-water-soluble resin and a water-insoluble solvent, an aqueous suspension containing an organic pigment, an aqueous suspension containing a dye derivative, a water-insoluble resin partially It can be obtained by mixing a resin solution dissolved in a water-soluble solvent and flushing a mixture of an organic pigment, a dye derivative, a water-insoluble resin and a water-insoluble solvent from water.

  Examples of the aqueous suspension containing the organic pigment used in the present invention include an unpurified aqueous suspension after synthesis of the organic pigment, a wet cake pigment obtained by once filtering and washing the unpurified aqueous suspension, and wet A cake pigment further pressed and dehydrated to an arbitrary solid content concentration and / or a wet cake pigment added with water to form an aqueous suspension again can be used.

  In addition, a surface treatment agent, a surfactant, a dispersant, a pigment derivative, and the like for making the pigment into fine particles at the time of synthesis may be added to the aqueous suspension of the organic pigment. In addition, an aqueous suspension after washing by applying an acid pasting method, a solvent salt milling method, or the like to the pigment once dried and powdered after synthesis can be used.

  As for the particle diameter of the organic pigment in the aqueous suspension, the average primary particle diameter is 1.0 μm or less. Preferably it is 0.5 micrometer or less. More preferably, it is 0.1 μm or less. If it exceeds 1.0 μm, a sufficient coloring effect cannot be obtained with coloring power, transparency, hue, contrast and the like. The primary particle diameter of the organic pigment can be controlled within an appropriate range using a known dispersing apparatus such as a bead mill, a sand mill, a kneader, or a roll mill. The average primary particle diameter means the diameter of the smallest unit pigment particle, and is measured with an electron microscope (for example, an electron microscope is measured with a transmission electron microscope JEM-1010 (manufactured by JEOL Ltd.) at an acceleration voltage of 100 kV). The The concentration of the pigment in the aqueous suspension containing the organic pigment varies depending on the type of pigment, but generally is a resin obtained by dissolving a water-insoluble resin in a water-insoluble solvent if it is more than 10% by weight and 80% by weight or less. By treating with a solution, the pigment can be phase-inverted from the aqueous phase to the oil phase. More preferably, the concentration of the pigment solid content of the aqueous suspension containing the organic pigment is 15% by weight or more and 70% by weight or less. This range is based on the amount of water that can effectively phase invert the pigment from the aqueous phase to the oil phase.

  Examples of organic pigments include dyed lake pigments such as triallylmethane and xanthene, azo pigments such as soluble azo pigments, insoluble azo pigments and condensed azo pigments, phthalocyanine pigments, and condensed polycyclic pigments. As an organic pigment, a well-known pigment can be used individually or in mixture of 2 or more types. Below, the specific example of the organic pigment which can be used for manufacture of a coloring composition is shown with a color index number.

  In the case of forming a red coloring composition, for example, C.I. I. Pigment Red 4, 7, 9, 14, 41, 48: 1, 48: 2, 48: 3, 48: 4, 81: 1, 81: 2, 81: 3, 97, 112, 122, 123, 146, 149, 168, 177, 178, 180, 184, 185, 187, 192, 200, 202, 208, 210, 215, 216, 217, 220, 223, 224, 226, 227, 228, 242, 240, 246, 254, 255, 264, 272 etc. and C.I. I. Pigment Violet 19 red pigment can be used. Moreover, a yellow pigment and an orange pigment can be used in combination with the red pigment dispersion.

  In the case of forming a yellow pigment dispersion, for example, C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 20, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 111, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 1 Yellow pigments such as 74, 175, 176, 177, 179, 180, 181, 182, 184, 185, 187, 188, 193, 194, 199 can be used.

  In the case of forming an orange pigment dispersion, for example, C.I. I. Orange pigments such as Pigment Orange 16, 36, 38, 43, 51, 55, 59, 61, 71, 73 can be used.

  In the case of forming a green pigment dispersion, for example, C.I. I. Green pigments such as Pigment Green 7, 10, 36, and 37 can be used. A yellow pigment can be used in combination with the green pigment dispersion.

  In the case of forming a blue pigment dispersion, for example, C.I. I. Blue pigments such as Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, and 64 can be used. Blue pigment dispersions include C.I. I. Pigment Violet 1, 19, 23, 27, 29, 30, 32, 37, 40, 42, 50, and other purple pigments can be used in combination.

  In the case of forming a cyan pigment dispersion, for example, C.I. I. Blue pigments such as Pigment Blue 15, 15: 1, 15: 2, 15: 4, 15: 3, 15: 6, 16, 60, and 81 can be used.

  When forming a magenta color pigment dispersion, for example, C.I. I. Pigment Violet 1, 19, C.I. I. Purple pigments such as Pigment Red 81, 122, 144, 146, 177, 169, 202, 208, 209 and red pigments can be used. A yellow pigment can be used in combination with the magenta pigment dispersion.

  The pigment derivative used in the present invention includes an unpurified aqueous suspension after synthesis of the pigment derivative, a wet cake obtained by once filtering and washing the unpurified aqueous suspension, and drying after filtration and washing. Or those obtained by further pulverizing them can be used. More preferably, an aqueous suspension containing a pigment derivative is preferable.

  Examples of the aqueous suspension containing the pigment derivative include an unpurified aqueous suspension, a wet cake obtained by once filtering and washing the unpurified aqueous suspension, or by further pressing the wet cake to obtain any solid content. Dehydrated to a concentration and / or a wet cake added with water again can be used.

  As the dye derivative, those having an acidic or neutral substituent and those having a basic substituent can be used. In using the dye derivative, it is possible to neutralize part or all of the basic derivative with the basic component and the acidic derivative to the basic derivative. The concentration of the pigment derivative in the aqueous suspension containing the pigment derivative varies depending on the type of the pigment derivative, but is generally 3% by weight or more and 80% by weight or less. The pigment derivative can be phase-shifted from the aqueous phase to the oil phase by treating with a resin solution dissolved in the aqueous solution. Preferably, the concentration of the pigment derivative in the aqueous suspension containing the pigment derivative is 5% by weight or more and 50% by weight or less. This range is based on the amount of water that can efficiently phase-invert the pigment derivative from the aqueous phase to the oil phase.

  A pigment derivative is a compound in which a substituent is introduced into an organic pigment. Organic dyes include light yellow aromatic polycyclic compounds such as phthalimide, naphthalene, naphthoquinone, anthracene, and anthraquinone that are not generally called dyes. Examples of the dye derivative include JP-A 63-305173, JP-B 57-15620, JP-B 59-40172, JP-B 63-17102, JP-B 5-9469, JP-A 06-06. What is described in 306301 gazette, Unexamined-Japanese-Patent No. 2001-220520, Unexamined-Japanese-Patent No. 2003-238842 etc. can be used, These can be used individually or in mixture of 2 or more types. In particular, a pigment derivative having a basic group or a triazine derivative having a basic group is preferably used because of a large pigment dispersion effect.

  Specific examples of the basic group possessed by the dye derivative include substituents represented by the following general formulas (1), (2), (3), (4) and (5).

Formula (1)

Formula (2)

Formula (3)

Formula (4)

Formula (5)

(Where
X: represents —SO ₂ —, —CO—, —CH ₂ NHCOCH ₂ —, —CH ₂ — or a direct bond.
n represents an integer of 1 to 10.

R ₁ and R ₂ : each independently an alkyl group which may be substituted, an alkenyl group which may be substituted, a phenyl group which may be substituted, or a combination of R ₁ and R ₂ Represents an optionally substituted heterocycle containing a nitrogen, oxygen or sulfur atom. As for carbon number of an alkyl group and an alkenyl group, 1-10 are preferable.

R ₃ : represents an optionally substituted alkyl group, an optionally substituted alkenyl group or an optionally substituted phenyl group. As for carbon number of an alkyl group and an alkenyl group, 1-10 are preferable.

R ₄ , R ₅ , R ₆ , R ₇ : each independently represents a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group or an optionally substituted phenyl group. As for carbon number of an alkyl group and an alkenyl group, 1-5 are preferable.

Y: represents —NR ₈ —Z—NR ₉ — or a direct bond.

R ₈ and R ₉ each independently represents a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group or an optionally substituted phenyl group. As for carbon number of an alkyl group and an alkenyl group, 1-5 are preferable.

  Z: represents an alkylene group that may be substituted, an alkenylene group that may be substituted, or a phenylene group that may be substituted. As for carbon number of an alkyl group and an alkenyl group, 1-8 are preferable.

P: The substituent shown by Formula (6) or the substituent shown by Formula (7) is represented.
Q: A hydroxyl group, an alkoxyl group, a substituent represented by the formula (6) or a substituent represented by the formula (7).

Formula (6)

Formula (7)

(Where
X _{1 is, -NR'SO 2 -, - SO 2} NR '-, - CONR'- or represents a group selected from _{-CH 2} NR'COCH 2 NR'-,
X ₂ represents a group selected from an arylene group having 20 carbon atoms or less or an optionally substituted arylene group having 20 or less carbon atoms, or a heteroaromatic ring having 20 or less carbon atoms (these groups are , —NR′—, —O—, —SO ₂ — or —CO— may be bonded to each other via a divalent linking group).
X ₃ represents -NR'-,
(R ′ may have a hydrogen atom, an optionally substituted alkyl group having 20 or less carbon atoms, an optionally substituted group, an alkenyl group having 20 or less carbon atoms, or a substituted group. Or an aryl group having 20 or less carbon atoms).
A represents a group represented by the following formula (8) or (9) or —O— (CH ₂ ) n 1 —R ₁₀ (R ₁₀ represents an optionally substituted nitrogen-containing heterocyclic residue, and n 1 represents Represents an integer of 0 to 20, and represents a group selected from
B is a group represented by the following formula (8) or (9): —O— (CH ₂ ) n 1 —R ₁₀ , —OR ₁₁ , —NR ₁₂ R ₁₃ , —Cl, —F or —X ₃ —. Represents a group selected from X ₂ -X ₁ -Q ₁ (R ₁₁ , R ₁₂ and R ₁₃ each independently represents a hydrogen atom, a substituent which may have an alkyl group having 20 or less carbon atoms, and a substituent; And an alkenyl group having 20 or less carbon atoms or an aryl group having 20 or less carbon atoms, and Q1 represents a quinophthalone residue.
t represents an integer of 1 to 3. )
Formula (8)

（式中、Ｙ_１は−ＮＲ’−または−Ｏ−を表し、Ｙ_２は、置換基を有していてもよく炭素数が２０以下のアルキレン基、置換基を有していてもよく炭素数が２０以下のアルキニレン基または置換基を有していてもよく炭素数が２０以下のアリーレン基から選ばれる基を表し（これらの基は、−ＮＲ’−、−Ｏ−、−ＳＯ_２−または−ＣＯ−から選ばれる２価の連結基で相互に結合されていてもよい。）、
Ｒ₁₄およびＲ₁₅は、それぞれ独立に、置換基を有していてもよく炭素数が２０以下のアルキル基または置換基を有していてもよく炭素数が２０以下のアルケニル基を表す（Ｒ₁₄とＲ₁₅が一体となって、更なる窒素原子、酸素原子または硫黄原子を含み置換されていてもよい複素環構造を形成してもよい。）。）
式（９）

(In the formula, Y ₁ represents —NR′— or —O—, and Y ₂ may have a substituent, an alkylene group having 20 or less carbon atoms, or an optionally substituted carbon. Represents a group selected from an alkynylene group having a number of 20 or less or an arylene group having a carbon number of 20 or less (these groups are —NR′—, —O—, —SO ₂ —). Or may be bonded to each other by a divalent linking group selected from -CO-).
R ₁₄ and R ₁₅ each independently have a substituent and may represent an alkyl group having 20 or less carbon atoms or an optionally substituted alkenyl group having 20 or less carbon atoms (R ₁₄ and R ₁₅ may be combined to form an optionally substituted heterocyclic structure containing a nitrogen, oxygen or sulfur atom. )
Formula (9)

（式中、Ｚ_１は、直接結合するか、−ＮＲ’−、−ＮＲ’−Ｇ−ＣＯ−、−ＮＲ’−Ｇ−ＣＯＮＲ"−、−ＮＲ’−Ｇ−ＳＯ_２−、−ＮＲ’−Ｇ−ＳＯ_２ＮＲ"−、−Ｏ−Ｇ−ＣＯ−、−Ｏ−Ｇ−ＣＯＮＲ’−、−Ｏ−Ｇ−ＳＯ_２−、または−Ｏ−Ｇ−ＳＯ_２ＮＲ’−を表し（Ｇは、置換基を有していてもよく炭素数が２０以下のアルキレン基、置換基を有していてもよく炭素数が２０以下のアルキニレン基または置換基を有していてもよく炭素数が２０以下のアリーレン基を表し、Ｒ"は、水素原子、置換基を有していてもよく炭素数が２０以下のアルキル基、置換基を有していてもよく炭素数が２０以下のアルケニル基または置換基を有していてもよく炭素数が２０以下のアリール基を表す。）、
Ｒ₁₆、Ｒ₁₇、Ｒ₁₈、Ｒ₁₉は、それぞれ独立に、水素原子、置換基を有していてもよく炭素数が２０以下のアルキル基、置換基を有していてもよく炭素数が２０以下のアルケニル基または置換基を有していてもよく炭素数が２０以下のアリール基を表し、
Ｒ₂₀は、置換基を有していてもよく炭素数が２０以下のアルキル基または置換基を有していてもよく炭素数が２０以下のアルケニル基を表す。）。

(Wherein either _{Z 1} is a direct bond, -NR '-, - NR'- G-CO -, - NR'-G-CONR "-, - NR'-G-SO 2 -, - NR' _{-G-SO 2 NR "-,} - O-G-CO -, - O-G-CONR '-, - O-G-SO 2 -, or _-O-G-SO 2 NR'- a represents (G May have a substituent, may have an alkylene group having 20 or less carbon atoms, may have a substituent, may have an alkynylene group having 20 or less carbon atoms, or may have a substituent. Represents an arylene group having 20 or less, and R ″ represents a hydrogen atom, an optionally substituted alkyl group having 20 or less carbon atoms, or an optionally substituted alkenyl group having 20 or less carbon atoms. Or an aryl group which may have a substituent and has 20 or less carbon atoms).
R ₁₆ , R ₁₇ , R ₁₈ , and R ₁₉ each independently have a hydrogen atom, a substituent, or an alkyl group having 20 or less carbon atoms or a substituent, and may have a carbon number. An alkenyl group having 20 or less or a substituent which may have an aryl group having 20 or less carbon atoms,
R ₂₀ represents an alkyl group having 20 or less carbon atoms which may have a substituent, or an alkenyl group having 20 or less carbon atoms which may have a substituent. ).

Examples of compounds that can form the structures of X ₁ , X ₂ , and X ₃ include, but are not limited to, the following examples. For example, 1,2-phenylenediamine, 1,3-phenylenediamine, 1,4-phenylenediamine, 2,5-diaminobenzenesulfonic acid, 1,5-diaminonaphthalene, 1,8-diaminonaphthalene, 2,4-diamino Pyrimidine, 4,5-diaminopyrimidine, 2,3-diaminopyridine, 2,5-diaminopyridine, 2,6-diaminopyridine, 3,4-diaminopyridine, 2,6-diaminopurine, 3,5-diamino- 1,2,4-triazole, acetoguanamine and the like can be mentioned.

  Examples of the compound that can form the structure represented by the formula (8) or the formula (9) include the following examples, but are not limited thereto. Examples of the amine component or alcohol component used to form the structure represented by the formula (8) include N, N-dimethylaminomethyl, N, N-dimethylaminoethyl, N, N-dimethylaminopropyl, N, N-dimethylaminoamyl, N, N-dimethylaminobutyl, N, N-diethylaminoethyl, N, N-diethylaminopropyl, N, N-diethylaminohexyl, N, N-diethylaminoethoxypropyl, N, N-diethylamino Butyl, N, N-diethylaminopentyl, N, N-dipropylaminobutyl, N, N-dibutylaminopropyl, N, N-dibutylaminoethyl, N, N-dibutylaminobutyl, N, N-diisobutylaminopentyl, N, N-methyl-laurylaminopropyl, N, N-ethyl-hexyl Minoethyl, N, N-distearylaminoethyl, N, N-dioleylaminoethyl, N, N-distearylaminobutyl amine or alcohol, or N-aminoethyl-4-pipecoline, N-aminoethylmorpholine, N -Aminoethylpiperidine, N-aminopropylpiperidine, N-aminopropyl-2-pipecoline, N-aminopropyl-4-pipecoline, N-aminopropylmorpholine, N-aminomethylpiperidine, or N-hydroxymethylpiperidine, N- Hydroxyethylpiperidine, N-hydroxypropylpiperidine, N-hydroxyethylpipecoline, N-hydroxypropylpipecoline, N-hydroxymethylpyrrolidine, N-hydroxybutylpyrrolidine, N-hydroxyethylmorpholine, N- Mud carboxybutyl morpholine and the like.

Examples of the amine component or alcohol component used to form the structure of formula (9) or —O— (CH ₂ ) n 1 —R ₁₀ include N-methylpiperazine, N-ethylpiperazine, N— Butyl piperazine, 1-amino-4-methylpiperazine, 1-amino-4-cyclopentylpiperazine, 1-cyclopentylpiperazine, N-methyl-3-piperidinemethanol, N-methyl-3-hydroxypiperidine, N-ethyl-3- Examples include hydroxypiperidine, N-methyl-4-piperidinol, N-methyl-2-hydroxyethylpyrrolidine and the like.

  Examples of the organic pigment constituting the dye derivative having a basic group include diketopyrrolopyrrole pigments, azo pigments such as azo, disazo, and polyazo, phthalocyanine pigments, diaminodianthraquinone, anthrapyrimidine, flavantrons, and ant Anthraquinone pigments such as anthrone, indanthrone, pyranthrone, violanthrone, quinacridone pigment, dioxazine pigment, perinone pigment, perylene pigment, thioindigo pigment, isoindoline pigment, isoindolinone pigment, quinophthalone pigment, sulphone Pigments, metal complex pigments, and the like. Moreover, the organic pigment used for the pigment dispersion mentioned above may be sufficient. Furthermore, organic dyes constituting dye derivatives having basic groups include light yellow aromatic polycyclic compounds such as phthalimide, naphthalene, naphthoquinone, anthracene, and anthraquinone that are not generally called dyes. It is. (Hereinafter, the organic pigment and the aromatic polycyclic compound are referred to as an organic pigment.) These organic pigments may have a substituent other than the aforementioned basic group.

  Triazines constituting triazine derivatives having basic groups are alkyl groups such as methyl and ethyl groups, amino groups or dimethylamino groups, alkylamino groups such as diethylamino groups and dibutylamino groups, nitro groups, hydroxyl groups and methoxy groups. Group, alkoxy group such as ethoxy group and butoxy group, halogen such as chlorine or methyl group, methoxy group, amino group, dimethylamino group, phenyl group which may be substituted with hydroxyl group, methyl group, ethyl group, methoxy group 1,3,5-triazine which may have a substituent such as phenylamino group which may be substituted with ethoxy group, amino group, dimethylamino group, diethylamino group, nitro group, hydroxyl group and the like.

The pigment derivative and isoindoline derivative having a basic group of the present invention can be synthesized by various synthetic routes. For example, after introducing a substituent represented by the following formula (10) to formula (13) into an organic pigment or isoindoline, it reacts with the substituent and is represented by formula (1) to formula (4). Amine components that form substituents such as N, N-dimethylaminopropylamine, N-methylpiperazine, diethylamine or 4- [4-hydroxy-6- [3- (dibutylamino) propylamino] -1,3 It can be obtained by reacting 5-triazin-2-ylamino] aniline or the like.
Formula (10) _-SO 2 Cl
Formula (11) -COCl
Equation ₍₁₂₎ -CH ₂ NHCOCH 2 Cl
Equation (13) _-CH 2 Cl

When the organic pigment is an azo pigment, a basic group is introduced by introducing a substituent represented by the general formulas (1) to (4) into a diazo component or a coupling component in advance and then performing a coupling reaction. It is also possible to produce an azo dye derivative having the same.
The triazine derivative having a basic group of the present invention can be synthesized by various synthetic routes. For example, starting from cyanuric chloride, an amine component that forms a substituent represented by the general formulas (1) to (4) on at least one chlorine of cyanuric chloride, such as N, N-dimethylaminopropylamine or N It is obtained by reacting methylpiperazine or the like and then reacting the remaining chlorine of cyanuric chloride with various amines or alcohols.

  Examples of the amine component used for forming the substituents represented by the general formulas (1) to (4) and (6) to (7) include dimethylamine, diethylamine, N, N-ethylisopropylamine. N, N-ethylpropylamine, N, N-methylbutylamine, N, N-methylisobutylamine, N, N-butylethylamine, N, N-tert-butylethylamine, diisopropylamine, dipropylamine, N, N -Sec-butylpropylamine, dibutylamine, di-sec-butylamine, diisobutylamine, N, N-isobutyl-sec-butylamine, diamylamine, diisoamylamine, dihexylamine, di (2-ethylhexyl) amine, dioctylamine N, N-methyloctadecylamine, didecylamine, Allylamine, N, N-ethyl-1,2-dimethylpropylamine, N, N-methylhexylamine, dioleylamine, distearylamine, N, N-dimethylaminomethylamine, N, N-dimethylaminoethylamine, N, N-dimethylaminoamylamine, N, N-dimethylaminobutylamine, N, N-diethylaminoethylamine, N, N-diethylaminopropylamine, N, N-diethylaminohexylamine, N, N-diethylaminobutylamine, N, N-diethylamino Pentylamine, N, N-dipropylaminobutylamine, N, N-dibutylaminopropylamine, N, N-dibutylaminoethylamine, N, N-dibutylaminobutylamine, N, N-diisobutylaminopentylamine, N, N- Methyl Laurylaminopropylamine, N, N-ethyl-hexylaminoethylamine, N, N-distearylaminoethylamine, N, N-dioleylaminoethylamine, N, N-distearylaminobutylamine, piperidine, 2-pipecholine, 3- Pipecoline, 4-Pipecoline, 2,4-Lupetidine, 2,6-Lupetidine, 3,5-Lupetidine, 3-Piperidinmethanol, Pipecolic acid, Isonipecotic acid, Methyl isonicopetinate, Ethyl isonicopetinate, 2-Piperidinethanol, Pyrrolidine, 3-hydroxypyrrolidine, N-aminoethylpiperidine, N-aminoethyl-4-pipecholine, N-aminoethylmorpholine, N-aminopropylpiperidine, N-aminopropyl-2-pipecoline, N-aminopropyl-4-pipe Examples thereof include choline, N-aminopropylmorpholine, N-methylpiperazine, N-butylpiperazine, N-methylhomopiperazine, 1-cyclopentylpiperazine, 1-amino-4-methylpiperazine, 1-cyclopentylpiperazine and the like.

  Examples of the acidic or neutral substituent include substituents represented by the following formula (14), formula (15), and formula (16).

Ｍ：水素原子、カルシウム原子、バリウム原子、ストロンチウム原子、マンガン原子、またはアルミニウム原子を表す。
ｌ：Ｍの価数 Formula (14)

M: represents a hydrogen atom, a calcium atom, a barium atom, a strontium atom, a manganese atom, or an aluminum atom.
l: Valency of M

Ｒ₂₁、Ｒ₂₂、Ｒ₂₃、Ｒ₂₄：水素原子または炭素数１〜３０のアルキル基を表す（ただし全てが水素原子である場合は除く）。 Formula (15)

R ₂₁ , R ₂₂ , R ₂₃ , R ₂₄ : each represents a hydrogen atom or an alkyl group having 1 to 30 carbon atoms (except when all are hydrogen atoms).

Ａ：水素原子、ハロゲン原子、−ＮＯ_２、−ＮＨ_２またはＳＯ_３Ｈを表す。
ｋ：１〜４の整数を表す。 Formula (16)

A: represents a hydrogen atom, a halogen atom, —NO ₂ , —NH ₂ or SO ₃ H.
k: represents an integer of 1 to 4.

  Examples of the dye residue constituting the acidic or neutral dye derivative include diketopyrrolopyrrole dyes, azo dyes such as azo, disazo, and polyazo, phthalocyanine dyes, diaminodianthraquinone, anthrapyrimidine, flavantrons, and antagonists. Anthraquinone dyes such as anthrone, indanthrone, pyranthrone, violanthrone, quinacridone dyes, dioxazine dyes, perinone dyes, perylene dyes, thioindigo dyes, isoindoline dyes, isoindolinone dyes, quinophthalone dyes, sulene Dyes, metal complex dyes, anthraquinone residues, triazine residues and the like. Moreover, the organic pigment used for the pigment dispersion mentioned above may be sufficient. Organic dyes constituting acidic or neutral dye derivatives include light yellow aromatic polycyclic compounds such as phthalimide, naphthalene, naphthoquinone, anthracene, and anthraquinone that are not generally called dyes. included. These dye residues or organic pigments may have a substituent other than the acidic group and neutral group described above.

  Moreover, as an anthraquinone derivative, the anthraquinone which has the said basic, acidic, or neutral substituent can be used. Triazine derivatives include alkyl groups such as methyl and ethyl groups, amino groups or dimethylamino groups, alkylamino groups such as diethylamino groups and dibutylamino groups, nitro or hydroxyl groups, methoxy groups, ethoxy groups, and butoxy groups. A phenyl group or a methyl group, an ethyl group, a methoxy group, an ethoxy group, an amino group, a dimethyl group, which may be substituted with an alkoxy group or a halogen such as chlorine or a methyl group, a methoxy group, an amino group, a dimethylamino group, a hydroxyl group, etc. 1,3,5-triazine which may have a substituent such as phenylamino group which may be substituted with amino group, diethylamino group, nitro group, hydroxyl group or the like, the above basic, acidic or neutral substitution A derivative into which a group has been introduced can be used.

  As the pigment derivative, the following can be used, but is not limited thereto. The pigment derivatives can be used alone or in admixture of two or more.

  The amount of the pigment derivative or the aqueous suspension containing the pigment derivative varies depending on the organic pigment, the water-insoluble resin or the water-insoluble solvent used, but is based on the solid content of the organic pigment in the aqueous suspension of the organic pigment. The solid content of the pigment derivative is 0.01% by weight to 50% by weight. More preferably, it is 0.5 to 40% by weight. This is determined by the phase inversion property of the pigment from the aqueous phase to the oil phase during the flushing treatment, the hue of the pigment dispersion, the viscosity stability, and the like.

  When using a pigment derivative or an aqueous suspension containing a pigment derivative, the pigment derivative or the aqueous suspension containing the pigment derivative is obtained by dissolving an aqueous suspension containing an organic pigment and a water-insoluble resin in a water-insoluble solvent. It can be included in an aqueous suspension containing an organic pigment at any state and time as long as it is before mixing with the resin solution. Examples include, but are not limited to, organic pigment synthesis, post-synthesis, post-synthesis salt milling, solvent salt milling, water washing, and reslurry. Moreover, what was agitated with a stirrer such as a kneader before flushing, what was previously kneaded in a stirrer / mixer for flushing, or the like can also be used. In these treatments, it is desirable that the organic pigment and the pigment derivative become uniform. When kneading an aqueous suspension containing an organic pigment and an aqueous suspension of a pigment derivative or an aqueous pigment suspension in advance with an agitator such as a kneader or an agitator / mixer that causes flushing before flushing, at room temperature (25 ° C.) Although it can be performed, it may be heated in a temperature range below the boiling point of water.

The water-insoluble resin of the Pigments dispersion can pigment dispersion is a resin which can satisfy the physical properties of interest. In addition, various resins used depending on the use of the pigment dispersion, or those having compatibility with these various resins, solvents and other additives and not impairing the physical properties of the obtained product may be used. it can. Furthermore, a resin that can be dissolved in a water-insoluble solvent described later can be used. As the water-insoluble resin, the acid value of the water-insoluble resin is preferably 0 or more and 300 or less (the number of mg of potassium hydroxide necessary for neutralizing the acid contained in 1 g of the sample). More preferably, it is 5 or more and 200 or less. Here, the water-insoluble resin refers to a resin that does not dissolve in water or a resin that dissolves in water at 30% by weight or less. The amount dissolved in water is preferably 25% by weight or less. When the amount exceeds 30% by weight, when water or a water-insoluble solvent having high solubility in water is used, the water-soluble solvent and water are dissolved in the mixed waste water and flow out, and sufficient phase inversion is performed. Absent.

  Specific examples of the water-insoluble resin include butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, polyurethane series Resin, phenol resin, polyester resin, acrylic resin, alkyd resin, styrene resin, polyamide resin, rubber resin, cyclized rubber, epoxy resin, celluloses, polybutadiene, polyethylene, polyimide resin, benzoguanamine resin, melamine resin, urea resin Rosin-modified phenolic resin, rosin-modified maleic acid resin, petroleum resin, ketone resin, natural resin, urethane resin, amino resin, nitrocellulose, cellulose acetate butyrate, etc. combination It can be used. Acrylic resin and polyester resin are preferably used. More preferably, an acrylic resin is used.

  A resin-type pigment dispersant can also be used as the water-insoluble resin. The resin-type pigment dispersant has a pigment affinity part that has the property of adsorbing to the pigment and a part that is compatible with the colorant carrier, and adsorbs to the pigment to stabilize the dispersion of the pigment into the colorant carrier. It works to do. Specific examples of resin-type pigment dispersants include polycarboxylic acid esters such as polyurethane and polyacrylate, unsaturated polyamides, polycarboxylic acids, polycarboxylic acid (partial) amine salts, polycarboxylic acid ammonium salts, and polycarboxylic acid alkylamines. Salts, polysiloxanes, long-chain polyaminoamide phosphates, hydroxyl group-containing polycarboxylic acid esters, their modified products, amides formed by the reaction of poly (lower alkyleneimines) with polyesters having free carboxyl groups, and the like Oil-based dispersants such as salts; vinyl-based copolymers having a carboxyl group, the vinyl copolymer containing (meth) acrylic acid, acrylic acid dimer, caprolactone adduct of (meth) acrylic acid, mono- ( (Meth) acryloyloxyalkyl succinate, mono- (meth) acryloyl Xyalkyl phthalate, mono- (meth) acryloyloxyalkyl maleate, mono- (meth) acryloyloxyalkyl hexahydrophthalate, mono- (meth) acryloyloxyalkyl trimellitate, mono- (meth) acryloyloxy Copolymer in which a carboxyl group-containing monomer selected from the group of alkyl pyromellitate and di- (meth) acryloyloxyalkyl pyromellitate is present as a constituent, (meth) acrylic acid-styrene copolymer , (Meth) acrylic acid- (meth) acrylic acid ester copolymers, styrene-maleic acid copolymers, water-soluble resins such as polyvinyl alcohol and polyvinylpyrrolidone, water-soluble polymer compounds, polyesters, modified polyacrylates, With ethylene oxide / propylene oxide Compound, phosphate ester-based and the like are used, it can be used alone or in admixture of two or more. Further, these resin-type pigment dispersants can be used by dissolving in a water-insoluble solvent described later. Furthermore, these resin-type pigment dispersants can be used simultaneously with the solution of the water-insoluble resin in the water-insoluble solvent, but often have the effect of increasing the water repellency of the pigment during flushing. If a solution of a water-insoluble resin in a water-insoluble solvent is applied before an aqueous suspension containing an organic pigment and a pigment derivative or an aqueous suspension of a pigment derivative, a better water-repellent effect or In many cases, a dispersion effect can be obtained.

  The water-insoluble resin may have crosslinking reactivity or a resin having a crosslinking functional group. Specifically, when isocyanate is used as a crosslinking agent, a resin having a functional group having active hydrogen, that is, a hydroxyl group, a carboxyl group, an amino group, or the like can be given. Moreover, when using an epoxy as a crosslinking agent, resin which has a carboxyl group, an amino group, a thiol group etc. is mentioned. Examples of the crosslinkable functional group include a hydroxyl group, a carboxyl group, a sulfonic acid group, a phosphoric acid group, and an alkoxyl group.

  In addition, examples of the crosslinkable functional group include radically crosslinkable ethylenically unsaturated double bonds, which can be cured using a heat-polymerizable initiator and an ultraviolet curable initiator, respectively. When an electron beam is used, it is possible to crosslink with a resin alone.

  As the resin having ultraviolet crosslinkability, the resins listed among the resins having radical crosslinkability can be used, but more preferably, the suppression of the oxygen inhibition effect at the time of polymerization crosslinking is relatively large. Then, it is more preferable in the present invention.

  The amount of the water-insoluble resin added to the aqueous suspension containing the organic pigment varies depending on the combination of the organic pigment, the dye derivative and the water-insoluble solvent, but the pigment content in the aqueous suspension containing the organic pigment is 100. The water-insoluble resin content of a resin solution obtained by dissolving a water-insoluble resin in a water-insoluble solvent is 1000 parts by weight or less with respect to parts by weight.

  As the water-insoluble solvent, a solvent that can satisfy the desired physical properties of the pigment dispersion can be selected. Moreover, what has compatibility with various resin used according to the use of a pigment dispersion, a solvent, and another additive, and does not impair the physical property of the product obtained can be selected. Furthermore, when forming the coating film using a pigment dispersion, what satisfy | fills the physical property of the coating film can be selected. Moreover, these water-insoluble solvents can be used by mixing two or more kinds. Preferred are ketone compounds, ester compounds, ether compounds and alkoxy ether compounds. Furthermore, a solvent that is azeotropic with water is more desirable. Here, the water-insoluble solvent refers to a solvent that does not dissolve in water or a solvent that dissolves in water at 25 ° C. in an amount of 30% by weight or less. The amount dissolved in water is preferably 25% by weight or less. When two or more solvents are mixed and used, the sum of the dissolved amounts of the mixed solvents may be 30% by weight or less based on the weight of water. Preferably it is 25 weight% or less. If it exceeds 30% by weight, the amount of water remaining in the pigment composition after phase inversion increases, and the subsequent drying process becomes longer.

  Specific examples of the solvent include ethyl cellosolve acetate, butyl cellosolve acetate, 1-methoxy-2-propyl acetate, diethylene glycol dimethyl ether, ethylbenzene, ethylene glycol diethyl ether, ethyl cellosolve, methyl-n-amyl ketone, toluene, methyl ethyl ketone, and acetic acid. Examples include ethyl, isopropyl alcohol, butanol, isobutyl ketone, and petroleum solvents. Further, 2-heptanone, 4-heptanone, cyclohexanone, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, isoamyl acetate, n-amyl acetate, methyl lactate, ethyl lactate, butyl lactate, propane lactate, ethyl amyl Ketone, methyl isobutyl ketone, n-butyl alcohol, ethylene glycol monoethyl ether, ethylene glycol diethyl ether, ethylene glycol monomethyl ether, ethylene glycol monopropyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether Acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol Nopropyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate N, N-dimethylformamide, 1,2,3-trichloropropane, o-chlorotoluene, o- Xylene, m-xylene, 3-methoxy-3-methyl-1-butanol, 1,3-butanediol, 3-methyl-1,3-butanediol, 2-methyl-1,3-propanediol, diisobutyl ketone, Isophorone, methylcyclohexanone, acetophenone, ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, ethylene glycol monobutyl ether acetate Ethylene glycol dibutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, diethylene glycol monoisopropyl ether, propylene glycol monobutyl ether, propylene glycol diacetate, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono Propyl ether, dipropylene glycol dimethyl ether, tripropylene glycol monomethyl ether, ethyl 3-ethoxypropionate, 3-methoxybutyl acetate, 3-methoxy-3-methylbutyl acetate, γ-butyrolactone, N, N-dimethylacetamide, N- Methylpyrrolidone, p- Rorotoruen, o- diethylbenzene, m- diethylbenzene, p- diethylbenzene, o- dichlorobenzene, m- dichlorobenzene, n- butylbenzene, sec- butylbenzene, tert- butylbenzene, cyclohexanol, methyl cyclohexanol. These solvents can be used alone or in combination of two or more. Furthermore, the solvent for printing ink in the case of manufacturing printing ink, the solvent in a varnish, etc. can also be used. As long as the solvent is suitable for printing ink, such as a high boiling point petroleum solvent, an aliphatic hydrocarbon solvent, a higher alcohol solvent, a solvent that does not contain an aromatic can be used alone or in combination of two or more. These solvents can be used alone or in combination of two or more.

  The resin concentration of a resin solution obtained by dissolving a water-insoluble resin in a water-insoluble solvent is defined by the viscosity of the resin solution. That is, the resin concentration of the resin solution may be any as long as the viscosity of the resin solution has fluidity within a temperature range of 0 ° C to 40 ° C. The fluidity here is a state where the viscosity in the above temperature range is 300000 mPa · s or less. More preferably, it is in a state of 200,000 Pa · s or less. When the viscosity exceeds 300,000 mPa · s, the phase inversion from the aqueous phase to the oil phase of the organic pigment and the dye derivative is deteriorated. When the viscosity of the water-insoluble resin in the above temperature range is 300000 Pa · s or less without being dissolved in the water-insoluble solvent, an amount of water-insoluble that satisfies the range of the solid content concentration of the pigment composition after the drying step The water-insoluble resin can be dissolved in a functional solvent.

A colored resin composition that can be obtained by further dispersing the pigment dispersion using small-diameter beads is also an embodiment of the present invention.
The particle diameter of the small-diameter beads is 1.5 mmφ or less. Preferably it is 0.5 mmφ or less. More preferably, it is 0.2 mmφ or less. When the particle size of the small-diameter beads exceeds 1.5 mmφ, the impact force increases, but the voids increase. As a result, even if the residence time in the disperser becomes long, the dispersion becomes insufficient, so that a sufficient contrast ratio can be obtained. Can not. The material of the small-diameter bead is determined by the balance with the hardness of the contact member material of the dispersing device, but is preferably made of chromium, titanium, stainless steel, steel, sodaless hard glass, silicon nitride, alumina, or zirconia. Any dispersing device can be used as long as the pigment dispersion can be dispersed using small-diameter beads. A sand mill, an agitator mill, a dyno mill, a cobol mill, a kneader, and a three roll are mentioned. A bead mill is particularly preferable. When there is a viscosity region suitable for pigment dispersion in each disperser, the viscosity is adjusted by changing the ratio of the resin and the pigment. Pigment dispersion, pigment, dye derivative, solvent, monomer, resin, polymerization initiator, sensitizer, surfactant, leveling agent, coupling agent, resin-type pigment dispersant, photosensitive resin, ink, paint, etc. What is necessary as a colored resin composition for use as a coloring material can be added and subjected to a dispersion treatment. These additives can also be added after the dispersion treatment.

Showing a method of manufacturing the Pigment dispersion.

A method for producing a pigment dispersion comprises a batch or continuous stirring and mixing device comprising an aqueous suspension containing an organic pigment and an organic pigment derivative and a resin solution obtained by dissolving a water-insoluble resin in a water-insoluble solvent. By kneading, the organic pigment, the organic dye derivative, the water-insoluble resin, and the water-insoluble solvent are separated from the aqueous phase (this is called flushing). Further, the obtained kneaded product is subjected to a drying process of residual moisture, and the solid content concentration is once adjusted to 50 wt% or more and 80 wt% or less, and then solidified by a resin solution or an organic solvent, a surfactant, a monomer, etc. The partial concentration can be adjusted to 50% by weight or less.

  The stirring and mixing device used in the production of the pigment dispersion is a machine capable of mixing and stirring an aqueous suspension containing an organic pigment and kneading. When a pigment derivative is used, the pigment derivative or an aqueous suspension of the pigment derivative and an organic suspension are mixed. This is a machine capable of stirring and mixing an aqueous suspension containing a pigment. In addition, when using an aqueous suspension containing an organic pigment and a dye derivative, a dye solution or an aqueous suspension of the dye derivative and a resin solution prepared by dissolving a water-insoluble resin in a water-insoluble solvent can be added and mixed with stirring. It is a machine that can knead in. That is, when using an organic pigment or dye derivative in an aqueous suspension in a stirring and mixing device, any machine can be used as long as the organic pigment and the dye derivative can be kneaded and phase-shifted from the aqueous phase to the oil phase. But there is no limit. In addition, either a batch type or a continuous type kneading method can be employed. Specifically, a pressurized or atmospheric pressure kneader, an attritor, a sand mill, a single-screw or multi-screw rotary screw extruder, or the like can be used. Moreover, a disper, a homogenizer, a planetary mixer, a trimix, a mix muller, a Banbury mixer, an attritor, a roll mill, an extruder, a conider, etc. are mentioned.

  When an aqueous suspension or dye derivative containing an organic pigment is used as a resin solution obtained by dissolving a water-insoluble resin in a water-insoluble solvent, an aqueous suspension containing an organic pigment and an aqueous solution containing a dye derivative or dye derivative As the process of processing into the suspension, as the amount of the resin solution obtained by dissolving the water-insoluble resin in the water-insoluble solvent increases, the organic pigment and the dye derivative are separated from the water-insoluble resin and the water-insoluble solvent. When water or a water-insoluble solvent with high water solubility is used, the waste water mixed with the water-insoluble solvent and water, and a highly viscous paste-like pigment dispersion or lump Are obtained separately.

  Any method may be used for adding the resin solution. When using an organic pigment and a dye derivative, the phase inversion time of the organic pigment and the dye derivative from the aqueous phase to the oil phase varies depending on the mixing stirrer used, the organic pigment, the dye derivative, the water-insoluble resin, and the water-insoluble solvent. However, it can be traced by the solid content concentration of the wastewater as the phase inversion process proceeds. The solid content concentration of the wastewater varies depending on the amount of the organic pigment, the dye derivative and the water-insoluble resin used, and the physical properties required for the pigment dispersion, but is preferably 10% by weight or less based on the weight of the obtained wastewater. More preferably, it is 5% by weight or less. More preferably, it is 1 weight% or less. The temperature at the time of phase inversion can be performed at room temperature (25 ° C.), but it may be higher.

  As a residual moisture drying step, the waste water discharged after treating the resin solution can be removed by decantation and then dried. Further, the waste water can be subjected to a drying treatment without being removed by decantation. The drying treatment can be performed at normal temperature / normal pressure, normal temperature / reduced pressure, heated / normal pressure, heated / reduced pressure, and the like. Preferably, the heating is performed under reduced pressure from the viewpoint of productivity. The temperature and pressure vary depending on the solvent used in the resin solution, and arbitrary conditions can be used.

  The pigment dispersion before the drying step is a high-viscosity paste or lump made of an organic pigment, a water-insoluble resin, a water-insoluble solvent, and water. When the pigment derivative is used, the pigment derivative is a highly viscous paste or block containing the pigment derivative. The water content of the pigment dispersion after drying is 5% by weight or less. Preferably it is 3 weight% or less. More preferably, it is 1 weight% or less. In the drying process, if the target moisture content is not satisfied even after the solid content concentration of the pigment dispersion reaches 80% by weight, the same water-insoluble solvent as that used when dissolving the water-insoluble resin is used. An arbitrary amount can be added to the pigment dispersion and the drying process can be performed again. It is preferable to adjust the solid content concentration of the residual water after the drying step to 50 wt% or more and 80 wt% or less.

Pigment dispersions for easily producing a colored resin composition of many kinds can be used as a high pigment dispersion of pigment concentration, the pigment dispersion to undergo a process of diluting a resin solution, solvent, etc. It is common. The pigment dispersion is characterized by good viscosity stability. It is preferable in the production process that the pigment dispersion having a high pigment concentration has good viscosity stability. Pigments are Pigment dispersion dye derivative, solvent, monomer, resin, polymerization initiator, a sensitizer, a surfactant, a leveling agent, a coupling agent, a resin type pigment dispersing agent, a photosensitive resin or the like, wear color resin What is necessary as a composition can be added and subjected to a dispersion treatment. For example, in a resist colored resin composition, the pigment dispersion is changed to a pigment, a resin, an additive such as a solvent or a pigment dispersant as necessary, a photosensitive resin and a polymerization initiator necessary as a resist colored resin composition, and the like. At the same time, it is put into a normal disperser and can be produced using a dispersion dispersed until a desired average particle size and particle size distribution are obtained. The pigment dispersion and additives may be mixed and dispersed all at once, or may be mixed and dispersed separately in consideration of the characteristics and economics of each raw material. Examples of the disperser include a sand mill, an agitator mill, a dyno mill, a cobol mill, a kneader, a roll mill, and a bead mill. In particular, a bead mill is preferable in view of quality. When there is a viscosity region suitable for pigment dispersion in each disperser, the viscosity is adjusted by changing the ratio of the resin and the pigment.

  A resist coloring resin composition for a color filter containing the pigment dispersion is also an embodiment of the present invention. The resist-colored resin composition preferably contains a transparent resin, a photopolymerization initiator, and the like in addition to the pigment dispersion.

  The resist-colored resin composition is composed of the pigment dispersion or a dispersion of the pigment dispersion and a transparent resin, a precursor thereof, or a mixture thereof. The transparent resin is a resin having a transmittance of preferably 80% or more, more preferably 95% or more in the entire wavelength region of 400 to 700 nm in the visible light region. Transparent resins include thermoplastic resins, thermosetting resins, and photosensitive resins, and precursors thereof include monomers or oligomers that are cured by irradiation with active energy rays to form transparent resins. It can be used alone or in combination of two or more.

  When the composition is cured by ultraviolet irradiation, a photopolymerization initiator or the like is added to the resist-colored resin composition.

  Examples of the thermoplastic resin include butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, polyurethane resin, and phenol resin. , Polyester resins, acrylic resins, alkyd resins, styrene resins, polyamide resins, rubber resins, cyclized rubbers, celluloses, polybutadiene, polyimide resins, and the like. Examples of the thermosetting resin include epoxy resins, benzoguanamine resins, rosin-modified maleic acid resins, rosin-modified fumaric acid resins, melamine resins, and urea resins.

  As the photosensitive resin, a (meth) acrylic compound having a reactive substituent such as an isocyanate group, an aldehyde group or an epoxy group on a linear polymer having a reactive substituent such as a hydroxyl group, a carboxyl group or an amino group, A resin obtained by reacting cinnamic acid and introducing a photocrosslinkable group such as a (meth) acryloyl group or a styryl group into the linear polymer is used. In addition, a linear polymer containing an acid anhydride such as a styrene-maleic anhydride copolymer or an α-olefin-maleic anhydride copolymer is converted into a (meth) acrylic compound having a hydroxyl group such as hydroxyalkyl (meth) acrylate. Half-esterified products are also used.

  Monomers and oligomers include methyl (meth) acrylate, ethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, cyclohexyl (meth) acrylate, β-carboxyethyl (meth) acrylate , Polyethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, triethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol Tri (meth) acrylate, 1,6-hexanediol diglycidyl ether di (meth) acrylate, bisphenol A diglycidyl ether di (meth) acrylate, ne Various acrylics such as pentyl glycol diglycidyl ether di (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tricyclodecanyl (meth) acrylate, ester acrylate, melamine (meth) acrylate, epoxy (meth) acrylate, urethane acrylate Acid ester and methacrylate ester, (meth) acrylic acid, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, N-vinylformamide Acrylonitrile and the like, and these can be used alone or in combination of two or more.

  Examples of the photopolymerization initiator include 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- Acetophenone photopolymerization initiators such as hydroxycyclohexyl phenyl ketone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl Benzoin photopolymerization initiators such as ether and benzyldimethyl ketal, benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzene Benzophenone-based photopolymerization initiators such as zoyl-4′-methyldiphenyl sulfide, thioxanthone-based light such as thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone Polymerization initiator, 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxyphenyl) -4,6-bis (trichloro) Methyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2-pienyl-4,6-bis (trichloromethyl) -s-triazine, 2,4 -Bis (trichloromethyl) -6-styryl-s-triazine, 2- (naphth-1-yl) -4,6-bis ( Lichloromethyl) -s-triazine, 2- (4-methoxy-naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2,4-trichloromethyl- (piperonyl) -6-triazine, Triazine photopolymerization initiators such as 2,4-trichloromethyl (4′-methoxystyryl) -6-triazine, borate photopolymerization initiators, carbazole photopolymerization initiators, imidazole photopolymerization initiators, and the like are used. .

  The above photopolymerization initiators are used alone or in combination of two or more. As sensitizers, α-acyloxime ester, acylphosphine oxide, methylphenylglyoxylate, benzyl, 9,10-phenanthrenequinone. , Camphorquinone, ethylanthraquinone, 4,4′-diethylisophthalophenone, 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone, 4,4′-diethylaminobenzophenone, etc. It can also be used together.

  The resist coloring resin composition can be adjusted in the form of a solvent developing type or alkali developing type coloring resist material. The colored resist material is obtained by further dispersing the pigment dispersion in a composition containing a thermoplastic resin, a thermosetting resin or a photosensitive resin, and a photopolymerization initiator. The pigment dispersion composed of the above-mentioned pigment dispersion is further refined by using various dispersing means such as a three-roll mill, a two-roll mill, a sand mill, and a kneader in a pigment carrier together with a photopolymerization initiator as necessary. It can be dispersed and manufactured. The resist-colored resin composition can also be produced by mixing several types of pigment dispersions further dispersed on a pigment carrier.

  When producing a resist colored resin composition, in order to easily produce a variety of colored resin compositions, first, a dispersion having a high pigment concentration is produced, and then this dispersion is diluted with a resin solution, a solvent, or the like. The pigment dispersion is generally characterized by having a good viscosity stability. It is preferable in the production process of the resist coloring composition that the dispersion having a high pigment concentration has good viscosity stability.

The resist-colored resin composition is formed by means of centrifugal separation, sintering filter, membrane filter, etc., and coarse particles of 5 μm or more, preferably coarse particles of 1 μm or more, more preferably coarse particles of 0.5 μm or more and mixed dust Is preferably removed.
When dispersing the pigment dispersion in a pigment carrier, a dispersion aid such as a resin-type pigment dispersant, a surfactant, and a dye derivative can be appropriately used. Since the dispersion aid is excellent in pigment dispersion and has a great effect of preventing reaggregation of the pigment after dispersion, a colored resin composition obtained by dispersing the pigment dispersion in a pigment carrier using a dispersion aid is used. When used, a color filter excellent in transparency can be obtained. In addition, the resist-colored resin composition may contain a dye within a range that does not reduce heat resistance for color matching.

  The resin-type pigment dispersant has a pigment affinity part that has the property of adsorbing to the pigment and a part that is compatible with the pigment carrier, and acts to stabilize the dispersion of the pigment on the pigment carrier by adsorbing to the pigment. It is something to do. Specific examples of resin-type pigment dispersants include polycarboxylic acid esters such as polyurethane and polyacrylate, unsaturated polyamides, polycarboxylic acids, polycarboxylic acid (partial) amine salts, polycarboxylic acid ammonium salts, and polycarboxylic acid alkylamines. Salts, polysiloxanes, long-chain polyaminoamide phosphates, hydroxyl group-containing polycarboxylic acid esters, their modified products, amides formed by the reaction of poly (lower alkyleneimines) with polyesters having free carboxyl groups, and the like Salt or the like is used. In addition, water-soluble resins such as (meth) acrylic acid-styrene copolymer, (meth) acrylic acid- (meth) acrylic acid ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol, and polyvinylpyrrolidone, and water-soluble Polymer compounds, polyesters, modified polyacrylates, ethylene oxide / propylene oxide adducts, and the like are used. These can be used alone or in admixture of two or more.

Surfactants include sodium lauryl sulfate, polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium stearate, sodium alkyl naphthalene sulfonate, sodium alkyl diphenyl ether disulfonate. Anionic surfactants such as monoethanolamine lauryl sulfate, triethanolamine lauryl sulfate, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer; poly Oxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene sorbita Nonionic surfactants such as monostearate and polyethylene glycol monolaurate; chaotic surfactants such as alkyl quaternary ammonium salts and their ethylene oxide adducts; alkylbetaines such as alkyldimethylaminoacetic acid betaine, alkylimidazolines, etc. These amphoteric surfactants can be used, and these can be used alone or in admixture of two or more. For the resist coloring resin composition, the above-mentioned dye derivatives can be used. These can be used alone or in admixture of two or more. In particular, a pigment derivative having a basic group or a triazine derivative having a basic group is preferably used because of a large pigment dispersion effect.

  In the resist coloring resin composition, the above pigment dispersion is sufficiently dispersed in a pigment carrier, and applied to a transparent substrate such as a glass substrate so that the dry film thickness is 0.2 to 5 μm to form a filter segment. A solvent can be included to facilitate the process. Examples of the solvent include cyclohexanone, ethyl cellosolve acetate, butyl cellosolve acetate, 1-methoxy-2-propyl acetate, diethylene glycol dimethyl ether, ethylbenzene, ethylene glycol diethyl ether, xylene, ethyl cellosolve, methyl-n amyl ketone, propylene glycol monomethyl ether toluene, methyl ethyl ketone. , Ethyl acetate, methanol, ethanol, isopropyl alcohol, butanol, isobutyl ketone, petroleum solvent and the like, and these are used alone or in combination.

  The resist-colored resin composition can contain a storage stabilizer in order to stabilize the viscosity with time of the composition. Examples of storage stabilizers include quaternary ammonium chlorides such as benzyltrimethyl chloride and diethylhydroxyamine, organic acids such as lactic acid and oxalic acid, and organic acids such as methyl ether, t-butylpyrocatechol, tetraethylphosphine, and tetraphenylphosphine. Examples thereof include phosphine and phosphite. The pigment is preferably contained in the colored resin composition in a proportion of 1.5 to 7% by weight. Further, the pigment is preferably contained in the final filter segment in a proportion of 10 to 40% by weight, more preferably 20 to 40% by weight, and the remainder substantially consists of a resinous binder provided by the pigment carrier. .

  A color filter that can be obtained using the resist-colored resin composition is also an embodiment of the present invention.

  The color filter in the present invention is a transparent or reflective substrate in which three color filter segments of R (red), G (green), and B (blue) are formed, or Y (yellow) and M (magenta). , C (cyan) three-color filter segments are formed, and the like. Each color filter segment can be formed by using the coloring composition of the present invention by a printing method or a photolithography method.

As the transparent substrate, a glass plate such as quartz glass, borosilicate glass, alumina silicate glass, soda lime glass whose surface is coated with silica, or a resin plate such as polycarbonate, polymethyl methacrylate, or polyethylene terephthalate is used.
As the reflective substrate, silicon or a substrate in which an aluminum, silver, silver / copper / palladium alloy thin film or the like is formed on the transparent substrate is used.

  The formation of each color filter segment by the printing method can be patterned simply by repeating the printing and drying of the colored composition prepared as the above various printing inks. Therefore, the color filter manufacturing method is low-cost and excellent in mass productivity. ing. Furthermore, it is possible to print a fine pattern having high dimensional accuracy and smoothness by the development of printing technology. In order to perform printing, it is preferable that the ink does not dry and solidify on the printing plate or on the blanket. Control of ink fluidity on a printing press is also important, and ink viscosity can be adjusted with a dispersant or extender pigment.

  When forming each color filter segment by a photolithography method, the colored composition prepared as the solvent developing type or alkali developing type colored resist material is applied on a transparent substrate, such as spray coating, spin coating, slit coating, roll coating, etc. By a coating method, coating is performed so that the dry film thickness is 0.2 to 5 μm. If necessary, the dried film is exposed to ultraviolet light through a mask having a predetermined pattern provided in contact with or non-contact with the film. Then, after immersing in a solvent or an alkaline developer, or spraying the developer with a spray or the like to remove the uncured portion to form a desired pattern, the same operation is repeated for other colors to produce a color filter. be able to. Furthermore, in order to accelerate the polymerization of the colored resist material, heating can be performed as necessary. According to the photolithography method, a color filter with higher accuracy than the above printing method can be manufactured.

In development, an aqueous solution such as sodium carbonate or sodium hydroxide is used as an alkali developer, and an organic alkali such as dimethylbenzylamine or triethanolamine can also be used. Moreover, an antifoamer and surfactant can also be added to a developing solution.
In order to increase the UV exposure sensitivity, after coating and drying the colored resist material, a water-soluble or alkali-soluble resin such as polyvinyl alcohol or a water-soluble acrylic resin is applied and dried to form a film that prevents polymerization inhibition by oxygen. Thereafter, ultraviolet exposure can also be performed.

The color filter of the present invention can be produced by an electrodeposition method, a transfer method or the like in addition to the above method, but the colored resin composition of the present invention can be used in any method. The electrodeposition method is a method for producing a color filter by using a transparent conductive film formed on a transparent substrate and forming each color filter segment on the transparent conductive film by electrophoresis of colloidal particles. is there.
The transfer method is a method in which a color filter layer is formed in advance on the surface of a peelable transfer base sheet, and this color filter layer is transferred to a desired transparent substrate.

  If a black matrix is formed in advance before forming the filter segment on the transparent substrate or the reflective substrate, the contrast ratio of the liquid crystal display panel can be further increased. As the black matrix, a chromium, chromium / chromium oxide multilayer film, an inorganic film such as titanium nitride, or a resin film in which a light-shielding agent is dispersed is used, but is not limited thereto. In addition, a thin film transistor (TFT) may be formed in advance on the transparent substrate or the reflective substrate, and then a filter segment may be formed. By forming the filter segment on the TFT substrate, the aperture ratio of the liquid crystal display panel can be increased and the luminance can be improved.

On the color filter of the present invention, an overcoat film, a columnar spacer, a transparent conductive film, a liquid crystal alignment film, and the like are formed as necessary.
The color filter preferably has a small degree of depolarization, and the evaluation of the degree of depolarization can be performed by measuring the contrast ratio of the color filter. Such a contrast ratio can be obtained by sandwiching a color filter between two polarizing films, measuring the brightness of transmitted light when the polarizing axis of the polarizing film is parallel and perpendicular, and calculating the ratio. it can.

  The greater the contrast ratio, the smaller the degree of depolarization. The smaller the degree of depolarization of the color filter, in other words, the greater the contrast ratio of the color filter, the greater the contrast ratio of the liquid crystal display panel and the better the visibility. For this reason, the contrast ratio of the color filter is preferably as large as possible, specifically preferably 1000 or more, more preferably 1200 or more, and further preferably 1500 or more.

The color filter is bonded to the counter substrate using a sealant, and after injecting liquid crystal from the injection port provided in the seal part, the injection port is sealed, and if necessary, a polarizing film or a retardation film is placed outside the substrate. A liquid crystal display panel is manufactured by bonding.
Such liquid crystal display panels include twisted nematic (TN), super twisted nematic (STN), in-plane switching (IPS), vertical alignment (VA), and optically convented bend (OCB). It can be used for a liquid crystal display mode in which colorization is performed using a color filter.

Examples of the present invention will be described, but the present invention is not limited to the examples. In the examples, parts and% represent parts by weight and% by weight. Moreover, the weight average molecular weight of resin was measured using GPC and calculated | required in polystyrene conversion.
[Evaluation of pigment dispersion for color filter]
Prior to Examples, a method for measuring a contrast ratio will be described as a method for measuring the dispersion state of a pigment dispersion used in the present invention. That is, the dispersion stability varies depending on the dispersion state of the pigment particles. The contrast ratio has a correlation with the dispersion state of the pigment particles, and the higher the contrast ratio, the more finely dispersed the pigment particles. Using this, it was shown that the dispersion state of the example and the comparative example are almost the same. The pigment dispersion was evaluated as a paste by performing a dispersion treatment and a dilution treatment under certain conditions shown in the following examples and comparative examples.

(1) Description of contrast ratio A pigment dispersion-coated substrate is sandwiched between two polarizing plates, and light is irradiated from one polarizing plate side using a backlight unit. The light emitted from the backlight unit passes through the first polarizing plate, is polarized, then passes through the pigment dispersion-coated substrate, and reaches the second polarizing plate. If the polarization planes of the first polarizing plate and the second polarizing plate are parallel, light passes through the second polarizing plate, but if the polarization plane is perpendicular, the light passes through the second polarizing plate. Are blocked by the polarizing plate. However, when the light polarized by the first polarizing plate passes through the pigment dispersion coated substrate, scattering by pigment particles or the like causes a deviation in a part of the polarization plane. The amount of light transmitted through the second polarizing plate is reduced, and when the deflection plate is perpendicular, a part of the light is transmitted through the second polarizing plate. This transmitted light is measured as the luminance on the polarizing plate, and the ratio between the luminance when the polarizing plate is parallel and the luminance when the polarizing plate is orthogonal is defined as the contrast ratio.
Contrast ratio = (Luminance when parallel) / (Luminance when direct)
Accordingly, when scattering occurs due to the pigment in the pigment dispersion coating film, the brightness when parallel is reduced and the brightness when perpendicular is increased, the contrast ratio is lowered. On the other hand, the higher the contrast ratio, the finer the pigment particles are dispersed.
In addition, the luminance meter used the Topcon Co., Ltd. product and the color luminance meter BM-5A, and the polarizing plate used the Sanritsu Co., Ltd. polarizing film LLC2-92-18. In the measurement, in order to block unnecessary light, measurement was performed by applying a black mask having a 1 cm square hole in the measurement portion.

(2) Adjustment of Resin Solution Next, a production example of a resin solution for producing a pigment dispersion is shown below.
(Preparation of resin solution 1)
450 parts of cyclohexanone was placed in a reaction vessel, heated to 80 ° C. while injecting nitrogen gas into the vessel, and a mixture of the following monomer and thermal polymerization initiator was added dropwise at the same temperature over 1 hour to carry out a polymerization reaction.
Methacrylic acid; 20.0 parts methyl methacrylate; 10.0 parts n-butyl methacrylate; 55.0 parts 2-hydroxyethyl methacrylate; 15.0 parts 2,2′-azobisisobutyronitrile; 4.0 parts dropwise After completion of the reaction, the mixture was further reacted at 80 ° C. for 3 hours, then 1.0 part of azobisisobutyronitrile dissolved in 50 parts of cyclohexanone was added, and the reaction was further continued at 80 ° C. for 1 hour to obtain a weight average. An acrylic resin solution having a molecular weight of about 40,000 and an acid value of 130 was obtained. (The weight average molecular weight used here is based on the gel permeation chromatography method.)
After cooling to room temperature, about 2 g of the resin solution was sampled, heated and dried at 180 ° C. for 20 minutes to measure the nonvolatile content, and cyclohexanone was added to the previously synthesized resin solution so that the nonvolatile content was 30% by weight. Resin solution 1 was prepared.

(Preparation of resin solution 2)
450 parts of cyclohexanone was placed in a reaction vessel, heated to 80 ° C. while injecting nitrogen gas into the vessel, and a mixture of the following monomer and thermal polymerization initiator was added dropwise at the same temperature over 1 hour to carry out a polymerization reaction.
Methacrylic acid; 20.0 parts methyl methacrylate; 10.0 parts n-butyl methacrylate; 55.0 parts 2-hydroxyethyl methacrylate; 15.0 parts 2,2′-azobisisobutyronitrile; 4.0 parts dropwise After completion of the reaction, the mixture was further reacted at 80 ° C. for 3 hours, then 1.0 part of azobisisobutyronitrile dissolved in 50 parts of propylene glycol monomethyl ether acetate was added, and the reaction was further continued at 80 ° C. for 1 hour. Thus, an acrylic resin solution having a weight average molecular weight of about 40,000 and an acid value of 130 was obtained. (The weight average molecular weight used here is based on the gel permeation chromatography method.)
After cooling to room temperature, about 2 g of the resin solution was sampled, heated and dried at 180 ° C. for 20 minutes to measure the nonvolatile content, and propylene glycol monomethyl ether so that the nonvolatile content was 30% by weight in the previously synthesized resin solution. Acetate was added to prepare Resin Solution 2.

(Preparation of resin solution 3)
450 parts of cyclohexanone was placed in a reaction vessel, heated to 80 ° C. while injecting nitrogen gas into the vessel, and a mixture of the following monomer and thermal polymerization initiator was added dropwise at the same temperature over 1 hour to carry out a polymerization reaction.
Methacrylic acid; 20.0 parts methyl methacrylate; 10.0 parts n-butyl methacrylate; 55.0 parts 2-hydroxyethyl methacrylate; 15.0 parts 2,2′-azobisisobutyronitrile; 4.0 parts dropwise After completion of the reaction, the mixture was further reacted at 80 ° C. for 3 hours, then 1.0 part of azobisisobutyronitrile dissolved in 50 parts of ethyl acetate was added, and the reaction was further continued at 80 ° C. for 1 hour. An acrylic resin solution having an average molecular weight of about 40,000 and an acid value of 130 was obtained. (The weight average molecular weight used here is based on the gel permeation chromatography method.)
After cooling to room temperature, sample approximately 2g of the resin solution, heat dry at 180 ° C for 20 minutes, measure the nonvolatile content, and add ethyl acetate to the previously synthesized resin solution so that the nonvolatile content is 30 wt% Thus, a resin solution 3 was prepared.

(Preparation of resin solution 4)
450 parts of cyclohexanone was placed in a reaction vessel, heated to 80 ° C. while injecting nitrogen gas into the vessel, and a mixture of the following monomer and thermal polymerization initiator was added dropwise at the same temperature over 1 hour to carry out a polymerization reaction.
Methacrylic acid; 6.0 parts methyl methacrylate; 10.0 parts n-butyl methacrylate; 55.0 parts 2-hydroxyethyl methacrylate; 15.0 parts 2,2′-azobisisobutyronitrile; After completion of the reaction, the mixture was further reacted at 80 ° C. for 3 hours, then 1.0 part of azobisisobutyronitrile dissolved in 50 parts of ethyl acetate was added, and the reaction was further continued at 80 ° C. for 1 hour. An acrylic resin solution having an average molecular weight of about 40,000 and an acid value of 39 was obtained. (The weight average molecular weight used here is based on the gel permeation chromatography method.)
After cooling to room temperature, sample approximately 2g of the resin solution, heat dry at 180 ° C for 20 minutes, measure the nonvolatile content, and add ethyl acetate to the previously synthesized resin solution so that the nonvolatile content is 30 wt% Thus, a resin solution 4 was prepared.

(Preparation of resin solution 5)
450 parts of cyclohexanone was placed in a reaction vessel, heated to 80 ° C. while injecting nitrogen gas into the vessel, and a mixture of the following monomer and thermal polymerization initiator was added dropwise at the same temperature over 1 hour to carry out a polymerization reaction.
Methacrylic acid; 2.0 parts methyl methacrylate; 10.0 parts n-butyl methacrylate; 55.0 parts 2-hydroxyethyl methacrylate; 15.0 parts 2,2′-azobisisobutyronitrile; 4.0 parts dropwise After completion of the reaction, the mixture was further reacted at 80 ° C. for 3 hours, then 1.0 part of azobisisobutyronitrile dissolved in 50 parts of ethyl acetate was added, and the reaction was further continued at 80 ° C. for 1 hour. An acrylic resin solution having an average molecular weight of about 40,000 and an acid value of 13 was obtained. (The weight average molecular weight used here is based on the gel permeation chromatography method.)
After cooling to room temperature, sample approximately 2g of the resin solution, heat dry at 180 ° C for 20 minutes, measure the nonvolatile content, and add ethyl acetate to the previously synthesized resin solution so that the nonvolatile content is 30 wt% Thus, a resin solution 5 was prepared.

(3) Preparation of pigment dispersion, colored resin composition, and paste [Example 1]
160 parts of ε-type copper phthalocyanine pigment (CI Pigment Blue 15: 6) (“Lionol Blue E” manufactured by Toyo Ink Manufacturing Co., Ltd.), 1600 parts of sodium chloride, and 190 parts of diethylene glycol are made of 1 gallon kneader (manufactured by Inoue Seisakusho). And kneaded at 60 ° C. for 10 hours. Next, the kneaded product is poured into 3 liters of warm water, stirred for 1 hour with a high-speed mixer while heating to about 80 ° C., and the mixture is filtered and washed repeatedly to remove sodium chloride and solvent, and then filter. 450 parts by weight of blue pigment aqueous suspension 1 having an ε-type copper phthalocyanine pigment content of 30% by weight was obtained by filtration and dehydration by pressing (the average primary particle size was 0.02 to 0.03 μm as measured by an electron microscope). Met.). To 100 parts by weight of the blue pigment aqueous suspension 1, 12 parts by weight of an aqueous suspension having a 45% content of a phthalocyanine dye derivative (the derivative 48) is added, and the kneader is heated at room temperature (25 ° C.). And kneaded and stirred. 80 parts by weight of resin solution 1 (viscosity: 175.9 mPa · s (25 ° C., 2.5 rpm, E-type viscometer (manufactured by Toki Sangyo Co., Ltd.)) was added to the mixed aqueous suspension, and room temperature (25 ° C.) Then, phase inversion treatment was performed using a kneader (primary wastewater solid concentration: 0.5%), after which the primary wastewater was removed by decantation, 40 parts by weight of cyclohexanone was added thereto, and the mixture was stirred with a kneader. The solid content concentration of the primary wastewater removed by the aeration was 0.2% by weight, followed by dehydration as a secondary wastewater by heating to 60 ° C. under vacuum. A pigment dispersion 1 in which an ε-type copper phthalocyanine pigment and a phthalocyanine pigment derivative (derivative 48) are dispersed in an acrylic resin and cyclohexane prepared in the resin solution 1 is performed until the solid concentration reaches 80% by weight. 18.8 was obtained parts. (Water content 0.9 wt% solids content 40 wt%)
Next, a mixture having the following composition was stirred and mixed uniformly, then dispersed with a bead mill for 2 hours using 0.5 mmφ zirconia beads, and then filtered with a 5 μm filter to prepare a blue colored resin composition 1.
Pigment Dispersion 1; 25.0 parts by weight cyclohexanone; 16.7 parts by weight Further, a mixture having the following composition was stirred and mixed to be uniform, and then filtered through a 1 μm filter to prepare Blue Paste 1.
Blue colored resin composition 1; 25.0 parts by weight cyclohexanone; 12.5 parts by weight

[Example 2]
160 parts of DPP pigment (CI Pigment RED 254) ("Irga Four Red B-CF" manufactured by Ciba Specialty Chemicals), 1600 parts of sodium chloride, and 190 parts of diethylene glycol 1 gallon kneader made of stainless steel (manufactured by Inoue Seisakusho) And kneaded at 60 ° C. for 10 hours. Next, the kneaded product is poured into 3 liters of warm water, stirred for 1 hour with a high-speed mixer while heating to about 80 ° C., and the mixture is filtered and washed repeatedly to remove sodium chloride and solvent, and then filter. 450 parts by weight of red pigment aqueous suspension 1 having a DPP pigment content of 30% by weight was obtained by filtration and dehydration by pressing (the average primary particle size measured by an electron microscope was 0.02 to 0.03 μm). .) To 100 parts by weight of the red pigment aqueous suspension 1, 5.0 parts by weight of an aqueous suspension having a pigment derivative (Table 1e) content of 45% is added, and the kneader is heated at room temperature (25 ° C.). And kneaded and stirred. 72 parts by weight of resin solution 2 (viscosity: 165.5 mPa · s (25 ° C., 2.5 rpm, E-type viscometer) manufactured by Toki Sangyo Co., Ltd.) was added to the mixed aqueous suspension, and room temperature (25 ° C.). Then, the phase of the pigment was converted into a resin phase using a kneader, and the primary waste water at this time was removed by decantation, and 40 parts by weight of propylene glycol monomethyl ether acetate was added thereto, followed by stirring with the kneader. The solid content concentration of the primary waste water removed by the above was 0.4% by weight, followed by dehydration as a secondary waste water by heating to 60 ° C. under vacuum. The DPP pigment and the dye derivative (see the above table) were added to the acrylic resin and propylene glycol monomethyl ether acetate prepared in the resin solution 2 until the partial concentration reached 80% by weight. e) to obtain a pigment dispersion 2 which is dispersed 107.0 parts by weight. (water content 0.8 wt% solids content 40 wt%)
Next, a mixture having the following composition was uniformly stirred and mixed, then dispersed with a bead mill for 2 hours using 0.5 mmφ zirconia beads, and then filtered through a 5 μm filter to prepare a red colored resin composition 1.
Pigment Dispersion 2; 25.0 parts by weight Propylene glycol monomethyl ether acetate; 16.7 parts by weight Further, a mixture having the following composition was stirred and mixed to be uniform, and then filtered through a 1 μm filter to obtain red paste 1 It was adjusted.
Red colored resin composition 1; 25.0 parts by weight propylene glycol monomethyl ether acetate; 12.5 parts by weight

[Example 3]
160 parts of ε-type copper phthalocyanine pigment (CI Pigment Blue 15: 6) (“Lionol Blue E” manufactured by Toyo Ink Manufacturing Co., Ltd.), 1600 parts of sodium chloride, and 190 parts of diethylene glycol are made of 1 gallon kneader (manufactured by Inoue Seisakusho). And kneaded at 60 ° C. for 10 hours. Next, the kneaded product is poured into 3 liters of warm water, stirred for 1 hour with a high-speed mixer while heating to about 80 ° C., and the mixture is filtered and washed repeatedly to remove sodium chloride and solvent, and then filter. 450 parts by weight of blue pigment aqueous suspension 1 having an ε-type copper phthalocyanine pigment content of 30% by weight was obtained by filtration and dehydration by pressing (the average primary particle diameter measured by an electron microscope was 0.02 to 0.03 μm). there were.). To 100 parts by weight of the blue pigment aqueous suspension 1, 12 parts by weight of an aqueous suspension having a 45% content of a phthalocyanine dye derivative (the derivative 48) is added, and the kneader is heated at room temperature (25 ° C.). And kneaded and stirred. 80 parts by weight of the resin solution 3 (viscosity: 332.3 mPa · s (25 ° C.) was added to the mixed aqueous suspension, and a phase inversion treatment was performed using a kneader at room temperature (25 ° C.) (primary waste water). After that, the primary wastewater was removed by decantation, and 40 parts by weight of ethyl acetate was added thereto and stirred with a kneader.The solid content concentration of the primary wastewater removed by decantation was 0.00. Next, dehydration was performed by heating to 60 ° C. under vacuum as secondary wastewater until the solid content concentration of the obtained pigment dispersion reached 5080 wt%, and resin solution 3 118.8 parts by weight of a pigment dispersion 3 in which an ε-type copper phthalocyanine pigment and a phthalocyanine pigment derivative (derivative 48) were dispersed in the acrylic resin and ethyl acetate prepared in Step 1 were obtained (solid content 40% by weight).
Next, a mixture having the following composition was uniformly stirred and mixed, then dispersed with a bead mill for 2 hours using 0.5 mmφ zirconia beads, and then filtered with a 5 μm filter to prepare a blue colored resin composition 2.
Pigment Dispersion 3; 25.0 parts by weight cyclohexanone; 16.7 parts by weight Further, a mixture having the following composition was stirred and mixed to be uniform, and then filtered through a 1 μm filter to prepare a blue colored paste 2.
Blue colored resin composition 2; 25.0 parts by weight cyclohexanone; 12.5 parts by weight

[Example 4]
When the blue aqueous suspension is measured with an electron microscope, the average primary particle diameter of the organic pigment is 0.12 μm to 0.15 μm, and a 5 μm filter is used as a filter for filtering the blue colored paste. A blue colored paste 3 was obtained in the same manner as in Example 1 except that.

[Example 5]
When the red aqueous suspension is measured with an electron microscope, the average primary particle diameter of the organic pigment is 0.12 μm to 0.15 μm, and a filter of 5 μm is used as a filter for filtering the red colored paste. A red colored paste 2 was obtained in the same manner as in Example 2 except for the above.

[Example 6]
When the blue aqueous suspension is measured with an electron microscope, the average primary particle diameter of the organic pigment is 0.12 μm to 0.15 μm, and a 5 μm filter is used as a filter for filtering the blue colored paste. A blue colored paste 4 was obtained in the same manner as in Example 3 except for the above.

[Example 7]
A blue colored paste 5 was obtained in the same manner as in Example 1 except that the 0.5 mmφ zirconia beads used in Example 1 were 0.1 mmφ zirconia beads.

[Example 8]
A red colored paste 3 was obtained in the same manner as in Example 2 except that the 0.5 mmφ zirconia beads used in Example 2 were 0.1 mmφ zirconia beads.

[Example 9]
A blue colored paste 6 was obtained in the same manner as in Example 1 except that the 0.5 mmφ zirconia beads used in Example 1 were 0.8 mmφ zirconia beads.

[Example 10]
A red colored paste 4 was obtained in the same manner as in Example 2 except that the 0.5 mmφ zirconia beads used in Example 2 were 0.8 mmφ zirconia beads.

[Comparative Example 1]
An aqueous suspension of the phthalocyanine pigment derivative of Example 1 (the aforementioned derivative 48) (the content of the pigment derivative is 45% by weight; the same shall apply hereinafter) is used as a dry powder 5 of the phthalocyanine pigment derivative (derivative 48). A blue colored paste 7 was obtained in the same manner as in Example 1 except that the amount was changed to 4 parts by weight.

[Comparative Example 2]
A red colored paste 5 was obtained in the same manner as in Example 2, except that the aqueous suspension of the pigment derivative of Example 2 (Table 1e) was changed to 2.25 parts by weight of the dry powder of the pigment derivative (Table 1e). .

[Comparative Example 3]
Blue-colored in the same manner as in Example 3 except that the aqueous suspension of the phthalocyanine dye derivative (derivative 48) in Example 3 was changed to 5.4 parts by weight of the dry powder of the phthalocyanine dye derivative (derivative 48). A paste 8 was obtained.

[Comparative Example 4]
The aqueous suspension of the phthalocyanine dye derivative (derivative 48) of Example 1 was changed to 5.4 parts by weight of a dry powder of the phthalocyanine dye derivative (derivative 48), and the blue aqueous suspension used in Example 1 was used. Blue colored paste in the same manner as in Example 1 except that the average primary particle size of the turbid material is 0.12 μm to 0.15 μm and the filter used for filtering the blue colored paste is 5 μm. 9 was obtained.

[Comparative Example 5]
The aqueous suspension of the pigment derivative of Example 2 (Table 1e) was changed to 2.25 parts by weight of the dry powder of the pigment derivative (Table 1e), and the average primary of the red aqueous suspension used in Example 2 A red colored paste 6 was obtained in the same manner as in Example 2 except that the particle diameter was 0.12 μm to 0.15 μm and the filter used for filtering the red colored paste was 5 μm.

[Comparative Example 6]
The aqueous suspension of the phthalocyanine dye derivative (derivative 48) of Example 3 was changed to 5.4 parts by weight of a dry powder of the phthalocyanine dye derivative (derivative 48), and the blue aqueous suspension used in Example 3 was used. Blue colored paste in the same manner as in Example 3 except that the average primary particle size of the turbid material is 0.12 μm to 0.15 μm and the filter used for filtering the blue colored paste is 5 μm. 10 was obtained.

(4) Evaluation of Paste The pastes obtained in Examples 1 to 10 and Comparative Examples 1 to 6 were rotated at 1000 rpm, 2000 rpm, and 3000 rpm on a 100 mm × 100 mm, 1.1 mm thick glass substrate using a spin coater. The three coated substrates having different film thicknesses were obtained. The paste coated substrate was dried at 70 ° C. for 15 minutes. Next, the chromaticity (Y, x, y) of the coating film with a C light source was measured using a microspectrophotometer (“OSP-SP100” manufactured by Olympus Optical Co., Ltd.). From the three sets of contrast ratio and chromaticity measurement results, Example 1, Example 3, Example 4, Example 6, Example 7, Example 9, Example 9, Comparative Example 1, Comparative Example 3, Comparative Example 4, and Comparative Example For the colored composition-coated substrate obtained in Step 6, the contrast ratio at y = 0.14 was changed to that obtained in Example 2, Example 5, Example 8, Example 10, Comparative Example 2, and Comparative Example 5. For the composition-coated substrate, the contrast ratio at x = 0.65 was determined using an approximation method.

  Next, the viscosities of the pastes obtained in Examples 1 to 10 and Comparative Examples 1 to 6 were measured using an E-type viscometer (manufactured by Toki Sangyo Co., Ltd.). The EML type was used for measuring the paste. Table 2 below shows the results of Examples and Comparative Examples of the blue colored paste (y = 0.14), and Table 3 shows Examples and Comparative Examples of the red colored paste (x = 0.65).

(5) Re-solubility evaluation
[Example 11]
A pigment dispersion 4 having a solid concentration of 50% by weight was obtained in the same manner as in Example 1.

[Comparative Example 7]
A pigment dispersion 5 was obtained in the same manner as in Example 1 except that the solid content concentration of the pigment dispersion in the drying step of Example 1 was changed to 100% by weight.

The pigment dispersions 4 and 5 obtained in Example 11 and Comparative Example 7 were added to the following amounts while stirring with a disper for 10 minutes. The dispersion value (unit: μm) of each coating solution was measured using a grindometer. The smaller this value, the better the solubility. If the dissolution is insufficient, the dispersity becomes a large value. This evaluated the re-solubility of the pigment dispersion.
Example 11
Pigment Dispersion 4; 25.0 parts by weight cyclohexanone; 16.7 parts by weight Comparative Example 7
Pigment Dispersion 5; 12.5 parts by weight cyclohexanone; 29.2 parts by weight The results of Example 11 and Comparative Example 7 are shown in Table 4 below.

実施例１１の分散度値は表４に示したように２０μｍ以下であり良好な分散性が得られており、溶解性が良かった。一方、顔料分散体の乾燥工程で固形分濃度を１００％とした比較例７では分散度値は目視で数ｍｍ程度のブツが観察され、十分に溶解していなかった。

As shown in Table 4, the dispersity value of Example 11 was 20 μm or less, good dispersibility was obtained, and the solubility was good. On the other hand, in Comparative Example 7 in which the solid content concentration was 100% in the drying process of the pigment dispersion, the dispersion value was visually observed to be about several mm, and was not sufficiently dissolved.

(6) Preparation of resist ink [Example 12]
A blue colored resin composition 3 was prepared in the same manner as in Example 1.

Further, a mixture having the following composition was stirred and mixed so as to be uniform, and then filtered through a 1 μm filter to obtain a blue resist coloring composition 1.
Blue colored resin composition 3; 41.7 parts by weight Resin solution 1; 36.2 parts by weight trimethylolpropane triacrylate; 9.0 parts by weight (“NK Ester ATMPT” manufactured by Shin-Nakamura Chemical Co., Ltd.)
Photopolymerization initiator ("Irgacure 907" manufactured by Ciba Geigy); 2.95 parts by weight sensitizer ("EAB-F" manufactured by Hodogaya Chemical Co.); 0.296 parts by weight cyclohexanone; 118.2 parts by weight

[Example 13]
A red colored resin composition 2 was prepared in the same manner as in Example 2.

Further, a mixture having the following composition was stirred and mixed so as to be uniform, and then filtered through a 1 μm filter to obtain a red resist landing composition 1.
Red colored resin composition 2; 41.7 parts by weight Resin solution 2; 36.2 parts by weight trimethylolpropane triacrylate; 9.0 parts by weight (“NK ester ATMPT” manufactured by Shin-Nakamura Chemical Co., Ltd.)
Photopolymerization initiator ("Irgacure 907" manufactured by Ciba Geigy); 2.95 parts by weight sensitizer ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.); 0.296 parts by weight propylene glycol monomethyl ether acetate; Part

[Example 14]
The resin solution 1 used in Example 12 was changed to the resin solution 3 to obtain a pigment dispersion 6, and then a mixture having the following composition was stirred and mixed uniformly, and then a 0.5 mmφ zirconia bead was used in a bead mill. After dispersing for 2 hours, the mixture was filtered through a 5 μm filter to prepare a blue colored resin composition 4.
Pigment Dispersion 6; 25.0 parts by weight cyclohexanone; 16.7 parts by weight Further, a mixture having the following composition was stirred and mixed to be uniform, and then filtered through a 1 μm filter to obtain a blue resist coloring composition 2. It was.
Blue colored resin composition 4; 41.7 parts by weight of resin solution 3; 36.2 parts by weight of trimethylolpropane triacrylate; 9.0 parts by weight (“NK ester ATMPT” manufactured by Shin-Nakamura Chemical Co., Ltd.)
Photopolymerization initiator ("Irgacure 907" manufactured by Ciba Geigy); 2.95 parts by weight sensitizer ("EAB-F" manufactured by Hodogaya Chemical Co.); 0.296 parts by weight cyclohexanone; 118.2 parts by weight

[Example 15]
When the blue aqueous suspension is measured with an electron microscope, the average primary particle diameter of the organic pigment is 0.12 μm to 0.15 μm, and a filter for filtering the blue resist coloring composition is 5 μm. A blue resist coloring composition 3 was obtained in the same manner as in Example 12 except that it was used.

[Example 16]
The organic pigment has an average primary particle diameter of 0.12 μm to 0.15 μm when the red aqueous suspension is measured with an electron microscope, and a filter having a thickness of 5 μm for filtering the red resist coloring composition. A red resist coloring composition 2 was obtained in the same manner as in Example 13 except that it was used.

[Example 17]
When the blue aqueous suspension is measured with an electron microscope, the average primary particle diameter of the organic pigment is 0.12 μm to 0.15 μm, and a filter for filtering the blue resist coloring composition is 5 μm. A blue resist coloring composition 4 was obtained in the same manner as in Example 14 except that it was used.

[Comparative Example 8]
A mixture having the following composition was uniformly stirred and mixed, then dispersed with a bead mill for 2 hours using 0.5 mmφ zirconia beads, and then filtered with a 5 μm filter to prepare a blue colored resin composition 5.
ε-type copper phthalocyanine pigment (CI Pigment Blue 15: 6) (“Lionol Blue E” manufactured by Toyo Ink Co., Ltd.); 30 parts by weight phthalocyanine dye derivative (derivative 48); 5.4 parts by weight resin solution 1; 80 Part by weight cyclohexanone; 82.6 parts by weight Further, a mixture having the following composition was stirred and mixed so as to be uniform, and then filtered through a 1 μm filter to obtain a blue resist coloring composition 5.
Blue colored resin composition 5; 41.7 parts by weight of resin solution 1; 36.2 parts by weight of trimethylolpropane triacrylate; 9.0 parts by weight (“NK Ester ATMPT” manufactured by Shin-Nakamura Chemical Co., Ltd.)
Photopolymerization initiator ("Irgacure 907" manufactured by Ciba Geigy); 2.95 parts by weight sensitizer ("EAB-F" manufactured by Hodogaya Chemical Co.); 0.296 parts by weight cyclohexanone; 118.2 parts by weight

[Comparative Example 9]
A mixture having the following composition was stirred and mixed uniformly, then dispersed with a bead mill for 2 hours using 0.5 mmφ zirconia beads, and then filtered through a 5 μm filter to prepare a red colored resin composition 3.
DPP pigment ("Irga Four Red B-CF" manufactured by Ciba Specialty Chemicals, CI Pigment RED254); 30.0 parts by weight pigment derivative (Table 1e); 2.25 parts by weight resin solution 2; 72 parts by weight propylene glycol Monomethyl ether acetate: 75.3 parts by weight Further, a mixture of the following composition was stirred and mixed so as to be uniform, and then filtered through a 1 μm filter to obtain a red resist landing composition 3.
Red colored resin composition 3; 41.7 parts by weight of resin solution 2; 36.2 parts by weight of trimethylolpropane triacrylate; 9.0 parts by weight (“NK ester ATMPT” manufactured by Shin-Nakamura Chemical Co., Ltd.)
Photopolymerization initiator ("Irgacure 907" manufactured by Ciba Geigy); 2.95 parts by weight sensitizer ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.); 0.296 parts by weight propylene glycol monomethyl ether acetate; Part

[Comparative Example 10]
A mixture having the following composition was stirred and mixed uniformly, then dispersed with a bead mill for 2 hours using 0.5 mmφ zirconia beads, and then filtered with a 5 μm filter to prepare a blue colored resin composition 6.
ε-type copper phthalocyanine pigment (CI Pigment Blue 15: 6) (“Lionol Blue E” manufactured by Toyo Ink Co., Ltd.); 30 parts by weight phthalocyanine dye derivative (derivative 48); 5.4 parts by weight resin solution 3; 80 Part by weight: cyclohexanone: 82.6 parts by weight Further, a mixture having the following composition was stirred and mixed so as to be uniform, and then filtered through a 1 μm filter to obtain a blue resist landing composition 6.
Blue colored resin composition 6; 41.7 parts by weight Resin solution 3; 36.2 parts by weight trimethylolpropane triacrylate; 9.0 parts by weight (“NK ester ATMPT” manufactured by Shin-Nakamura Chemical Co., Ltd.)
Photopolymerization initiator ("Irgacure 907" manufactured by Ciba Geigy); 2.95 parts by weight sensitizer ("EAB-F" manufactured by Hodogaya Chemical Co.); 0.296 parts by weight cyclohexanone; 118.2 parts by weight

(7) Evaluation of resist ink The resist coloring compositions obtained in Examples 12 to 17 and Comparative Examples 8 to 10 were placed on a glass substrate having a thickness of 100 mm × 100 mm and a thickness of 1.1 mm using a spin coater at 500 rpm, 1000 rpm, Coating was performed at a rotation speed of 1500 rpm, and three types of coated substrates having different film thicknesses were obtained. The resist coloring composition coating substrate was dried at 70 ° C. for 15 minutes. Next, the chromaticity (Y, x, y) of the coating film with a C light source was measured using a microspectrophotometer (“OSP-SP100” manufactured by Olympus Optical Co., Ltd.). From the three sets of contrast ratios and chromaticity measurement results, the color composition coated substrates obtained in Example 12, Example 14, Example 15, Example 17, Comparative Example 8, and Comparative Example 10 were y = 0. 14 for the resist-colored composition-coated substrates obtained in Examples 13, 16 and Comparative Example 9, the contrast ratio at x = 0.65 was determined using an approximation method.

  Next, an E-type viscometer (Toki Sangyo Co., Ltd.) was used for the resist coloring compositions obtained in Examples 12 to 17 and Comparative Examples 8 to 10 which had been subjected to aging for 7 days immediately after adjustment and in an oven at 40 ° C. ). The EML type was used for the measurement of the resist coloring composition. Table 5 shows examples and comparative examples of blue resist coloring compositions (y = 0.14), and Table 6 shows examples and comparative examples of red resist coloring compositions (x = 0.65).

  Comparing Examples 12 to 17 and Comparative Examples 8 to 9, the viscosity of the resist coloring composition prepared using the pigment dispersion obtained by the present invention was stable over time regardless of the type and presence of additives. It was. From this, it can be seen that the resist coloring composition prepared using the pigment dispersion obtained in the present invention is stable at low viscosity regardless of the preparation conditions.

The present invention may be a display, a resist colored composition for a color filter can be utilized as a color filter formed by using the same.

Claims (3)

It is manufactured by a manufacturing method in which an aqueous suspension containing an organic pigment, an aqueous suspension of a pigment derivative, and a resin solution obtained by dissolving a water-insoluble resin in a water-insoluble solvent are mixed and flushed from water. A colored resin for a color filter, wherein the pigment dispersion is dispersed using chromium, titanium, stainless steel, steel, sodaless hard glass, silicon nitride, alumina or zirconia beads having a diameter of 1.5 mmφ or less in the dispersion step. A method for producing the composition. A colored resin composition for a color filter produced by the production method according to claim 1 . The colored resin composition for a color filter according to claim 2, wherein the residual water content is 0.5% by weight or more and 3.0% by weight or less of the entire colored resin composition.